JPH059352A - Poly 1-butene resin composition - Google Patents
Poly 1-butene resin compositionInfo
- Publication number
- JPH059352A JPH059352A JP3227913A JP22791391A JPH059352A JP H059352 A JPH059352 A JP H059352A JP 3227913 A JP3227913 A JP 3227913A JP 22791391 A JP22791391 A JP 22791391A JP H059352 A JPH059352 A JP H059352A
- Authority
- JP
- Japan
- Prior art keywords
- poly
- molecular weight
- butene
- butene resin
- average molecular
- 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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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明はポリ1−ブテン樹脂組成
物に関し、特に、耐衝撃性、耐クリープ性に優れるとと
もに、高速成形性に優れたポリ1−ブテン樹脂組成物に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a poly-1-butene resin composition, and more particularly to a poly-1-butene resin composition having excellent impact resistance and creep resistance as well as high-speed moldability.
【0002】[0002]
【従来の技術】従来、給水・給湯用の配管材として、鉛
めっき鋼管、銅管または鉛管等の金属製の管材が使用さ
れている。しかし、鋼管は、錆により赤水や黒水が発生
し、銅管は電蝕によりピンホールや青水が発生するおそ
れがあるなどの問題があるため、これらの問題がない配
管材が求められている。そこで、既に一部では錆、電蝕
によりピンホールが発生しないポリ塩化ビニル、ポリエ
チレン、ポリ−1−ブテン等の合成樹脂からなる管材が
使用される傾向にある。2. Description of the Related Art Conventionally, a metal pipe material such as a lead-plated steel pipe, a copper pipe or a lead pipe has been used as a pipe material for supplying water and hot water. However, steel pipes have problems such as red water and black water being generated due to rust, and copper pipes being likely to generate pinholes and blue water due to electrolytic corrosion.Therefore, piping materials that do not have these problems are required. . Therefore, there is a tendency that a pipe material made of a synthetic resin such as polyvinyl chloride, polyethylene, and poly-1-butene, which does not cause pinholes due to rust or electrolytic corrosion, is already used in some parts.
【0003】このような合成樹脂製の管材の中でも、ポ
リ1−ブテン樹脂からなる管材は、ポリ1−ブテン樹脂
が耐圧強度、高温の耐クリープ性、耐熱性および低温衝
撃強度、耐摩耗性、ならびに可撓性に優れるため、給水
・給湯用の配管材として最も好適なものの一つである。
そこで、このポリ1−ブテン樹脂からなるパイプに対
する需要の増加が予想される。Among such synthetic resin tubing materials, the tubing material made of poly 1-butene resin includes poly 1-butene resin in which the pressure resistance, high temperature creep resistance, heat resistance and low temperature impact strength, wear resistance, In addition, since it is excellent in flexibility, it is one of the most suitable piping materials for water supply and hot water supply.
Therefore, it is expected that the demand for the pipe made of this poly-1-butene resin will increase.
【0004】[0004]
【発明が解決しようとする課題】しかし、従来、入手で
きるポリ1−ブテン樹脂は、剛性、クリープ特性、耐衝
撃強度および結晶化速度等においては、優れているが、
重量平均分子量(Mw)と数平均分子量(Mn)の比
(Mw/Mn)が6以下の分子量分布が狭いものである
ため、これを口径30mm以下のパイプに成形する場合
に、低速(3m/min以下)の成形速度では十分に成
形可能であるが、より高速の成形速度でパイプに成形す
ると、得られるパイプの内外面に肌荒れを生じ、外観が
良好なものが得られず、高速成形性に問題があった。However, conventionally available poly 1-butene resins are excellent in rigidity, creep characteristics, impact strength, crystallization rate, etc.,
The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 6 or less, and the molecular weight distribution is narrow. Therefore, when this is molded into a pipe having a diameter of 30 mm or less, a low speed (3 m / (Min or less) can be sufficiently molded, but when molded into a pipe at a higher molding speed, the inner and outer surfaces of the resulting pipe are roughened, and a good appearance cannot be obtained, resulting in high-speed moldability. I had a problem with.
【0005】そこで本発明の目的は、ポリ1−ブテン樹
脂が本来有する、優れた剛性、クリープ特性、耐衝撃強
度などの特性を備えるとともに、さらに成形性、特に高
い成形速度での成形性、いわゆる高速成形性に優れたポ
リ1−ブテン樹脂組成物を提供することにある。Therefore, an object of the present invention is to provide characteristics such as excellent rigidity, creep characteristics, impact resistance and the like, which the poly 1-butene resin originally has, and further to improve moldability, especially at high molding speed, so-called. It is intended to provide a poly-1-butene resin composition excellent in high-speed moldability.
【0006】[0006]
【課題を解決するための手段】本発明は、前記課題を解
決するために、メルトフローレート0.01〜5g/1
0分、分子量分布を表す重量平均分子量(Mw)と数平
均分子量(Mn)との比(Mw/Mn)が6以下、かつ
アイソタクチック値が93%以上であるポリ1−ブテン
樹脂(A)60〜95重量部、およびメルトフローレー
トが(A)のポリ1−ブテン樹脂の20倍以上であり、
分子量分布を表す重量平均分子量(Mw)と数平均分子
量(Mn)との比(Mw/Mn)が6以下、かつアイソ
タクチック値が93%以上であるポリ1−ブテン樹脂
(B)40〜5重量部を含むポリ1−ブテン樹脂組成物
(以下、単に「組成物」と略す)を提供するものであ
る。In order to solve the above-mentioned problems, the present invention has a melt flow rate of 0.01 to 5 g / 1.
A poly-1-butene resin (A having a ratio (Mw / Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn) of 6 minutes or less and an isotactic value of 93% or more (A) ) 60 to 95 parts by weight, and the melt flow rate is 20 times or more that of the poly-1-butene resin of (A),
Poly 1-butene resin (B) 40-having a ratio (Mw / Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn) representing a molecular weight distribution of 6 or less and an isotactic value of 93% or more A poly-1-butene resin composition containing 5 parts by weight (hereinafter simply referred to as "composition") is provided.
【0007】また、本発明は、前記組成物にさらに核剤
を含むと、好ましい。The present invention preferably further comprises a nucleating agent in the composition.
【0008】以下、本発明の組成物について詳細に説明
する。The composition of the present invention will be described in detail below.
【0009】本発明の組成物の主成分であるポリ1−ブ
テン樹脂(A)は、1−ブテンの単独重合体、もしくは
1−ブテンと、該1−ブテンと他の炭素数2〜20のα
−オレフィンとの共重合体である。The poly-1-butene resin (A), which is the main component of the composition of the present invention, is a homopolymer of 1-butene or 1-butene, and the 1-butene and other C2-20. α
A copolymer with an olefin.
【0010】このポリ1−ブテン樹脂(A)のメルトフ
ローレート(MFR(E):ASTM D1238,
E)は、得られる組成物の押出成形性が良好である点
で、0.01〜5g/10分、好ましくは0.1〜2g
/10分である。This poly 1-butene resin (A) has a melt flow rate (MFR (E): ASTM D1238,
E) is 0.01 to 5 g / 10 minutes, preferably 0.1 to 2 g, in that the composition obtained has good extrusion moldability.
