JPH05278142A - Polybutene resin pipe - Google Patents

Polybutene resin pipe

Info

Publication number
JPH05278142A
JPH05278142A JP4077600A JP7760092A JPH05278142A JP H05278142 A JPH05278142 A JP H05278142A JP 4077600 A JP4077600 A JP 4077600A JP 7760092 A JP7760092 A JP 7760092A JP H05278142 A JPH05278142 A JP H05278142A
Authority
JP
Japan
Prior art keywords
pipe
polybutene
resin
molding
polybutene resin
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.)
Pending
Application number
JP4077600A
Other languages
Japanese (ja)
Inventor
Hideki Matsunaga
秀樹 松永
Masakazu Okita
雅一 大北
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Corp
Original Assignee
Sumitomo Metal Industries Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sumitomo Metal Industries Ltd filed Critical Sumitomo Metal Industries Ltd
Priority to JP4077600A priority Critical patent/JPH05278142A/en
Publication of JPH05278142A publication Critical patent/JPH05278142A/en
Pending legal-status Critical Current

Links

Abstract

PURPOSE:To provide a polybutene resin pipe having sufficient mechanical strength characteristics as a fluid transport pipe by using a polybutene-1 resin having a specific degree of crystallization after molding. CONSTITUTION:A polybuteme resin pipe is composed of a polybutene-1 resin of which the degree of crystallization after molding is set to 50-70% over the total wall thickness of the pipe by adjusting a cooling speed. When this polybutene resin pipe is obtained, the cooling speed of the polybutene resin in the vicinity of the crystallizing temp. thereof at the time of melt extrusion molding may be set to 5-450 deg.C/min. Molding is usually performed by a melt extrusion method. When the pipe is produced by the melt extrusion method, for example, the polybutene resin is melted at 180-240 deg.C within an extruder 2 to be extruded from an annular extrusion die 2 and the extrudate is adjusted in its diameter by sizing to be cooled in a cooling water tank 3 at 10-25 deg.C and the solidified pipe is drawn up by a drawing-up device 4 to be cut into a predetermined length or taken up. Therefore, the pipe suitable as a liquid supply pipe and enhanced in mechanical strength can be obtained.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、給水・給湯管、配水管
や薬品配管等の流体輸送用管として好適な機械的強度の
優れたポリブテン樹脂パイプおよびその製造方法に関す
る。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polybutene resin pipe having excellent mechanical strength, which is suitable as a pipe for fluid transportation such as a water supply / hot water supply pipe, a water distribution pipe and a chemical pipe, and a method for producing the same.

【0002】[0002]

【従来の技術】ポリブテン−1樹脂(以下、ポリブテン
樹脂と略記する)は、耐圧強度、高温での内圧クリープ
耐久性、高・低温特性、耐磨耗性などに優れ、可撓性に
も良好であることから、給水・給湯管の材料として最適
な樹脂の一つである。
2. Description of the Related Art Polybutene-1 resin (hereinafter abbreviated as polybutene resin) is excellent in pressure resistance, internal pressure creep durability at high temperature, high / low temperature characteristics, abrasion resistance, and is also excellent in flexibility. Therefore, it is one of the most suitable resins as a material for water and hot water supply pipes.

【0003】給水・給湯配管用のポリブテン樹脂パイプ
については、JIS K 6778の付属書1に規定されており、
材料としては密度が0.905 g/cm3 以上、0.940 g/cm3
満のポリブテン樹脂を主原料とすることが定められてい
る。この0.905 g/cm3 以上、0.940 g/cm3 未満の密度範
囲は、結晶化度に換算すると43.75 %以上、87.50 %未
満である。しかし、この規格を満たすポリブテン樹脂を
材料としてパイプを製造しても、十分な延性および靱性
を示さない、すなわち十分な衝撃強度や引張強度等の機
械的強度を示さないことがしばしば経験された。機械的
強度が十分でないと、給水・給湯管として使用した場合
に破裂、水漏れの危険性を完全には排除できず、従って
給水・給湯管に安全に使用することができない。
Polybutene resin pipes for water and hot water supply pipes are specified in Annex 1 of JIS K 6778,
As a material, it is stipulated that a polybutene resin having a density of 0.905 g / cm 3 or more and less than 0.940 g / cm 3 is used as a main raw material. The density range of 0.905 g / cm 3 or more and less than 0.940 g / cm 3 is 43.75% or more and less than 87.50% in terms of crystallinity. However, it has often been experienced that even if a pipe is manufactured using a polybutene resin satisfying this standard as a material, it does not exhibit sufficient ductility and toughness, that is, does not exhibit sufficient mechanical strength such as impact strength and tensile strength. If the mechanical strength is not sufficient, the risk of rupture and water leakage cannot be completely eliminated when used as a water / hot water supply pipe, and therefore cannot be used safely as a water / hot water supply pipe.

