JP4182852B2 - Low adhesion polyethylene pellets - Google Patents

Low adhesion polyethylene pellets Download PDF

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JP4182852B2
JP4182852B2 JP2003343249A JP2003343249A JP4182852B2 JP 4182852 B2 JP4182852 B2 JP 4182852B2 JP 2003343249 A JP2003343249 A JP 2003343249A JP 2003343249 A JP2003343249 A JP 2003343249A JP 4182852 B2 JP4182852 B2 JP 4182852B2
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修一 谷口
博之 谷村
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Sumitomo Chemical Co Ltd
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本発明は、低互着性ポリエチレンペレットに関するものであり、特に、粘着性を有する直鎖状低密度ポリエチレンの保管中における、ペレット同士の互着性が低減されたペレットに関するThe present invention relates to a low-interbonding polyethylene pellet , and more particularly to a pellet in which the inter-bonding property between pellets is reduced during storage of a linear low-density polyethylene having adhesiveness.

ポリエチレン等の樹脂は通常ペレット状に加工され、乾燥空気をブロワーにて発生させ、配管に流れている空気流に乗せてペレットをサイロへ移送する空気輸送(以下空送という)を行って、一旦貯蔵用サイロに貯蔵した後、樹脂ペレットの形態でユーザーに供給される。   Resin such as polyethylene is usually processed into pellets, dry air is generated by a blower, and air transport (hereinafter referred to as air transport) is performed to transfer the pellets to a silo on the airflow flowing through the pipe. After being stored in a storage silo, it is supplied to the user in the form of resin pellets.

低密度ポリエチレン、特に直鎖状低密度ポリエチレンはペレット自体の粘着性のため互着してしまい、サイロ内においてペレットの塊が生じ、サイロから抜き出すことができず出荷が困難になる等の問題、製造直後の樹脂ペレットに残留している残留有機溶剤等の除去、乾燥を行うために、通常加熱空気をサイロ内へ導入し、樹脂内部からの溶剤の拡散を利用して空気中へ溶剤を移行させ除去する操作を行うが、この場合に加熱空気温度を高くすると残留溶剤の除去には有利であるが、ペレット同士の互着あるいはサイロ壁面への付着等が生じ易くなる等の問題、出荷に際し、フレコンや紙袋に充填後倉庫保管中にペレットが互着しその後の作業に支障が生じる等の問題があった。   Low-density polyethylene, especially linear low-density polyethylene, will adhere to each other due to the stickiness of the pellet itself, resulting in a pellet lump in the silo that cannot be pulled out of the silo and difficult to ship, In order to remove and dry the residual organic solvent remaining in the resin pellets immediately after production, normally heated air is introduced into the silo, and the solvent is transferred into the air using diffusion of the solvent from the inside of the resin. In this case, increasing the heated air temperature is advantageous for removing the residual solvent, but problems such as adhesion of pellets to each other or adhesion to the silo wall are likely to occur. However, after filling into flexible containers and paper bags, the pellets adhered to each other during storage in the warehouse, causing problems in subsequent operations.

従来、かかる問題を解決するため、EVAエマルジョンやステアリン酸カルシウム等の互着防止剤をペレット表面に噴霧し、ペレット同士の互着や配管への付着を防止する等の方法は知られていた。しかし、これらの方法ではペレット表面に互着防止剤を均一に噴霧することが難しい、表面に付着した互着防止剤は剥離しやすく十分な互着防止効果が得られない、空送配管やサイロ等に残留した互着防止剤が、製品を汚染し品種によっては品質が損なわれる等の問題があった。   Conventionally, in order to solve such a problem, a method of spraying an anti-adhesion agent such as an EVA emulsion or calcium stearate onto the surface of the pellet to prevent the adhesion of the pellets to each other or adhesion to the piping has been known. However, with these methods, it is difficult to spray the anti-adhesion agent uniformly on the pellet surface, and the anti-adhesion agent adhering to the surface is easily peeled off and cannot provide a sufficient anti-adhesion effect. There was a problem that the anti-tacking agent remaining in the etc. contaminated the product and the quality was deteriorated depending on the variety.