/ 10 minutes.
【0011】また、このポリ1−ブテン樹脂(A)は、
分子量分布を表す重量平均分子量(Mw)と数平均分子
量(Mn)の比(Mw/Mn)が、6以下のものであ
り、得られる組成物の耐衝撃性が優れる点で、5以下の
ものが好ましい。この重量平均分子量(Mw)と数平均
分子量(Mn)の比(Mw/Mn)は、下記の方法によ
って測定される。
(a)分子量既知の標準ポリスチレン(単分散ポリスチ
レン、東洋曹達社製)を用い、異なる分子量のポリスチ
レンを、下記測定条件:
装置:ウオーター社製、Model 1 150C
カラム: 東洋曹達社製、TSKGMH−6.6mmφ×
600
サンプル量:400μ
温度:135℃
流量:1 m /min
で、GPC(ゲルパーミェーションクロマトグラフィ
ー)分析に供し、分子量MとEV値(Elution Volum
e :溶出体積)の校正曲線を作成する。
(b)試料の調製
分子量を測定するポリマー試料と溶媒o−ジクロロベン
ゼンとを、フラスコに入れ、ポリマー15mgに対して
溶媒20mlの割合の溶液を調製する。得られたポリマ
ー溶液に、安定剤として2,6−ジ−t−ブチル−クレ
ゾ−ルを0.1重量%の濃度に加える。この溶液を14
0℃で1時間加熱した後、1時間撹拌して、ポリマーお
よび安定剤を完全に溶解させる。次に、135〜140
℃の温度で0.5μmのフィルターで溶液を瀘過する。
得られた瀘過液を、上記の(a)と同じ測定条件でGP
C分析に供し、得られたEV値から、前記で作成してお
いた校正曲線により、数平均分子量:
Mn=ΣMi Ni /ΣNi
および
重量平均分子量:Mw=ΣMi2Ni /ΣMi Ni
を求め、(Mw/Mn)を計算する。The poly-1-butene resin (A) is
The ratio (Mw / Mn) of the weight average molecular weight (Mw) representing the molecular weight distribution and the number average molecular weight (Mn) is 6 or less, and 5 or less in that the resulting composition has excellent impact resistance. Is preferred. The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is measured by the following method. (A) Standard polystyrene having a known molecular weight (monodisperse polystyrene, manufactured by Toyo Soda Co., Ltd.) was used to measure polystyrenes having different molecular weights under the following measurement conditions: Device: Water Co., Model 1 150C column: Toyo Soda Co., Ltd., TSKGMH-6 6.6 mmφ x
600 sample amount: 400μ temperature: 135 ° C flow rate: 1 m / min, subjected to GPC (gel permeation chromatography) analysis, molecular weight M and EV value (Elution Volume)
e: Elution volume) to create a calibration curve. (B) Preparation of sample A polymer sample whose molecular weight is to be measured and solvent o-dichlorobenzene are placed in a flask to prepare a solution having a ratio of 20 ml of solvent to 15 mg of polymer. 2,6-Di-t-butyl-cresol as a stabilizer is added to the obtained polymer solution at a concentration of 0.1% by weight. Add this solution to 14
After heating at 0 ° C. for 1 hour, stirring is performed for 1 hour to completely dissolve the polymer and the stabilizer. Next, 135-140
Filter the solution through a 0.5 μm filter at a temperature of ° C.
The obtained filtered solution was subjected to GP under the same measurement conditions as in (a) above.
The number average molecular weight: Mn = ΣMi Ni / ΣNi and the weight average molecular weight: Mw = ΣMi 2 Ni / ΣMi Ni were obtained from the EV value obtained by C analysis using the calibration curve prepared above. Calculate Mw / Mn).
【0012】さらに、このポリ1−ブテン樹脂(A)の
アイソタクチック値は、93%以上であり、好ましく
は、得られる組成物の剛性、耐熱性および耐クリープ性
が優れる点で、93〜98%である。このアイソタクチ
ック値(II)は、以下の方法により測定した。1−ブ
テン樹脂1gをn−デカン100mlに溶解した後、 0
℃に冷却し、0℃で24時間放置して高立体規則性成分
を析出させ、不溶部の重量%をIIとした。Further, the isotactic value of the poly-1-butene resin (A) is 93% or more, and preferably 93 to 10 in terms of excellent rigidity, heat resistance and creep resistance of the obtained composition. 98%. This isotactic value (II) was measured by the following method. After dissolving 1 g of 1-butene resin in 100 ml of n-decane, 0
The mixture was cooled to 0 ° C. and left at 0 ° C. for 24 hours to precipitate a highly stereoregular component, and the weight% of the insoluble portion was set to II.
【0013】本発明の組成物のもう1つの主成分である
ポリ1−ブテン樹脂(B)は、前記ポリ1−ブテン樹脂
(A)と同様に、1−ブテンの単独重合体、もしくは1
−ブテンと、該1−ブテンと他の炭素数2〜20のα−
オレフィンとの共重合体であり、この炭素数2〜20の
他のα−オレフィンを含む場合は、その含有量も前記ポ
リ1−ブテン樹脂(A)と同様である。The poly-1-butene resin (B), which is another main component of the composition of the present invention, is a homopolymer of 1-butene, or 1-butene, as in the case of the poly-1-butene resin (A).
-Butene, the 1-butene and other α having 2 to 20 carbon atoms-
When it is a copolymer with an olefin and contains another α-olefin having 2 to 20 carbon atoms, the content thereof is also the same as that of the poly-1-butene resin (A).
【0014】このポリ1−ブテン樹脂(B)のメルトフ
ローレート(MFR(E):ASTM D1238,
E)は、得られる組成物の押出成形性が良好である点
で、前記(A)のポリ1−ブテン樹脂のメルトフローレ
ートの20倍以上、好ましくは50〜1000倍であ
る。The melt flow rate of this poly-1-butene resin (B) (MFR (E): ASTM D1238,
E) is 20 times or more, preferably 50 to 1000 times, the melt flow rate of the poly (1-butene) resin of (A) in that the composition obtained has good extrusion moldability.
【0015】また、このポリ1−ブテン樹脂(B)は、
分子量分布を表す重量平均分子量(Mw)と数平均分子
量(Mn)の比(Mw/Mn)が、6以下のものであ
り、得られる組成物の耐衝撃性が優れる点で、5以下の
ものが好ましい。The poly-1-butene resin (B) is
The ratio (Mw / Mn) of the weight average molecular weight (Mw) representing the molecular weight distribution and the number average molecular weight (Mn) is 6 or less, and 5 or less in that the resulting composition has excellent impact resistance. Is preferred.
【0016】さらに、このポリ1−ブテン樹脂(B)の
アイソタクチック値(II)は、93%以上であり、得
られる組成物が剛性、耐熱性および耐クリープ性に優れ
る点で、93〜98%が好ましい。Further, the isotactic value (II) of the poly-1-butene resin (B) is 93% or more, and the composition obtained has excellent rigidity, heat resistance and creep resistance. 98% is preferable.