【0004】[0004]

【発明が解決しようとする課題】本発明の目的は、給水
・給湯配管等の流体輸送用パイプとして十分な機械的強
度特性を有するポリブテン樹脂パイプを提供することで
ある。
SUMMARY OF THE INVENTION An object of the present invention is to provide a polybutene resin pipe having sufficient mechanical strength characteristics as a pipe for fluid transportation such as water supply / hot water supply piping.

【0005】[0005]

【課題を解決するための手段】ポリブテン樹脂パイプの
機械的強度の向上については、これまでポリブテン樹脂
自体の改質などが検討されてきているが、成形されたパ
イプの樹脂物性に着目した例はなかった。
[Means for Solving the Problems] In order to improve the mechanical strength of a polybutene resin pipe, modification of the polybutene resin itself has been studied so far, but an example focusing on the resin physical properties of a molded pipe is There wasn't.

【0006】本発明者らはポリブテン樹脂パイプ自体の
物性の検討、具体的には成形パイプの結晶性と、延性お
よび靱性との関連について検討した。その結果、ポリブ
テン樹脂パイプの延性および靱性は、パイプ成形後のポ
リブテン樹脂の結晶化度に影響され、この結晶化度が特
定の範囲内であるとパイプの機械的強度に優れること、
および結晶化度を目的の範囲とするためには、溶融押出
成形によりパイプを製造する際の結晶化温度における冷
却速度を特定範囲とすることが有効であることを見い出
した。
The present inventors examined the physical properties of the polybutene resin pipe itself, specifically, the relationship between the crystallinity of the molded pipe and the ductility and toughness. As a result, the ductility and toughness of the polybutene resin pipe are affected by the crystallinity of the polybutene resin after pipe molding, and if the crystallinity is within a specific range, the pipe has excellent mechanical strength,
It has been found that it is effective to set the cooling rate at the crystallization temperature in producing a pipe by melt extrusion to a specific range in order to bring the crystallinity into a target range.

【0007】本発明の要旨は、成形後の結晶化度が50%
〜70%であるポリブテン−1樹脂からなるポリブテン樹
脂パイプ、である。このポリブテン樹脂パイプは、溶融
押出成形法によりポリブテン樹脂パイプを製造する方法
において、結晶化温度における速度が5℃/分〜450 ℃
/分とすることを特徴とする製造方法により製造しう
る。
The gist of the present invention is that the crystallinity after molding is 50%.
Polybutene resin pipe consisting of 70% to 70% polybutene-1 resin. This polybutene resin pipe has a rate of crystallization temperature of 5 ° C./min to 450 ° C. in the method of producing a polybutene resin pipe by a melt extrusion molding method.
It can be manufactured by a manufacturing method characterized in that it is / min.

【0008】本明細書においてポリブテン樹脂の結晶化
度とは、次に述べる方法で求めたものである。ポリブテ
ンパイプの肉厚方向の中央部から3mm×3mm×1mm(管
肉厚方向に1mm)の直方体状試料を切り出し、密度勾配
管法(JIS K 7112) により密度 (d)を測定し、次式によ
り結晶化度を計算する。
In the present specification, the crystallinity of the polybutene resin is obtained by the method described below. A 3 mm × 3 mm × 1 mm (1 mm in the pipe thickness direction) rectangular parallelepiped sample was cut out from the center of the polybutene pipe in the thickness direction and the density (d) was measured by the density gradient pipe method (JIS K 7112). Calculate the crystallinity by.