そこで、例えば酢酸ビニルとエチレンの共重合体のペレットに滑剤を練り込んでペレットの表面を被膜し、互着性を低下させる方法も提案されている(例えば特許文献1参照)。本発明者は、先に直鎖状低密度ポリエチレンのペレットにタルクを練り込みペレット表面に凹凸を施し互着性を低下させ方法を提案した(特許文献2参照)。しかし、特に直鎖状ポリエチレンペレットの保管において、これらの方法によっても長期保管中の外気の温度変化によっては、ペレットの互着が生じる場合があり、より高い温度条件下においてペレットの互着防止を図り、長期間保管が可能な方法の開発が要望されていた。   Thus, for example, a method has been proposed in which a lubricant is kneaded into pellets of a copolymer of vinyl acetate and ethylene to coat the surface of the pellets to reduce the adhesion (for example, see Patent Document 1). The present inventor has previously proposed a method in which talc is kneaded into a linear low density polyethylene pellet to give unevenness to the surface of the pellet to reduce the adhesion (see Patent Document 2). However, especially in the storage of linear polyethylene pellets, these methods may cause the sticking of pellets depending on the temperature change of the outside air during long-term storage, and prevent the pellets from sticking under higher temperature conditions. There has been a demand for the development of a method that can be stored for a long time.

特公昭63−29893号公報(第1頁〜第2頁)Japanese Examined Patent Publication No. 63-29893 (pages 1 and 2) 特願2002−126187号(第1頁)Japanese Patent Application No. 2002-126187 (first page)

かかる現状において、本発明は、低密度で粘着性を有する直鎖状低密度ポリエチレンの保管に際し、ペレット同士の互着防止を図り、より長期の保管が可能なペレットを提供することを目的とする。 Under such circumstances, an object of the present invention is to prevent pellets from sticking to each other when storing linear low density polyethylene having low density and adhesiveness, and to provide pellets that can be stored for a longer period of time. .

すなわち、本発明は、密度860〜880kg/m  That is, the present invention has a density of 860 to 880 kg / m. 3Three の直鎖状低密度ポリエチレンに、少なくともタルクを0.8〜1.0wt%、滑剤を1000〜2000wtppm含有してなる低互着性ポリエチレンペレットであって、該滑剤がエルカ酸アミドである低互着性ポリエチレンペレットに係るものである。A low-adhesion polyethylene pellet comprising at least 0.8 to 1.0 wt% of talc and 1000 to 2000 wtppm of a lubricant, wherein the lubricant is erucamide. This relates to a wearable polyethylene pellet.

本発明により、ペレット同士が互着しにくく、ペレット中の未反応モノマーの脱気、サイロからの抜き出しおよび保管等の取扱いが容易な低互着性ポリエチレンペレットの提供が可能になった。According to the present invention, it has become possible to provide low-adhesion polyethylene pellets that are difficult to adhere to each other and that are easy to handle, such as deaeration of unreacted monomers in the pellets, extraction from a silo, and storage.

本発明で用いられる直鎖状低密度ポリエチレン(LLDPE)は、通常高圧イオン重合法、気相重合法、溶液重合法等で製造することができる。高圧イオン重合法では、エチレン圧約80MPa、反応温度180〜260℃で、均一系触媒としてはメタロセン触媒等が用いられる。密度は860〜880kg/m 3 であり、共重合されるコモノマーの例としてブテン−1、ヘキセン−1等が挙げられ、これらは粘着性が高く取扱いに注意を要する。 The linear low density polyethylene (LLDPE) used in the present invention can be usually produced by a high pressure ion polymerization method, a gas phase polymerization method, a solution polymerization method or the like. In the high-pressure ion polymerization method, an ethylene pressure is about 80 MPa, a reaction temperature is 180 to 260 ° C., and a metallocene catalyst or the like is used as a homogeneous catalyst. The density is 860 to 880 kg / m 3 , and examples of comonomers to be copolymerized include butene-1, hexene-1 and the like. These are highly tacky and require attention in handling.

樹脂ペレットは、通常直径約3mm、長さ約4mmの楕円球状のものである。サイロは、樹脂ペレット等を貯蔵するための容器として汎用されており、通常、ステンレスやアルミニウム等の金属製で高さ15〜20m、直径3〜4mの円筒状で、下部は逆円錐状のコーン部を形成して、製品の出荷時の抜出し容易になるように設計されており、ペレットを100トン程度貯蔵することができる。   The resin pellets are usually oval and spherical with a diameter of about 3 mm and a length of about 4 mm. A silo is widely used as a container for storing resin pellets, etc., and is usually made of a metal such as stainless steel or aluminum and has a cylindrical shape with a height of 15 to 20 m and a diameter of 3 to 4 m. It is designed so that the product can be easily extracted when the product is shipped, and about 100 tons of pellets can be stored.