【0017】本発明の組成物において、得られる組成物
の溶融パリソンのメルトテンションが高くなるため成形
加工性が良好となり、高速でパイプに成形することが可
能となる。また良好な衝撃強度を有する成形品が得られ
る点で、ポリ1−ブテン樹脂(A)/ポリ1−ブテン樹
脂(B)の配合割合は、重量比で60/40〜95/
5、好ましくは90/10〜70/30である。In the composition of the present invention, the melt tension of the molten parison of the resulting composition is high, so that the moldability is good and it is possible to mold it into a pipe at a high speed. Further, from the viewpoint that a molded product having good impact strength can be obtained, the compounding ratio of poly 1-butene resin (A) / poly 1-butene resin (B) is 60/40 to 95 / by weight.
5, preferably 90/10 to 70/30.
【0018】また、本発明の組成物は、前記ポリ1−ブ
テン樹脂(A)および(B)に加えて、さらに核剤を含
有していると、パイプ成形時にダイスから押し出された
溶融樹脂の固化速度が早くなるため、より安定した高速
成形性が得られること、および固化した後もポリ1−ブ
テン樹脂に特有の結晶転移の速度を促進し、さらに剛性
向上に効果がある点で、好ましい。If the composition of the present invention further contains a nucleating agent in addition to the poly-1-butene resins (A) and (B), the composition of the molten resin extruded from the die during pipe molding can be obtained. Since the solidification rate becomes faster, more stable high-speed moldability is obtained, and the rate of crystal transition peculiar to the poly-1-butene resin is promoted even after solidification, which is effective in further improving rigidity, which is preferable. .
【0019】この核剤としては、例えば、ポリエチレン
樹脂、ポリエチレンワックス、エチレンビスステアロア
マイド、ポリプロピレン樹脂等が挙げられる。Examples of the nucleating agent include polyethylene resin, polyethylene wax, ethylenebisstearamide, polypropylene resin and the like.
【0020】本発明の組成物に、この核剤を配合する場
合、その配合量は、通常、0.01〜2%程度であり、
0.05〜0.5%程度が好ましい。When the nucleating agent is blended with the composition of the present invention, the blending amount is usually about 0.01 to 2%,
It is preferably about 0.05 to 0.5%.
【0021】本発明の組成物の製造は、前記ポリ1−ブ
テン樹脂(A)、ポリ1−ブテン樹脂(B)、および必
要に応じて前記核剤等を、前記配合割合でヘンシェルミ
キサー、V−ブレンダー、リボンブレンダー、タンブラ
ーブレンダー等を用いて混合する方法;さらに混合後、
単軸押出機、多軸押出機、バンバリーミキサー、ニーダ
ー等を用いて溶融混練した後、造粒または粉砕する方法
によって行なうことができる。また、ポリ1−ブテン樹
脂(A)および(B)をそれぞれ重合し、それぞれ得ら
れる重合溶液をそのまま撹拌混合することによっても製
造することができる。The composition of the present invention can be produced by using the poly-1-butene resin (A), the poly-1-butene resin (B), and, if necessary, the nucleating agent and the like in the above blending ratio by a Henschel mixer, V. -A method of mixing using a blender, a ribbon blender, a tumbler blender, etc .;
It can be carried out by a method of granulating or pulverizing after melt-kneading using a single-screw extruder, a multi-screw extruder, a Banbury mixer, a kneader or the like. It can also be produced by polymerizing the poly-1-butene resins (A) and (B), and stirring and mixing the resulting polymerization solutions as they are.
【0022】さらに、本発明の組成物には、成形して得
られる成形品の耐熱老化性、耐塩素水性等の長期耐久性
を向上させるために、酸化防止剤を含有していてもよ
い。この酸化防止剤としては、例えば、2,6−ジ−t
−ブチル−4−ヒドロキシベンゾエート、n−ヘキサデ
シル−3,5−ジ−t−ブチル−4−ヒドロキシベンゾ
エート、1,3,5−トリメチル−2,4,6−トリス
(3,5−ジ−t−ブチル−4−ヒドロキシベンジル)
ベンゼン、1,3,5−トリス(4−t−ブチル−3−
ヒドロキシ−2,6−ジメチルフェニル)イソシアヌレ
ート、トリス(3,5−ジ−t−ブチル−4−ヒドロキ
シフェニル)イソシアヌレート、n−オクタデシル−3
(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)
プロピオネート、ビス(3,5−ジ−t−ブチル−4−
ヒドロキシベンゾイルホスホン酸)モノエチルエステル
のニッケル塩、2,2’−ジヒドロキシ−3,3’−ジ
(α−メチルシクロヘキシル)−5,5’−ジメチル−
ジフェニルメタン、4,4−チオ−ビス(3−メチル−
6−t−ブチルフェノール)、1,1,3−トリス(2
−メチル−4−ヒドロキシ−5−t−ブチル−フェニ
ル)ブタン、テトラキス[メチレン−3(3,5−ジ−
t−ブチル−4−ヒドロキシフェニル)プロピオネー
ト]メタン、2,6−ジ−t−ブチル−p−クレゾー
ル、4,4’−メチレン−ビス(2,6−ジ−t−ブチ
ル−フェノール、トリス(2,4−ジ−t−ブチル−フ
ェニル)ホスファイト、ビタミンE等のフェノール系ま
たはリン系のものが挙げられる。これらは1種単独でも
2種以上を組合せても用いられる。Further, the composition of the present invention may contain an antioxidant in order to improve the long-term durability such as heat aging resistance and chlorine water resistance of the molded product obtained by molding. Examples of the antioxidant include 2,6-di-t
-Butyl-4-hydroxybenzoate, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t -Butyl-4-hydroxybenzyl)
Benzene, 1,3,5-tris (4-t-butyl-3-
Hydroxy-2,6-dimethylphenyl) isocyanurate, tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, n-octadecyl-3
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, bis (3,5-di-t-butyl-4-
(Hydroxybenzoylphosphonic acid) monoethyl ester nickel salt, 2,2′-dihydroxy-3,3′-di (α-methylcyclohexyl) -5,5′-dimethyl-
Diphenylmethane, 4,4-thio-bis (3-methyl-
6-t-butylphenol), 1,1,3-tris (2
-Methyl-4-hydroxy-5-t-butyl-phenyl) butane, tetrakis [methylene-3 (3,5-di-
t-butyl-4-hydroxyphenyl) propionate] methane, 2,6-di-t-butyl-p-cresol, 4,4′-methylene-bis (2,6-di-t-butyl-phenol, tris ( Examples thereof include 2,4-di-t-butyl-phenyl) phosphite, phenol-based and phosphorus-based compounds such as vitamin E. These may be used alone or in combination of two or more.
【0023】この酸化防止剤を含む場合、その含有量
は、通常、樹脂分((A)+(B))100重量部に対
して、0.1〜2重量部程度、好ましくは0.5〜1.