【0009】 χ= (d− da ) /(dc − da ) ×100 (%) χ:単位容積中の結晶化度 d:試料の密度 da =0.87g/cm3 :ポリブテンの完全な非晶の密度 dc =0.95g/cm3 :ポリブテンの完全な結晶の密度 なお、本明細書で、成形後のポリブテン樹脂の結晶化度
あるいは密度という場合、成形に使用した原料ポリブテ
ン樹脂の値ではなく、成形により得られた樹脂パイプに
ついて測定した値である。
Χ = (d−d a ) / (d c −d a ) × 100 (%) χ: Crystallinity in unit volume d: Density of sample d a = 0.87 g / cm 3 : Complete polybutene Amorphous density d c = 0.95 g / cm 3 : complete crystal density of polybutene In the present specification, the crystallinity or density of the polybutene resin after molding refers to that of the raw material polybutene resin used for molding. It is not a value but a value measured for a resin pipe obtained by molding.

【0010】[0010]

【作用】本発明のポリブテン樹脂パイプは、パイプを構
成する樹脂(成形後の樹脂)の結晶化度が50〜70%であ
ることを特徴とする。この結晶化度は好ましくは60〜68
%である。結晶化度が70%を超えると延性および靱性が
劣り、その結果、十分な衝撃強度、引張強度等の機械的
強度を示さなくなる。また、結晶化度が50%未満では、
弾性率、降伏強度が小さくなり、耐熱特性なども劣る。
The polybutene resin pipe of the present invention is characterized in that the crystallinity of the resin forming the pipe (resin after molding) is 50 to 70%. This crystallinity is preferably 60-68.
%. If the crystallinity exceeds 70%, the ductility and toughness are poor, and as a result, sufficient mechanical strength such as impact strength and tensile strength cannot be exhibited. When the crystallinity is less than 50%,
The elastic modulus and yield strength are reduced, and the heat resistance is also poor.

【0011】機械的強度へ影響する要因として、ポリブ
テン樹脂の分子量、結晶サイズ、分子のからみ合い程度
も考えられるが、本発明者らは、ポリブテン樹脂の場合
は、押出成形により分子量、結晶サイズ、分子のからみ
合い程度はほとんど変化しないことも見い出した。これ
は、ポリブテンの場合、元来、重量平均分子が約100万
と超高分子量であるために、押出成形時に分子量、結晶
サイズ、分子のからみ合い程度の変化は起こりにくいと
推測される。従って、ポリブテン樹脂パイプの押出成形
時に変動し易く、かつ成形品パイプの物性を左右するの
は主に結晶化度であり、この結晶化度を適切な値に制御
すれば、パイプの機械的強度を向上させることができ
る。
As factors affecting the mechanical strength, the molecular weight, crystal size, and degree of entanglement of molecules of the polybutene resin may be considered. However, in the case of the polybutene resin, the inventors have found that the molecular weight, crystal size, and It was also found that the degree of entanglement of molecules hardly changed. This is presumably because polybutene originally has an ultrahigh molecular weight of about 1 million and has a molecular weight, a crystal size, and a degree of entanglement of molecules hardly change during extrusion molding. Therefore, it is easy to change during extrusion molding of polybutene resin pipe, and it is the crystallinity that mainly affects the physical properties of the molded product pipe, and if the crystallinity is controlled to an appropriate value, the mechanical strength of the pipe Can be improved.

【0012】本発明のポリブテン樹脂パイプを製造する
際に使用する原料ポリブテン樹脂は、成形後、上記範囲
の結晶化度を有するものであれば、その組成、製造法、
分子量等については何ら制限されない。
The raw material polybutene resin used in the production of the polybutene resin pipe of the present invention has a composition, a production method, and a molding method as long as it has a crystallinity in the above range after molding.
There is no limitation on the molecular weight.