本発明で用いる滑剤はエルカ酸アマイドである。添加量は1000〜2000wtppmである。タルクは、いわゆる含水珪酸マグネシウムであり、好ましくは平均粒子径約5μmの白色粉末を用いる。添加量は0.8〜1wt%である。 The lubricant used in the present invention is erucic acid amide. The addition amount is 1000 to 2000 wtppm. Talc is so-called hydrous magnesium silicate, and white powder having an average particle diameter of about 5 μm is preferably used. The amount added is 0.8-1 wt%.

本発明においては、タルクおよび滑剤を併用することが必要である。何れか一方が欠けても望む効果は得られない。ペレット表面に凹凸が形成され、ペレット同士の接触面積を減少するタルクの添加効果、滑剤がペレットの表面にブリードし、ペレットの滑り性を改良する滑剤の添加効果の相乗作用により、より好ましいペレットの互着防止効果を得ることができる。   In the present invention, it is necessary to use talc and a lubricant in combination. Even if either one is missing, the desired effect cannot be obtained. Due to the synergistic effect of the addition of talc, which forms irregularities on the pellet surface and reduces the contact area between the pellets, and the additive effect of the lubricant that bleeds the surface of the pellet and improves the slipperiness of the pellet, A mutual adhesion preventing effect can be obtained.

図1は、本発明におけるポリエチレンペレット製造工程の一例を示す概略図である。LLDPEは、重合反応器1で重合され、ガス分離機2を経てポリマー分離器3に溶融樹脂4として供給される。押出機7には小型押出機5が結合されている。押出機7にLLDPEの溶融樹脂を供給すると同時に、小型押出機5から滑剤1〜5wt%、タルク20〜40wt%と高い濃度を含有するLLDPEを溶融樹脂として押出機7に供給する。押出機7では、小型押出機5から供給される溶融樹脂と重合反応器6から供給される溶融樹脂をさらに溶融混練して、最終的にタルク含有量0.5〜25wt%、滑剤含有量が100〜10000wtppmとなるように調製し、冷却水が循環されているチャンバー8で水中カッティングされてペレット形状となる。チャンバー8のペレットは、循環冷却水と共にペレット分離器10に送られて脱水、篩分等の工程を経てサイロへ空送される。サイロでは残留溶剤の除去等を行い出荷される。   FIG. 1 is a schematic view showing an example of a polyethylene pellet manufacturing process in the present invention. LLDPE is polymerized in the polymerization reactor 1 and supplied as a molten resin 4 to the polymer separator 3 via the gas separator 2. A small extruder 5 is coupled to the extruder 7. At the same time as supplying the molten resin of LLDPE to the extruder 7, LLDPE containing a high concentration of 1 to 5 wt% lubricant and 20 to 40 wt% talc is supplied from the small extruder 5 to the extruder 7 as a molten resin. In the extruder 7, the molten resin supplied from the small extruder 5 and the molten resin supplied from the polymerization reactor 6 are further melt-kneaded to finally have a talc content of 0.5 to 25 wt% and a lubricant content. It is prepared so as to be 100 to 10000 wtppm, and is cut in water in a chamber 8 in which cooling water is circulated to form a pellet. The pellets in the chamber 8 are sent to the pellet separator 10 together with the circulating cooling water, and are sent to the silo through steps such as dehydration and sieving. The silo is shipped after removing the residual solvent.

小型押出機5から供給する高濃度のタルクおよび滑剤を含有するLLDPEは、予め別途タルク、滑剤とLLDPEを溶融混練してペレットにしたものを、押出機5に供給して、再度溶融混練を行いながら押出機7に供給してもよいし、小型押出機5の原料入口から直接、LLDPE、タルクおよび滑剤を供給しながら溶融混練を行い、連続的に押出機7に供給してもよい。   The LLDPE containing high-concentration talc and lubricant supplied from the small extruder 5 is separately supplied with talc, lubricant and LLDPE previously melt-kneaded into pellets, supplied to the extruder 5, and melt-kneaded again. The melt may be kneaded while supplying LLDPE, talc and lubricant directly from the raw material inlet of the small extruder 5 and may be continuously supplied to the extruder 7.