8重量部程度である。When the antioxidant is contained, its content is usually about 0.1 to 2 parts by weight, preferably 0.5 parts by weight, based on 100 parts by weight of the resin component ((A) + (B)). ~ 1.
It is about 8 parts by weight.
【0024】本発明の組成物は、上記の酸化防止剤に加
えて、必要に応じて他の紫外線吸収剤、防かび剤、発錆
防止剤、滑剤、充填剤、顔料、耐熱安定剤等を添加する
こともできる。 さらに、本発明の組成物は、耐衝撃性
の改良のために、例えば、エチレン−プロピレンコポリ
マー樹脂等のオレフィン系エラストマーを15重量%以
下の範囲で含んでいてもよい。In addition to the above-mentioned antioxidant, the composition of the present invention may further contain other ultraviolet absorbers, fungicides, rust inhibitors, lubricants, fillers, pigments, heat stabilizers, etc. It can also be added. Further, the composition of the present invention may contain, for example, an olefinic elastomer such as an ethylene-propylene copolymer resin in an amount of 15% by weight or less in order to improve impact resistance.
【0025】本発明の組成物のメルトフローレートは、
通常、成形加工上、0.2〜5g/10分程度であるの
が、好ましい。The melt flow rate of the composition of the present invention is
Generally, it is preferably about 0.2 to 5 g / 10 minutes in terms of molding processing.
【0026】[0026]
【実施例】以下、本発明の実施例および比較例を挙げ、
本発明を具体的に説明する。EXAMPLES Examples and comparative examples of the present invention will be given below.
The present invention will be specifically described.
【0027】(参考例A)
(チタン触媒成分(A)の調製)無水塩化マグネシウム
4.76g(50mmol)、デカン25mlおよび2
−エチルヘキシルアルコール23.4ml(150mm
ol)を、130℃で2時間加熱して反応させ、均一溶
液を得た。次に、この均一溶液中に無水フタル酸1.1
1g(7.5mmol)を添加し、130℃でさらに1
時間攪拌して混合して、無水フタル酸を均一溶液に溶解
させた。この均一溶液を室温に冷却した後、−20℃に
保持された四塩化チタン200ml(1.8ml)中に
1時間かけて全量を滴下して加えた。次いで、得られた
混合液の温度を4時間かけて110℃に昇温し、110
℃に達したところでジイソブチルフタレート2.68m
l(12.5mmol)を添加し、2時間温度を保持し
て攪拌して反応させた。2時間の反応終了後、反応混合
物を熱時濾過して固形分を採取し、この固形分をTiC
l4 200ml中に投入して懸濁させ、再び110℃で
2時間、加熱して反応させた。反応終了後、再び反応混
合物を熱時濾過し、固形分を採取し、この固形分を11
0℃のデカンおよびヘキサンで、洗液中に遊離のチタン
化合物が検出されなくなるまで、十分に洗浄してチタン
触媒成分(A)を得た。Reference Example A Preparation of Titanium Catalyst Component (A) 4.76 g (50 mmol) of anhydrous magnesium chloride, 25 ml of decane and 2
-Ethylhexyl alcohol 23.4 ml (150 mm
ol) was heated at 130 ° C. for 2 hours for reaction to obtain a uniform solution. Then, add phthalic anhydride 1.1 in this homogeneous solution.
Add 1 g (7.5 mmol) and add another 1 at 130 ° C.
The phthalic anhydride was dissolved in a homogeneous solution by stirring and mixing for hours. After cooling this homogeneous solution to room temperature, the whole amount was added dropwise to 200 ml (1.8 ml) of titanium tetrachloride kept at -20 ° C over 1 hour. Then, the temperature of the obtained mixed liquid was raised to 110 ° C. over 4 hours, and 110
Diisobutyl phthalate 2.68m when reaching ℃
1 (12.5 mmol) was added, and the reaction was carried out by stirring while maintaining the temperature for 2 hours. After completion of the reaction for 2 hours, the reaction mixture was filtered while hot to collect the solid content,
l 4 was suspended was poured into 200 ml, followed by reaction for 2 hours, heated again at 110 ° C.. After the reaction was completed, the reaction mixture was filtered again while hot, and the solid content was collected.
Titanium catalyst component (A) was obtained by thoroughly washing with decane and hexane at 0 ° C. until no free titanium compound was detected in the washing liquid.
【0028】以上のようにして得られたチタン触媒成分
(A)をヘキサンスラリーとして保存し、またその一部
を乾燥して触媒組成を分析した。分析の結果、得られた
チタン触媒成分(A)の組成は、チタン3.1重量%、
塩素56.0重量%、マグネシウム17.0重量%およ
びジイソブチルフタレート20.9重量%であった。The titanium catalyst component (A) thus obtained was stored as a hexane slurry, and a part thereof was dried to analyze the catalyst composition. As a result of analysis, the composition of the titanium catalyst component (A) obtained was 3.1% by weight of titanium,
It was 56.0% by weight of chlorine, 17.0% by weight of magnesium and 20.9% by weight of diisobutyl phthalate.
【0029】(重合)内容積200lのSUS製反応器
に、ヘキサン50l/hr、液体1−ブテン50l/h
r、上記チタン触媒成分(A)0.6mM/hr、トリ
イソブチルアルミニウム100mM/hr、シクロヘキ
シルメチルジメトキシシラン5mM/hrと水素を連続
的に供給し、重合温度60℃、重合圧力4.7barで
反応させた。このとき、水素の供給量は、反応器の気相
部における水素/1−ブテンのモル比が0.01となる
ように調整した。反応器内の液量を100lに保ちなが
ら、液状の反応混合物を連続的に抜き出した。抜き出し
た反応混合物に1l/hrのメタノールを添加して1−
ブテンを除去し、さらに280℃に昇温してフラッシュ
蒸留してヘキサンを除去した後、得られたポリ1−ブテ
ン樹脂を250℃でペレット化した。この重合反応にお
ける重合活性は7600g/mM・Tiであった。以
下、このようにして得られたポリ1−ブテン樹脂を「P
B−A」という。(Polymerization) Hexane 50 l / hr and liquid 1-butene 50 l / h were placed in a SUS reactor having an internal volume of 200 l.
r, the above titanium catalyst component (A) 0.6 mM / hr, triisobutylaluminum 100 mM / hr, cyclohexylmethyldimethoxysilane 5 mM / hr and hydrogen were continuously supplied, and reacted at a polymerization temperature of 60 ° C. and a polymerization pressure of 4.7 bar. Let At this time, the amount of hydrogen supplied was adjusted so that the molar ratio of hydrogen / 1-butene in the gas phase part of the reactor was 0.01. The liquid reaction mixture was continuously withdrawn while maintaining the liquid volume in the reactor at 100 l. To the extracted reaction mixture, 1 l / hr of methanol was added to
After removing butene, the temperature was further raised to 280 ° C. and flash distillation was performed to remove hexane, and then the obtained poly-1-butene resin was pelletized at 250 ° C. The polymerization activity in this polymerization reaction was 7,600 g / mM · Ti. Hereinafter, the poly 1-butene resin thus obtained is referred to as "P
B-A ".