【0013】原料ポリブテン樹脂としては、通常、1−
ブテンの単独重合体を使用するのが好適であるが、1−
ブテンと少量の他のα−オレフィンとの共重合体でもよ
い。このα−オレフィンには、例えばエチレン、プロピ
レン、1−ペンテン、1−オクテン、1−デセン、1−
ドデセン、4−メチル−1−ペンテンなどが例示でき
る。また、原料樹脂には慣用の添加剤、例えば耐候安定
剤、耐熱安定剤、スリップ剤、核剤、顔料、染料、潤滑
剤等を添加してもよい。本発明パイプの製造に好適に使
用できる樹脂組成物としては、例えば特公昭63-42932号
公報に示される、耐圧強度、耐塩素水性に優れた給水・
給湯配管用ポリ−1−ブテン樹脂組成物が挙げられる。
The raw material polybutene resin is usually 1-
Although it is preferable to use a homopolymer of butene, 1-
It may be a copolymer of butene and a small amount of other α-olefin. Examples of the α-olefin include ethylene, propylene, 1-pentene, 1-octene, 1-decene, 1-
Examples include dodecene and 4-methyl-1-pentene. Further, conventional additives such as weather resistance stabilizer, heat resistance stabilizer, slip agent, nucleating agent, pigment, dye, lubricant and the like may be added to the raw material resin. As a resin composition that can be suitably used for producing the pipe of the present invention, for example, as shown in JP-B-63-42932, pressure resistance, water supply excellent in chlorine water resistance
Examples thereof include a poly-1-butene resin composition for hot water supply piping.

【0014】原料ポリブテン樹脂の密度は制限されない
が、前述のポリブテン管のJIS 規格であるJIS K 6778を
満たすには、0.905 g/cm3 以上、0.940 未満の密度範囲
である。この密度範囲は43.75 %以上、87.50 未満の結
晶化度に相当する。成形前の結晶化度を初期値と称す
る。ポリブテン樹脂から溶融押出成形法によりパイプを
成形すると、成形時の加熱溶融・再結晶化に伴い樹脂の
結晶化度が変化し、初期値とは異なる値となる。従っ
て、同一の樹脂原料を使用しても、冷却速度が変動する
と、得られる樹脂パイプの結晶化度は変化する。従来の
ポリブテン管の成形では成形後の結晶化度については配
慮しておらず、また、結晶化度を一定の範囲とするため
に冷却速度を特性範囲とすればよいことについても全く
認識されていなかった。
The density of the raw material polybutene resin is not limited, but in order to meet the JIS standard of JIS K 6778 of the polybutene pipe described above, the density range is 0.905 g / cm 3 or more and less than 0.940. This density range corresponds to a crystallinity of more than 43.75% and less than 87.50. The crystallinity before molding is called the initial value. When a pipe is molded from a polybutene resin by a melt extrusion molding method, the crystallinity of the resin changes due to heat melting and recrystallization during molding, and the value becomes different from the initial value. Therefore, even if the same resin material is used, the crystallinity of the obtained resin pipe changes when the cooling rate changes. In the conventional molding of polybutene pipes, no consideration was given to the crystallinity after molding, and it is also completely recognized that the cooling rate may be set to the characteristic range in order to keep the crystallinity within a certain range. There wasn't.

【0015】これに対し、本発明のポリブテン樹脂パイ
プは、冷却速度を調整して、成形後のポリブテン樹脂の
結晶化度を管の肉厚全体にわたって50〜70%としたもの
である。このようなポリブテン樹脂パイプを得るには、
溶融押出成形の際、結晶化温度付近の冷却速度を5〜45
0 ℃/分とすればよい。
On the other hand, in the polybutene resin pipe of the present invention, the cooling rate is adjusted so that the crystallinity of the molded polybutene resin is 50 to 70% over the entire wall thickness of the pipe. To obtain such a polybutene resin pipe,
During melt extrusion molding, the cooling rate near the crystallization temperature is 5 to 45
It may be 0 ° C./minute.

【0016】本発明ポリブテン樹脂パイプの成形は、通
常、溶融押出法により行う。溶融押出法によりパイプを
製造するには、例えば、押出機内でポリブテン樹脂を18
0 〜240 ℃の温度で溶融し、環状の押出ダイから押出し
た後、サイジングにより径を調整し、次いで水温10〜25
℃の冷却水槽で冷却し、固化したパイプを引取装置で引
取り、所定長に切断するか、巻き取る。押出機には、一
般に単軸型のメタリングタイプのスクリューを備えたも
のが用いられるが、特に制限されない。使用できるダイ
には、ストレートヘッド式、クロスヘッド式、オフセッ
ト式等が例示できる。押出後のサイジングは、サイジン
グプレート法、アウトサイドマンドレル法、サイジング
ボックス法、インサイドマンドレル法等の方法を用いて
行うことができる。
Molding of the polybutene resin pipe of the present invention is usually carried out by a melt extrusion method. To produce pipes by the melt extrusion method, for example, polybutene resin is used in an extruder.
It is melted at a temperature of 0 to 240 ℃ and extruded from an annular extrusion die, the diameter is adjusted by sizing, and then the water temperature is set at 10 to 25
The pipe which is cooled in a cooling water tank at ℃ and solidified is taken by a take-up device and cut into a predetermined length or wound up. As the extruder, one having a single-screw type metering type screw is generally used, but it is not particularly limited. Examples of the die that can be used include a straight head type, a cross head type, and an offset type. The sizing after extrusion can be performed by using a method such as a sizing plate method, an outside mandrel method, a sizing box method, an inside mandrel method or the like.