次に、本発明を実施例により詳しく説明するが、本発明は、これらの例によってなんら限定されるものではない。
実施例1
本発明によるLLDPEを下記の如くの製造した。
図1に示したポリエチレンペレット製造工程により、重合反応器1で重合された結晶化密度870kg/mのLLDPEを、ポリマー分離器3から、押出機7に4000kg/hrで供給した。一方小型押出機5に予め製造しておいたタルク20wt%とエルカ酸アミド3wt%を含有するLLDPEのペレットを供給し、190℃で溶融混練して押出機7に210kg/hrで供給した。押出機7では、重合反応器から供給されるLLDPEの溶融樹脂と160℃で溶融混練して、タルク含有量1.0wt%、エルカ酸アミド含有量1500wtppmとなるようにした。
EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not limited at all by these examples.
Example 1
An LLDPE according to the present invention was prepared as follows.
1, LLDPE having a crystallization density of 870 kg / m 3 polymerized in the polymerization reactor 1 was supplied from the polymer separator 3 to the extruder 7 at 4000 kg / hr. On the other hand, LLDPE pellets containing 20 wt% talc and 3 wt% erucamide prepared in advance were supplied to the small extruder 5, melt-kneaded at 190 ° C., and supplied to the extruder 7 at 210 kg / hr. In the extruder 7, melt-kneading was performed at 160 ° C. with a molten resin of LLDPE supplied from the polymerization reactor so that the talc content was 1.0 wt% and the erucic acid amide content was 1500 wtppm.

比較例1、比較例2
実施例1と同様にしてタルクを含有し、エルカ酸アミドを含有しないLLDPEペレット(比較例1)は、小型押出機からタルクのみ含有する溶融樹脂を供給し、タルクおよびエルカ酸アミドを共に含まないLLDPEペレット(比較例2)は、小型押出機からタルクおよびエルカ酸アミドを含有しない溶融樹脂を供給し製造した。
Comparative Example 1 and Comparative Example 2
The LLDPE pellets containing talc and not containing erucamide (Comparative Example 1) in the same manner as in Example 1 supplied a molten resin containing only talc from a small extruder and did not contain both talc and erucamide. LLDPE pellets (Comparative Example 2) were produced by supplying a molten resin containing no talc and erucamide from a small extruder.

実施例2
実施例1、比較例1、比較例2で製造したLLDPEペレットのサイロ内における互着性の評価を、図2、図3に示したような模型サイロを作って下記のように行った。
図2は実験に使用した模型サイロの各部分の寸法を示す断面図、図3は実験の方法を示す模型サイロの断面図である。サイロの模型は、100トンサイロと相似形になるように製作した。各寸法は次のとおりである。内径D80mm、直胴部高さD80mm、コーン部高さH70mm、コーン部傾斜角θ29°。
Example 2
Evaluation of mutual adhesion in the silo of the LLDPE pellets produced in Example 1, Comparative Example 1 and Comparative Example 2 was performed as follows by making a model silo as shown in FIGS.
FIG. 2 is a sectional view showing the dimensions of each part of the model silo used in the experiment, and FIG. 3 is a sectional view of the model silo showing the method of the experiment. The silo model was made to be similar to the 100-ton silo. Each dimension is as follows. Inner diameter D80 mm, straight body height D80 mm, cone height H70 mm, cone angle of inclination θ 29 °.

100トンサイロ(実機)と模型サイロとの間で、ペレットにかかる圧力(ペレット圧)を合わせるため、垂直円筒状の容器に充填されたペレット層内の応力分布を与える式(1)(Janssenの式)を用いてコーン部と直胴部の境でのペレット圧を計算した。

Figure 0004182852
(但し、コーン部と直胴部の境でのペレット圧PS(kg/m)は直胴部高さD(m)、ペレットの嵩密度ρa(kg/m)、ペレットと壁面の摩擦係数μw(=tanφ’;φ’=壁摩擦角=φi(内部摩擦角)=35°と仮定)、水平方向の圧力k(=tan2(π/4−φi/2))、コーン部と直胴部の境からの任意の高さh(m)、コーン部と直胴部の境での荷重Mにより表される。) Formula (1) (Janssen's formula) giving stress distribution in the pellet layer filled in a vertical cylindrical container to match the pressure (pellet pressure) applied to the pellet between the 100-ton silo (actual machine) and the model silo ) Was used to calculate the pellet pressure at the boundary between the cone part and the straight body part.