【0030】また、このPB−Aのメルトフローレー
ト、分子量分布を表す重量平均分子量(Mw)と数平均
分子量(Mn)との比(Mw/Mn)、およびアイソタ
クチック値を測定したところ、それぞれMFR:0.2
g/10分(ASTM:D1238,E)、Mw/Mn
=4.5、II=95%であった。Further, the melt flow rate of PB-A, the ratio (Mw / Mn) of the weight average molecular weight (Mw) representing the molecular weight distribution to the number average molecular weight (Mn), and the isotactic value were measured. MFR: 0.2 each
g / 10 minutes (ASTM: D1238, E), Mw / Mn
= 4.5, II = 95%.
【0031】(参考例B)反応器の気相部における水素
/1−ブテンのモル比を0.5に調整した以外は、参考
例Aと同様にして重合を行い、ポリ1−ブテン樹脂を得
た。このポリ1−ブテン樹脂を「PB−B」という。(Reference Example B) Polymerization was carried out in the same manner as in Reference Example A except that the hydrogen / 1-butene molar ratio in the gas phase of the reactor was adjusted to 0.5 to give a poly-1-butene resin. Obtained. This poly 1-butene resin is referred to as "PB-B".
【0032】また、このPB−Bのメルトフローレー
ト、分子量分布を表す重量平均分子量(Mw)と数平均
分子量(Mn)との比(Mw/Mn)、およびアイソタ
クチック値を測定したところ、それぞれMFR: 20
g/10分(ASTM:D1238,E)、Mw/Mn
=4.5、II=95%であった。Further, the melt flow rate of PB-B, the ratio (Mw / Mn) of the weight average molecular weight (Mw) representing the molecular weight distribution to the number average molecular weight (Mn), and the isotactic value were measured. MFR: 20 each
g / 10 minutes (ASTM: D1238, E), Mw / Mn
= 4.5, II = 95%.
【0033】(参考例C)シクロヘキシルメチルジメト
キシシランの供給量を20mM/hrに変更し、反応器
の気相部における水素/1−ブテンのモル比を0.00
6に調整した以外は、参考例Aと同様にして重合を行
い、ポリ1−ブテン樹脂を得た。このポリ1−ブテン樹
脂を「PB−C」という。(Reference Example C) The supply amount of cyclohexylmethyldimethoxysilane was changed to 20 mM / hr and the molar ratio of hydrogen / 1-butene in the gas phase part of the reactor was 0.00.
Polymerization was performed in the same manner as in Reference Example A except that the amount was adjusted to 6, to obtain a poly-1-butene resin. This poly 1-butene resin is referred to as "PB-C".
【0034】また、このPB−Cのメルトフローレー
ト、分子量分布を表す重量平均分子量(Mw)と数平均
分子量(Mn)との比(Mw/Mn)、およびアイソタ
クチック値を測定したところ、それぞれMFR:0.0
5g/10分、Mw/Mn=5、II=97%であっ
た。Further, the melt flow rate of PB-C, the ratio (Mw / Mn) of the weight average molecular weight (Mw) representing the molecular weight distribution to the number average molecular weight (Mn), and the isotactic value were measured. MFR: 0.0
It was 5 g / 10 minutes, Mw / Mn = 5, and II = 97%.
【0035】(参考例D)シクロヘキシルメチルジメト
キシシランの供給量を20mM/hrに変更し、反応器
の気相部における水素/1−ブテンのモル比を1.5に
調整した以外は、参考例Aと同様にして重合を行い、ポ
リ1−ブテン樹脂を得た。このポリ1−ブテン樹脂を
「PB−D」という。Reference Example D Reference Example except that the supply amount of cyclohexylmethyldimethoxysilane was changed to 20 mM / hr and the hydrogen / 1-butene molar ratio in the gas phase part of the reactor was adjusted to 1.5. Polymerization was performed in the same manner as in A to obtain a poly-1-butene resin. This poly 1-butene resin is referred to as "PB-D".
【0036】また、このPB−Dのメルトフローレー
ト、分子量分布を表す重量平均分子量(Mw)と数平均
分子量(Mn)との比(Mw/Mn)、およびアイソタ
クチック値を測定したところ、それぞれMFR:100
g/10分、Mw/Mn=5、II=97%であった。The melt flow rate of PB-D, the ratio (Mw / Mn) of the weight average molecular weight (Mw) representing the molecular weight distribution to the number average molecular weight (Mn), and the isotactic value were measured. MFR: 100 each
g / 10 minutes, Mw / Mn = 5, II = 97%.
【0037】(参考例E)内容積200lのSUS製反
応器に、ヘキサン50l/hr、液体1−ブテン50l
/hr、三塩化チタン(東邦チタニウム(株)製、TA
C−141)100mM/hr、ジエチルアルミニウム
クロリド100mM/hr、ジエチルアルミニウムアイ
オダイド100mM/hrと水素を連続的に供給し、重
合温度60℃、重合圧力4.8barで反応させた。こ
のとき、水素の供給量は、反応器の気相部における水素
/1−ブテンのモル比が0.04となるように調整し
た。反応器内の液量を100lに保ちながら、液状の反
応混合物を連続的に抜き出した。抜き出した反応混合物
に1l/hrのメタノールを添加して1−ブテンを除去
し、水100l/hrを添加し、攪拌した。次に、水を
分離し、さらに280℃に昇温してフラッシュ蒸留して
ヘキサンを除去した後、得られたポリ1−ブテン樹脂を
250℃でペレット化した。この重合反応における重合
活性は63g/mM・Tiであった。このようにして得
られたポリ1−ブテン樹脂を「PB−E」という。(Reference Example E) 50 l / hr of hexane and 50 l of liquid 1-butene were placed in a SUS reactor having an internal volume of 200 l.
/ Hr, titanium trichloride (Toho Titanium Co., Ltd., TA
C-141) 100 mM / hr, diethylaluminum chloride 100 mM / hr, diethylaluminium iodide 100 mM / hr and hydrogen were continuously supplied, and reacted at a polymerization temperature of 60 ° C. and a polymerization pressure of 4.8 bar. At this time, the supply amount of hydrogen was adjusted so that the molar ratio of hydrogen / 1-butene in the gas phase part of the reactor was 0.04. The liquid reaction mixture was continuously withdrawn while maintaining the liquid volume in the reactor at 100 l. To the extracted reaction mixture, 1 l / hr of methanol was added to remove 1-butene, 100 l / hr of water was added, and the mixture was stirred. Next, water was separated, the temperature was further raised to 280 ° C., flash distillation was performed to remove hexane, and the obtained poly-1-butene resin was pelletized at 250 ° C. The polymerization activity in this polymerization reaction was 63 g / mM · Ti. The poly-1-butene resin thus obtained is referred to as "PB-E".