【0017】[0017]

【実施例】実施例1〜3および比較例1および2におい
ては、極限粘度〔η〕が1.9dl/g、分子量分布〔Mw/Mn]
が 4.7、アイソタクチック値 [κ] が95.8%であるポリ
ブテン樹脂を、パイプ成形用の原料樹脂として使用し
た。
EXAMPLES In Examples 1 to 3 and Comparative Examples 1 and 2, the intrinsic viscosity [η] was 1.9 dl / g, and the molecular weight distribution [Mw / Mn].
Was 4.7 and the isotactic value [κ] was 95.8%, but a polybutene resin was used as a raw material resin for pipe molding.

【0018】この原料樹脂を、直径60mmの単軸押出機
で、樹脂温度 170〜 230℃にて押出し、内径27mmのプレ
ート型サイジングダイを用いて外径27mm、肉厚2.4 mmの
ポリブテン管を成形した。製管速度は4m/分とした。
次いで、図1に示す押出成形設備中の冷却槽において冷
却し、パイプを固化させた。冷却速度は、表1に示すよ
うに、樹脂温度、冷却槽の長さ、冷却水温度を変化させ
ることにより種々の値に調整した。
This raw material resin is extruded with a single screw extruder having a diameter of 60 mm at a resin temperature of 170 to 230 ° C., and a plate type sizing die having an inner diameter of 27 mm is used to form a polybutene pipe having an outer diameter of 27 mm and a wall thickness of 2.4 mm. did. The pipe making speed was 4 m / min.
Next, the pipe was solidified by cooling in a cooling tank in the extrusion molding equipment shown in FIG. As shown in Table 1, the cooling rate was adjusted to various values by changing the resin temperature, the length of the cooling bath, and the cooling water temperature.

【0019】得られたパイプの結晶化度を測定した結
果、およびパイプの衝撃強度および引張強度の評価結果
をまとめて表2に示す。ポリブテン管の衝撃強度は、押
出成形したパイプより切り出した試験材の側面を、ASTM
D256の条件に基づき、23℃で60kg・cmのエネルギーに
よりアイゾット衝撃試験を行い、試験材が折れて破壊す
るか否かにより評価した。また、ポリブテン管の引張強
度は、JIS K 7113に準じて、23℃で、引張速度50mm/分
で引張試験を行い、破断伸び、降伏強度および弾性率で
評価した。
The results of measuring the crystallinity of the obtained pipes and the evaluation results of the impact strength and the tensile strength of the pipes are summarized in Table 2. The impact strength of a polybutene pipe is measured by ASTM
Based on the conditions of D256, an Izod impact test was performed at 23 ° C. with an energy of 60 kg · cm, and it was evaluated whether or not the test material was broken and destroyed. Further, the tensile strength of the polybutene pipe was evaluated by the elongation at break, the yield strength and the elastic modulus by performing a tensile test according to JIS K 7113 at 23 ° C. and a tensile speed of 50 mm / min.

【0020】[0020]

【表1】 [Table 1]

【0021】[0021]

【表2】 [Table 2]

【0022】表2の結果から明らかなように、50〜70%
の結晶化度を有する本発明ポリブテン樹脂パイプは延性
および靱性に優れ、衝撃強度および引張強度が大きい。
これに対して、結晶化度がこの範囲をはずれる比較例1
および2のポリブテン樹脂パイプは機械的強度に劣る。
As is clear from the results shown in Table 2, 50 to 70%
The polybutene resin pipe of the present invention having the above crystallinity has excellent ductility and toughness, and has high impact strength and tensile strength.
On the other hand, Comparative Example 1 in which the crystallinity is out of this range
The polybutene resin pipes of Nos. 2 and 2 are inferior in mechanical strength.