Figure 0004182852
(However, the pellet pressure PS (kg / m 2 ) at the boundary between the cone part and the straight body part is the straight body part height D (m), the pellet bulk density ρa (kg / m 3 ), and the friction between the pellet and the wall surface. Coefficient μw (= tan φ ′; φ ′ = wall friction angle = φi (internal friction angle) = 35 °), horizontal pressure k (= tan 2 (π / 4−φi / 2)), direct to cone (It is represented by an arbitrary height h (m) from the boundary of the trunk part, and a load M at the boundary between the cone part and the straight trunk part.)

この式と同様にしてコーン部におけるペレット層内の応力の釣合いを考えると(2)式となる。

Figure 0004182852
(但し、コーン部の逆円錐頂点からの任意の高さy(m)でのペレット圧P(kkg/m)はPSとy、コーン部の高さH(m)、サイロの形状と材質、およびペレットの性質によってきまる定数C(=2μWcotθ(kcos2θ+sin2))によって表される。) When considering the balance of stress in the pellet layer in the cone portion in the same manner as this equation, equation (2) is obtained.

Figure 0004182852
(However, the pellet pressure P (kkg / m 2 ) at an arbitrary height y (m) from the inverted cone apex of the cone is PS and y, the height H (m) of the cone, the shape and material of the silo , And a constant C determined by the nature of the pellet (= 2 μWcot θ (kcos 2θ + sin 2)).

これらの式より嵩密度は約560kg/mとして実機と模型サイロにおけるペレットへの圧力を同じとする荷重Mを計算した。
図3に示したように、LLDPEペレット78gを、模型サイロ12のコーン部と直胴部の境まで充填した後、計算により算出した11kg重量のおもり10をかけた。模型サイロ12を、所定の温度(30℃〜40℃)としたオーブンの中に24hr静置させ、その後模型サイロ12下部の排出ダンパー13を開け、ペレットの排出時間を測定した。
実験結果を表1に示す。LLDPEペレットの互着の状態は次の基準によって表した。◎:排出問題なし、〇:やや時間がかかるが全量排出、△:排出されるが残存量多い、×:排出不能
From these equations, the bulk density was about 560 kg / m 3 , and the load M with the same pressure on the pellets in the actual machine and the model silo was calculated.
As shown in FIG. 3, 78 g of LLDPE pellets were filled up to the boundary between the cone part and the straight body part of the model silo 12, and then a weight 10 calculated by calculation was applied. The model silo 12 was allowed to stand in an oven at a predetermined temperature (30 ° C. to 40 ° C.) for 24 hours, and then the discharge damper 13 below the model silo 12 was opened, and the pellet discharge time was measured.
The experimental results are shown in Table 1. The state of mutual adhesion of the LLDPE pellets was expressed by the following criteria. ◎: No discharge problem, ○: Slightly time consuming, but all discharged, △: Discharged but remaining, x: Unable to discharge

実施例1で製造されたLLDPEペレットは、37℃程度まで温度が上昇した場合においてもペレット排出に問題なかった。また、模型サイロ壁面へのタルク粉体の付着はみられず、評価後の洗浄も特に必要なかった。一方、比較例1として示したタルクのみを含有するLLDPEペレットでは、30℃程度まで温度が上昇すると、ペレット同士の互着および模型サイロ壁面への付着が生じ、36℃以上の温度では排出不能であった。また、比較例2として示したLLDPEのみのペレットでは、30℃以下でも残存量が多く排出が完全に行われなかった。


The LLDPE pellet produced in Example 1 had no problem in pellet discharge even when the temperature rose to about 37 ° C. Moreover, no talc powder adhered to the model silo wall, and no cleaning was required after evaluation. On the other hand, in the LLDPE pellet containing only talc shown as Comparative Example 1, when the temperature rises to about 30 ° C., the pellets adhere to each other and adhere to the model silo wall and cannot be discharged at a temperature of 36 ° C. or higher. there were. Further, in the pellet of only LLDPE shown as Comparative Example 2, the remaining amount was large even at 30 ° C. or less, and the discharge was not performed completely.