【0038】また、このPB−Eのメルトフローレー
ト、分子量分布を表す重量平均分子量(Mw)と数平均
分子量(Mn)との比(Mw/Mn)、およびアイソタ
クチック値を測定したところ、それぞれMFR:0.5
g/10分、Mw/Mn=12、II=95%であっ
た。The melt flow rate of PB-E, the ratio (Mw / Mn) of the weight average molecular weight (Mw) representing the molecular weight distribution to the number average molecular weight (Mn), and the isotactic value were measured. MFR: 0.5 each
g / 10 minutes, Mw / Mn = 12, II = 95%.
【0039】(参考例F)シクロヘキシルメチルジメト
キシシランの供給量を1mM/hrに変更し、反応器の
気相部における水素/1−ブテンのモル比を0.02に
調整した以外は、参考例Aと同様にして重合を行い、ポ
リ1−ブテン樹脂を得た。このポリ1−ブテン樹脂を
「PB−F」という。Reference Example F Reference Example except that the supply amount of cyclohexylmethyldimethoxysilane was changed to 1 mM / hr and the molar ratio of hydrogen / 1-butene in the gas phase part of the reactor was adjusted to 0.02. Polymerization was performed in the same manner as in A to obtain a poly-1-butene resin. This poly 1-butene resin is referred to as "PB-F".
【0040】また、このPB−Fのメルトフローレー
ト、分子量分布を表す重量平均分子量(Mw)と数平均
分子量(Mn)との比(Mw/Mn)、およびアイソタ
クチック値を測定したところ、それぞれMFR:0.5
g/10分、Mw/Mn=4.5、II=90%であっ
た。The melt flow rate of PB-F, the ratio (Mw / Mn) of the weight average molecular weight (Mw) representing the molecular weight distribution to the number average molecular weight (Mn), and the isotactic value were measured. MFR: 0.5 each
g / 10 minutes, Mw / Mn = 4.5, II = 90%.
【0041】(参考例G)反応器の気相部における水素
/1−ブテンのモル比を0.02に調整した以外は、参
考例Aと同様にして重合を行い、ポリ1−ブテン樹脂を
得た。このポリ1−ブテン樹脂を「PB−G」という。Reference Example G Polymerization was carried out in the same manner as in Reference Example A, except that the hydrogen / 1-butene molar ratio in the gas phase of the reactor was adjusted to 0.02, to give a poly-1-butene resin. Obtained. This poly 1-butene resin is referred to as "PB-G".
【0042】また、このPB−Gのメルトフローレー
ト、分子量分布を表す重量平均分子量(Mw)と数平均
分子量(Mn)との比(Mw/Mn)、およびアイソタ
クチック値を測定したところ、それぞれMFR:0.5
g/10分、Mw/Mn=4.5、II=95%であっ
た。The melt flow rate of PB-G, the ratio (Mw / Mn) of the weight average molecular weight (Mw) representing the molecular weight distribution to the number average molecular weight (Mn), and the isotactic value were measured. MFR: 0.5 each
g / 10 minutes, Mw / Mn = 4.5, II = 95%.
【0043】(実施例1〜3)PB−A(MFR:0.
2g/10分(ASTM:D1238,E)、Mw/M
n=4.5、II=95%)と、PB−B(MFR:
20g/10分(ASTM:D1238,E)、Mw/
Mn=4.5、II=95%)とを、表1に示す割合で
配合してなる混合物100重量部に、酸化防止剤として
Irganox 1330、Irganox 1010、 Irganox 1076をそれぞれ
0.4重量部、0.3重量部、0.2重量部の割合で添
加し、さらに各混合物に核剤としてポリエチレンを0.
2重量部、顔料としてイソインドリノン系の黄色有機顔
料0.05重量部と酸化チタン0.2重量部の割合で添
加した。次に、ヘンシェルミキサーで撹拌、混合した
後、65mmφ押出機を用いて溶融、混練し、 ポリ1−
ブテン樹脂組成物のペレットを製造した。(Examples 1 to 3) PB-A (MFR: 0.
2 g / 10 minutes (ASTM: D1238, E), Mw / M
n = 4.5, II = 95%) and PB-B (MFR:
20 g / 10 minutes (ASTM: D1238, E), Mw /
(Mn = 4.5, II = 95%) in an amount of 100 parts by weight of a mixture prepared by mixing the compounds in the proportions shown in Table 1.
Irganox 1330, Irganox 1010, and Irganox 1076 were added at a ratio of 0.4 parts by weight, 0.3 parts by weight, and 0.2 parts by weight, respectively, and polyethylene was used as a nucleating agent in each mixture in an amount of 0.
2 parts by weight, 0.05 parts by weight of an isoindolinone-based yellow organic pigment as a pigment, and 0.2 parts by weight of titanium oxide were added. Next, after stirring and mixing with a Henschel mixer, melting and kneading using a 65 mmφ extruder, poly 1-
Pellets of the butene resin composition were produced.
【0044】得られたペレットを温度200℃の加熱プ
レスで10分間溶融させた後、約30℃の冷却プレスで
5分間加圧して、厚さ2mmおよび3mmの2種類のプ
レスシートを作成した。このプレスシートを試料とし
て、下記の方法に従って、耐熱性、引張降伏応力、衝撃
強度を測定した。The pellets thus obtained were melted by a heating press at a temperature of 200 ° C. for 10 minutes and then pressed by a cooling press at a temperature of about 30 ° C. for 5 minutes to prepare two types of press sheets having a thickness of 2 mm and 3 mm. Using this press sheet as a sample, heat resistance, tensile yield stress and impact strength were measured according to the following methods.
【0045】また、ポリ1−ブテン樹脂組成物のペレッ
トを用いて、パイプ成形装置(日立造船産業株製)で、
内径:13mm、外径:17mmのパイプを作製し、下
記の方法に従って、熱管内圧クリープ特性およびパイプ
の成形性を評価した。結果を表1に示す。Further, using a pellet of the poly-1-butene resin composition, in a pipe molding machine (manufactured by Hitachi Zosen Sangyo Co., Ltd.),
A pipe having an inner diameter of 13 mm and an outer diameter of 17 mm was produced, and the heat pipe internal pressure creep property and the pipe formability were evaluated according to the following methods. The results are shown in Table 1.
【0046】耐熱性
JIS K7206(熱可塑性プラスチックのビカット
軟化温度試験方法)に準拠して、耐熱性を測定した。こ
のビカット軟化温度は樹脂の最高使用可能温度を示す1
つの尺度であり、給湯・給水用のパイプは、熱水と接触
する場合があるので、100℃が好ましい。Heat resistance The heat resistance was measured according to JIS K7206 (Vicat softening temperature test method for thermoplastics). This Vicat softening temperature indicates the maximum usable temperature of the resin 1
It is one of the measures, and a hot water supply / water supply pipe may come into contact with hot water, so 100 ° C. is preferable.
【0047】引張降伏応力
ASTM D638に準拠し、ASTM4号ダンベルを
用いて測定した。Tensile Yield Stress Measured using ASTM No. 4 dumbbell in accordance with ASTM D638.
【0048】衝撃強度
ASTM D256に準拠し、ノッチを入れて0℃で測
定した。Impact Strength Measured at 0 ° C. according to ASTM D256 with a notch.