【0023】[0023]

【発明の効果】以上詳述したように、特定範囲の結晶化
度を有する本発明のポリブテン樹脂パイプは、優れた延
性および靱性を示し、衝撃強度や引張強度等の機械的強
度が大きい。このようなポリブテン樹脂パイプは、成形
条件、特に冷却速度を制御して結晶化度を制御すること
により製造することができる。従って、本発明によれ
ば、給水・給湯管、配水管あるいは薬品配管などの液体
供給管として好適な機械的強度の向上したパイプを供給
できる。
As described above in detail, the polybutene resin pipe of the present invention having a crystallinity within a specific range exhibits excellent ductility and toughness, and has high mechanical strength such as impact strength and tensile strength. Such a polybutene resin pipe can be manufactured by controlling the molding conditions, particularly the cooling rate to control the crystallinity. Therefore, according to the present invention, a pipe having improved mechanical strength suitable as a liquid supply pipe such as a water supply / hot water supply pipe, a water distribution pipe or a chemical pipe can be supplied.

【図面の簡単な説明】[Brief description of drawings]

【図1】ポリブテン管の押出成形設備の装置配置図であ
る。
FIG. 1 is a device layout view of an extrusion molding facility for a polybutene pipe.

【符号の説明】[Explanation of symbols]

1 押出機 2 成形ダイス 3 冷却槽 4 引取機 5 ポリブテン管 1 Extruder 2 Molding die 3 Cooling tank 4 Take-up machine 5 Polybutene pipe

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 B29L 23:22 4F ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display location B29L 23:22 4F

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】 成形後の結晶化度が50%〜70%であるポ
リブテン−1樹脂からなる、ポリブテン樹脂パイプ。
1. A polybutene resin pipe comprising a polybutene-1 resin having a crystallinity of 50% to 70% after molding.
【請求項2】 溶融押出成形法によりポリブテン樹脂パ
イプを製造する方法において、結晶化温度における冷却
速度が5℃/分〜450 ℃/分であることを特徴とする、
請求項1記載のポリブテン樹脂パイプを製造する方法。
2. A method for producing a polybutene resin pipe by a melt extrusion molding method, wherein a cooling rate at a crystallization temperature is 5 ° C./min to 450 ° C./min.
A method for producing the polybutene resin pipe according to claim 1.
JP4077600A 1992-03-31 1992-03-31 Polybutene resin pipe Pending JPH05278142A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP4077600A JPH05278142A (en) 1992-03-31 1992-03-31 Polybutene resin pipe

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP4077600A JPH05278142A (en) 1992-03-31 1992-03-31 Polybutene resin pipe

Publications (1)

Publication Number Publication Date
JPH05278142A true JPH05278142A (en) 1993-10-26

Family

ID=13638439

Family Applications (1)

Application Number Title Priority Date Filing Date
JP4077600A Pending JPH05278142A (en) 1992-03-31 1992-03-31 Polybutene resin pipe

Country Status (1)

Country Link
JP (1) JPH05278142A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001523302A (en) * 1998-03-05 2001-11-20 モンテル テクノロジー カンパニー ビーブイ Polybutene-1 (co) polymer and method for producing them
WO2012008223A1 (en) * 2010-07-16 2012-01-19 積水化学工業株式会社 Polymer article and method for producing polymer article
JP2017226144A (en) * 2016-06-22 2017-12-28 株式会社ブリヂストン Manufacturing method of composite tube

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001523302A (en) * 1998-03-05 2001-11-20 モンテル テクノロジー カンパニー ビーブイ Polybutene-1 (co) polymer and method for producing them
WO2012008223A1 (en) * 2010-07-16 2012-01-19 積水化学工業株式会社 Polymer article and method for producing polymer article
JP4874432B1 (en) * 2010-07-16 2012-02-15 積水化学工業株式会社 Production method of polymer products
US8986590B2 (en) 2010-07-16 2015-03-24 Sekisui Chemical Co., Ltd. Polymer article and method for producing polymer article
JP2017226144A (en) * 2016-06-22 2017-12-28 株式会社ブリヂストン Manufacturing method of composite tube

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