Figure 0004182852
Figure 0004182852

注)◎:排出問題なし ○:やや時間がかかるが全量排出
△:排出されるが残存量が多い ×:排出不能
Note) ◎: There is no emission problem. ○: It takes some time, but the whole amount is discharged. △: It is discharged but the remaining amount is large.

実施例3
実施例1、比較例1、比較例2で製造したLLDPEペレットを倉庫に保管した場合の互着性の評価を次の如く行った。25kgの紙袋に充填したLLDPEペレットについて、8段積み重ねた状態で半年間静置させた後、紙袋を開封し内部の状態を観察したところ、実施例1のLLDPEペレットではペレット同士が互着し、塊が発生していた袋はなかったが、比較例1、比較例2のLLDPEペレットでは最上部の袋以外で塊が見られた。
Example 3
Evaluation of mutual adhesion when the LLDPE pellets produced in Example 1, Comparative Example 1, and Comparative Example 2 were stored in a warehouse was performed as follows. About LLDPE pellets filled in a 25 kg paper bag, after standing for half a year in a stacked state of 8 stages, the paper bag was opened and the internal state was observed. Although there was no bag in which lumps were generated, in the LLDPE pellets of Comparative Example 1 and Comparative Example 2, lumps were seen except for the uppermost bag.

本発明のポリエチレンペレット製造工程の一例を示す概略図である。It is the schematic which shows an example of the polyethylene pellet manufacturing process of this invention. 模型サイロの各部分の寸法を示す断面図である。It is sectional drawing which shows the dimension of each part of a model silo. 実験の方法を示す模型サイロの断面図である。It is sectional drawing of the model silo which shows the method of experiment.

符号の説明Explanation of symbols

1…重合反応器 、2…ガス分離器、3… ポリマー分離器、4… 溶融ポリエチレン、5…小型押出機、6…原料入口 、7…押出機、8… チャンバー、9…循環冷却水、10…ペレット脱水機、11…ペレット、12…模型サイロ、13…排出ダンパー、14…おもり、15… おもりの支柱、16…ペレット、D…模型サイロの内径および直胴部高さ、H…模型サイロのコーン部高さ、θ…模型サイロのコーン部傾斜角、y…模型サイロのコーン部の逆円錐頂点からの任意の高さ、h…模型サイロのコーン部と直胴部の境からの任意の高さ DESCRIPTION OF SYMBOLS 1 ... Polymerization reactor, 2 ... Gas separator, 3 ... Polymer separator, 4 ... Molten polyethylene, 5 ... Small extruder, 6 ... Raw material inlet, 7 ... Extruder, 8 ... Chamber, 9 ... Circulating cooling water, 10 ... Pellet dehydrator, 11 ... Pellets, 12 ... Model silo, 13 ... Discharge damper, 14 ... Weight, 15 ... Weight column, 16 ... Pellet, D ... Model silo inner diameter and straight body height, H ... Model silo Cone height of the model silo, θ: cone inclination angle of the model silo, y: arbitrary height from the inverted cone apex of the cone part of the model silo, h: arbitrary from the boundary between the cone part and the straight body part of the model silo Height of

Claims (1)

密度860〜880kg/m 3 直鎖状低密度ポリエチレンに、少なくともタルクを0.8〜1.0wt%、滑剤を1000〜2000wtppm含有してなる低互着性ポリエチレンペレットであって、該滑剤がエルカ酸アミドである低互着性ポリエチレンペレット。 A low-adhesion polyethylene pellet comprising a linear low-density polyethylene having a density of 860 to 880 kg / m 3 and containing at least 0.8 to 1.0 wt% of talc and 1000 to 2000 wtppm of a lubricant , Low-peeling polyethylene pellets whose lubricant is erucic acid amide .
JP2003343249A 2003-10-01 2003-10-01 Low adhesion polyethylene pellets Expired - Fee Related JP4182852B2 (en)

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JP2015013447A (en) * 2013-07-08 2015-01-22 日本ポリエチレン株式会社 Resin pellet surface treatment method, self-adhesion prevention method and surface treatment resin pellet

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