【0049】熱間内圧クリープ特性
90±1℃に調節された恒温槽中にパイプを浸漬し、パ
イプの円周方向に発生する応力が70kg/cm2 にな
るように90℃温水をパイプ内に通じて加圧し、パイプ
が破損するまでの時間を測定した。Creep characteristics of hot internal pressure The pipe is immersed in a constant temperature bath adjusted to 90 ± 1 ° C., and 90 ° C. hot water is introduced into the pipe so that the stress generated in the circumferential direction of the pipe becomes 70 kg / cm 2. The pipe was pressurized and the time until the pipe was broken was measured.
【0050】パイプの成形性
10m/minの成形速度でパイプを成形し、得られた
パイプの内外面を目視により観察し、下記の基準で評価
した。
○…成形性が良好であり、かつパイプの外観も良好
△…パイプ成形は一応可能であるが、パイプの内外面に
小さな凹凸状の肌荒れが発生
×…パイプ成形ができなかったMoldability of pipe The pipe was molded at a molding speed of 10 m / min, and the inner and outer surfaces of the obtained pipe were visually observed and evaluated according to the following criteria. ○: Good moldability and good appearance of pipe △: Pipe molding is possible, but small irregularities on the inner and outer surfaces of the pipe caused rough surface ×: Pipe molding was not possible
【0051】(実施例4)核剤としてエチレンビスステ
アロアマイド(EBSA)を添加する以外は、実施例2
と同様にして、ポリ1−ブテン樹脂組成物のペレットを
製造し、これを用いてプレスシートを作成し、耐熱性、
引張降伏応力、衝撃強度を測定し、また、パイプを作製
し、熱管内圧クリープ特性およびパイプの成形性を評価
した。結果を表1に示す。Example 4 Example 2 was repeated except that ethylenebisstearamide (EBSA) was added as a nucleating agent.
In the same manner as above, a pellet of the poly-1-butene resin composition is produced, a press sheet is prepared using the pellet, and heat resistance,
Tensile yield stress and impact strength were measured, pipes were prepared, and heat pipe internal pressure creep properties and pipe formability were evaluated. The results are shown in Table 1.
【0052】(実施例5)核剤を添加しない以外は、実
施例2と同様にして、ポリ1−ブテン樹脂組成物のペレ
ットを製造し、これを用いてプレスシートを作成し、耐
熱性、引張降伏応力、衝撃強度を測定し、また、パイプ
を作製し、熱管内圧クリープ特性およびパイプの成形性
を評価した。結果を表1に示す。(Example 5) Pellets of the poly-1-butene resin composition were produced in the same manner as in Example 2 except that the nucleating agent was not added, and a press sheet was prepared using the pellets to obtain heat resistance, Tensile yield stress and impact strength were measured, pipes were prepared, and heat pipe internal pressure creep properties and pipe formability were evaluated. The results are shown in Table 1.
【0053】(実施例6および7)PB−C(MFR:
0.05g/10分、Mw/Mn=5、II=97%)
と、PB−D(MFR:100g/10分、Mw/Mn
=5、II=97%)とを、表1に示す割合で配合する
以外は実施例2と同様にして、ポリ1−ブテン樹脂組成
物のペレットを製造し、これを用いてプレスシートを作
成し、耐熱性、引張降伏応力、衝撃強度を測定し、ま
た、パイプを作製し、熱管内圧クリープ特性およびパイ
プの成形性を評価した。結果を表1に示す。(Examples 6 and 7) PB-C (MFR:
0.05 g / 10 minutes, Mw / Mn = 5, II = 97%)
And PB-D (MFR: 100 g / 10 minutes, Mw / Mn
= 5, II = 97%) in the proportions shown in Table 1 in the same manner as in Example 2 to produce pellets of the poly-1-butene resin composition, and using this, a press sheet is prepared. Then, the heat resistance, the tensile yield stress, and the impact strength were measured, and pipes were prepared to evaluate the creep characteristics in the heat pipe and the formability of the pipe. The results are shown in Table 1.
【0054】(比較例1)PB−Bを使用しない以外
は、実施例1と同様にして組成物を製造し、実施例1と
同様にして、シートを作製して、耐熱性、引張降伏応
力、衝撃強度を測定し、また、パイプを作製し、熱管内
圧クリープ特性およびパイプの成形性を評価した。結果
を表1に示す。その結果、10m/minでパイプ成形
を行なうと、得られるパイプの内外面に著しい肌荒れが
生じていた。Comparative Example 1 A composition was prepared in the same manner as in Example 1 except that PB-B was not used, and a sheet was prepared in the same manner as in Example 1 to obtain heat resistance and tensile yield stress. The impact strength was measured, pipes were produced, and the heat pipe internal pressure creep properties and pipe formability were evaluated. The results are shown in Table 1. As a result, when the pipe was formed at 10 m / min, the inner and outer surfaces of the obtained pipe were significantly roughened.
【0055】(比較例2)PB−Aを使用しない以外
は、実施例1と同様にして組成物を製造し、実施例1と
同様にして、シートを作製して、耐熱性、引張降伏応
力、衝撃強度を測定し、また、パイプを作製し、熱管内
圧クリープ特性およびパイプの成形性を評価した。結果
を表2に示す。その結果、得られるシートは衝撃強度に
劣り、また、パイプ成形の際には、溶融パリソンの粘度
が著しく小さく、パイプ成形が不可能であった。(Comparative Example 2) A composition was prepared in the same manner as in Example 1 except that PB-A was not used, and a sheet was prepared in the same manner as in Example 1 to obtain heat resistance and tensile yield stress. The impact strength was measured, pipes were produced, and the heat pipe internal pressure creep properties and pipe formability were evaluated. The results are shown in Table 2. As a result, the obtained sheet was inferior in impact strength, and the viscosity of the molten parison was extremely small during pipe molding, and pipe molding was impossible.
【0056】(比較例3)PB−AおよびPB−Bの代
わりに、PB−E(MFR:0.5g/10分、Mw/
Mn=12、II=95%)を使用した以外は、実施例
1と同様にして組成物を製造し、実施例1と同様にし
て、シートを作製して、耐熱性、引張降伏応力、衝撃強
度を測定し、また、パイプを作製し、熱管内圧クリープ
特性およびパイプの成形性を評価した。結果を表2に示
す。(Comparative Example 3) Instead of PB-A and PB-B, PB-E (MFR: 0.5 g / 10 min, Mw /
(Mn = 12, II = 95%), a composition was produced in the same manner as in Example 1, and a sheet was produced in the same manner as in Example 1 to obtain heat resistance, tensile yield stress, and impact. The strength was measured, pipes were prepared, and the heat pipe internal pressure creep properties and pipe formability were evaluated. The results are shown in Table 2.
【0057】(比較例4)PB−AおよびPB−Bの代
わりに、PB−F(MFR:0.5g/10分、Mw/
Mn=4.5、II=90%)を使用した以外は、実施
例1と同様にして組成物を製造し、実施例1と同様にし
て、シートを作製して、耐熱性、引張降伏応力、衝撃強
度を測定し、また、パイプを作製し、熱管内圧クリープ
特性およびパイプの成形性を評価した。結果を表2に示
す。その結果、得られたシートは、引張降伏応力が低
く、パイプの熱管内圧クリープ試験においては、75k
g/cm2 の応力をかける途中でパイプが破裂した。ま
た、パイプ成形の際には、得られたパイプの内外面に著
しい肌荒れが生じていた。(Comparative Example 4) Instead of PB-A and PB-B, PB-F (MFR: 0.5 g / 10 min, Mw /
(Mn = 4.5, II = 90%) except that the composition was produced in the same manner as in Example 1, and a sheet was produced in the same manner as in Example 1 to obtain heat resistance and tensile yield stress. The impact strength was measured, pipes were produced, and the heat pipe internal pressure creep properties and pipe formability were evaluated. The results are shown in Table 2. As a result, the obtained sheet has a low tensile yield stress, and is 75k in the hot pipe internal pressure creep test.
The pipe ruptured while applying a stress of g / cm 2 . In addition, during pipe molding, the inner and outer surfaces of the obtained pipe were significantly roughened.
【0058】(比較例5)PB−AおよびPB−Bの代
わりに、PB−G(MFR:0.5g/10分、Mw/
Mn=4.5、II=95%)を使用した以外は、実施
例1と同様にして組成物を製造し、実施例1と同様にし
てシートを作製して、耐熱性、引張降伏応力、衝撃強度
を測定し、また、パイプを作製して、熱管内圧クリープ
特性およびパイプの成形性を評価した。結果を表2に示
す。(Comparative Example 5) Instead of PB-A and PB-B, PB-G (MFR: 0.5 g / 10 min, Mw /
(Mn = 4.5, II = 95%), a composition was produced in the same manner as in Example 1, and a sheet was produced in the same manner as in Example 1 to obtain heat resistance, tensile yield stress, and The impact strength was measured, and pipes were manufactured to evaluate the creep characteristics of the heat pipe internal pressure and the formability of the pipes. The results are shown in Table 2.
【0059】[0059]
【表1】 [Table 1]
【0060】[0060]
【表2】 [Table 2]
【0061】[0061]
【発明の効果】本発明の組成物は、ポリ1−ブテン樹脂
が本来有する、優れた剛性、クリープ特性、耐衝撃強度
などの特性を備えるとともに、さらに成形性、特に高い
成形速度での成形性、いわゆる高速成形性に優れたポリ
1−ブテン樹脂組成物を提供することにある。そのた
め、本発明の組成物は、パイプに成形して、給湯・給水
管用の配管材として好適なパイプを得ることができる。EFFECTS OF THE INVENTION The composition of the present invention has characteristics such as excellent rigidity, creep characteristics and impact strength, which are inherent in poly-1-butene resin, and further, moldability, especially at high molding speed. That is, to provide a poly-1-butene resin composition excellent in so-called high-speed moldability. Therefore, the composition of the present invention can be molded into a pipe to obtain a pipe suitable as a piping material for hot water supply / water supply pipes.
Claims (2)
分、分子量分布を表す重量平均分子量(Mw)と数平均
分子量(Mn)との比(Mw/Mn)が6以下、かつア
イソタクチック値が93%以上であるポリ1−ブテン樹
脂(A)60〜95重量部、およびメルトフローレート
が(A)のポリ1−ブテン樹脂の20倍以上であり、分
子量分布を表す重量平均分子量(Mw)と数平均分子量
(Mn)との比(Mw/Mn)が6以下、かつアイソタ
クチック値が93%以上であるポリ1−ブテン樹脂
(B)40〜5重量部を含むポリ1−ブテン樹脂組成
物。1. A melt flow rate of 0.01 to 5 g / 10.
The poly-1-butene resin (A) having a ratio (Mw / Mn) of the weight average molecular weight (Mw) representing the molecular weight distribution and the number average molecular weight (Mn) of 6 or less and an isotactic value of 93% or more. 60 to 95 parts by weight, and the melt flow rate is 20 times or more that of the poly-1-butene resin having (A), and the ratio (Mw / Mw) of the weight average molecular weight (Mw) representing the molecular weight distribution to the number average molecular weight (Mn). A poly 1-butene resin composition containing 40 to 5 parts by weight of a poly 1-butene resin (B) having an Mn) of 6 or less and an isotactic value of 93% or more.
物にさらに核剤を含むことを特徴とするポリ1−ブテン
樹脂組成物。2. A poly-1-butene resin composition comprising the poly-1-butene resin composition according to claim 1 further containing a nucleating agent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP03227913A JP3091534B2 (en) | 1990-09-21 | 1991-09-09 | Poly 1-butene resin composition |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25356890 | 1990-09-21 | ||
JP2-253568 | 1990-09-21 | ||
JP03227913A JP3091534B2 (en) | 1990-09-21 | 1991-09-09 | Poly 1-butene resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH059352A true JPH059352A (en) | 1993-01-19 |
JP3091534B2 JP3091534B2 (en) | 2000-09-25 |
Family
ID=26527946
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP03227913A Expired - Lifetime JP3091534B2 (en) | 1990-09-21 | 1991-09-09 | Poly 1-butene resin composition |
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Cited By (5)
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 |
JP2006169306A (en) * | 2004-12-14 | 2006-06-29 | Mitsui Chemicals Inc | Poly-1-butene resin composition and its use |
JP2007031699A (en) * | 2005-06-20 | 2007-02-08 | Bridgestone Corp | Highly chlorine water-resistant polyolefin resin and hose for supplying water and hot-water |
JP2007186563A (en) * | 2006-01-12 | 2007-07-26 | Mitsui Chemicals Inc | Polybutene resin composition |
WO2019182000A1 (en) | 2018-03-22 | 2019-09-26 | 三井化学株式会社 | Butene-based polymer composition |
-
1991
- 1991-09-09 JP JP03227913A patent/JP3091534B2/en not_active Expired - Lifetime
Cited By (7)
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 |
JP2011046953A (en) * | 1998-03-05 | 2011-03-10 | Basell Technology Co Bv | Polybutene-1 (co)polymer, and method for producing the same |
JP2006169306A (en) * | 2004-12-14 | 2006-06-29 | Mitsui Chemicals Inc | Poly-1-butene resin composition and its use |
JP4647989B2 (en) * | 2004-12-14 | 2011-03-09 | 三井化学株式会社 | Poly 1-butene resin composition and use thereof |
JP2007031699A (en) * | 2005-06-20 | 2007-02-08 | Bridgestone Corp | Highly chlorine water-resistant polyolefin resin and hose for supplying water and hot-water |
JP2007186563A (en) * | 2006-01-12 | 2007-07-26 | Mitsui Chemicals Inc | Polybutene resin composition |
WO2019182000A1 (en) | 2018-03-22 | 2019-09-26 | 三井化学株式会社 | Butene-based polymer composition |
Also Published As
Publication number | Publication date |
---|---|
JP3091534B2 (en) | 2000-09-25 |
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