JPH0637075B2 - Molding method for resin pipes - Google Patents
Molding method for resin pipesInfo
- Publication number
- JPH0637075B2 JPH0637075B2 JP1270907A JP27090789A JPH0637075B2 JP H0637075 B2 JPH0637075 B2 JP H0637075B2 JP 1270907 A JP1270907 A JP 1270907A JP 27090789 A JP27090789 A JP 27090789A JP H0637075 B2 JPH0637075 B2 JP H0637075B2
- Authority
- JP
- Japan
- Prior art keywords
- molding
- pipe
- resin
- ethylene
- phosphite
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 34
- 238000000465 moulding Methods 0.000 title claims description 31
- 239000011347 resin Substances 0.000 title claims description 25
- 229920005989 resin Polymers 0.000 title claims description 25
- 229920000573 polyethylene Polymers 0.000 claims description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 17
- 239000005977 Ethylene Substances 0.000 claims description 17
- -1 Di-t-butylphenyl Chemical group 0.000 claims description 13
- 239000004711 α-olefin Substances 0.000 claims description 12
- 238000004513 sizing Methods 0.000 claims description 11
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 10
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims description 8
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000037303 wrinkles Effects 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000012690 ionic polymerization Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000007613 slurry method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- FRCLQKLLFQYUJJ-UHFFFAOYSA-N P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C Chemical compound P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C FRCLQKLLFQYUJJ-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- JBTXGEJRJCNRLU-UHFFFAOYSA-N [2-(dihydroxyphosphanyloxymethyl)-3-hydroxy-2-(hydroxymethyl)propyl] dihydrogen phosphite Chemical compound OP(O)OCC(CO)(CO)COP(O)O JBTXGEJRJCNRLU-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000011990 phillips catalyst Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 230000037330 wrinkle prevention Effects 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Description
【発明の詳細な説明】 〔発明の背景〕 ＜産業上の利用分野＞ 本発明は、厚肉パイプの平滑性に優れた外径サイジング
成形法により成形するパイプの成形法に関する。Description: BACKGROUND OF THE INVENTION <Industrial field of use> The present invention relates to a pipe forming method for forming a thick pipe by an outer diameter sizing forming method having excellent smoothness.
＜従来の技術＞ 従来、ポリエチレン製パイプの成形法は、ジョイント接
続の施工上、パイプ寸法管理において内径よりも外径の
方が重要視されることから外径サイジング成形法を用
い、また材料として、押出成形性の観点より比較的分子
量分布の広い汎用の押出成形用高密度ポリエチレンおよ
び低密度ポリエチレンを使用するのが一般的であった。<Prior Art> Conventionally, the outer diameter sizing molding method is used as the material for the polyethylene pipe molding method because the outer diameter is more important than the inner diameter in the pipe size control in the construction of the joint connection. From the viewpoint of extrusion moldability, it is common to use general-purpose high-density polyethylene for extrusion molding and low-density polyethylene having a relatively wide molecular weight distribution.
ポリエチレン製パイプは長期性能、耐薬品性に優れ、し
かも安価で加工が容易であるため、その特性を活かして
古くから給排水管に主として用いられてきた。特に低密
度のエチレン・α−オレフィン共重合体（直鎖状低密度
ポリエチレン）は柔軟性、耐塩素水性等の優れた特徴を
有していることから、ＪＩＳ−Ｋ６７６２の一種管（軟
質管）にも近年使用されだしている。Since polyethylene pipes have excellent long-term performance and chemical resistance, are inexpensive, and are easy to process, they have been used mainly for water supply and drainage pipes for a long time due to their characteristics. In particular, low density ethylene / α-olefin copolymer (linear low density polyethylene) has excellent characteristics such as flexibility and chlorine water resistance, so it is a type of JIS-K6762 pipe (soft pipe). It has started to be used in recent years.
また、外径サイジング成形法により成形されたパイプの
場合、押出機ダイスから樹脂がいったん溶融状態で押し
出された後、外部冷却サイジング装置に導かれることか
ら、溶融状態での形状保持性、すなわちドローダウン性
に優れたものであることが必要とされ、比較的分子量分
布の広いエチレン単独重合体もしくは、エチレン・α−
オレフィン共重合体等が使用されてきた。Further, in the case of a pipe molded by the outer diameter sizing molding method, the resin is extruded from the extruder die in the molten state and then guided to the external cooling sizing device, so that the shape retention in the molten state, that is, the draw It is required to have excellent down property, and an ethylene homopolymer having a relatively wide molecular weight distribution or ethylene / α-
Olefin copolymers and the like have been used.
＜発明が解決しようとする課題＞ しかしながら、前述のような比較的分子量分布が広く押
出加工性のよい直鎖状エチレン系重合体を用いて厚肉の
パイプを外径サイジング成形法により成形しようとする
と、パイプ内面（内壁）にランダムな筋状の皺が発生
し、外観上の商品価値を損なうと同時に管内流量抵抗の
増加等が生じて実用上大きな問題となることが判明し
た。<Problems to be Solved by the Invention> However, it is attempted to mold a thick pipe by an outer diameter sizing molding method using the linear ethylene polymer having a relatively wide molecular weight distribution and good extrusion processability as described above. Then, it was found that random streaky wrinkles are generated on the inner surface (inner wall) of the pipe, which impairs the commercial value in appearance and at the same time increases the flow resistance in the pipe, which is a serious problem in practical use.
このような皺の発生の詳細なメカニズムは不明である
が、溶融樹脂の流動状態が不安定（一種の脈動）になる
こと、サイジングダイスで溶融樹脂の外径よりも絞られ
ていること、パイプ製品の肉厚が厚くなると外表面から
先に冷却されるため、その結果として内表面が外表面側
へ収縮されること等が原因ではないかと考えられる。Although the detailed mechanism of the occurrence of such wrinkles is unclear, the flow state of the molten resin becomes unstable (a kind of pulsation), the sizing die narrows the outer diameter of the molten resin, and the pipe When the wall thickness of the product becomes thicker, the outer surface is cooled first, and as a result, it is considered that the inner surface is contracted to the outer surface side.
一方、比較的分子量分布の狭い樹脂を用いて成形すれば
皺は発生しないが、樹脂の溶融張力不足によってドロー
ダウン性が低下し、その結果として溶融樹脂が垂れて成
形が困難になるばかりでなく、特に低温、高速押出成形
の条件下ではパイプの内外面に肌荒れ現象（通称シャー
クスキン）が発生し、これも大きな問題となることが知
られている。On the other hand, wrinkling does not occur if molding is performed using a resin with a relatively narrow molecular weight distribution, but drawdown is deteriorated due to insufficient melt tension of the resin, and as a result, the molten resin sags and molding becomes difficult. It is known that a skin roughening phenomenon (commonly referred to as sharkskin) occurs on the inner and outer surfaces of a pipe particularly under conditions of low temperature and high speed extrusion molding, and this is also a serious problem.
＜要 旨＞ 本発明者らは、前述の問題点を解決するために、外径サ
イジング成形法による厚肉パイプ内面の皺の発生を防止
すべく鋭意研究を重ねた結果、特定のエチレン系樹脂に
特定の添加剤を配合することにより、ドローダウン性に
優れ、かつ皺の発生しないパイプ用樹脂組成物となるこ
とを見い出して本発明を完成した。<Summary> In order to solve the above-mentioned problems, the present inventors have earnestly studied to prevent the wrinkles on the inner surface of the thick pipe by the outer diameter sizing molding method, and as a result, a specific ethylene resin has been obtained. The present invention has been completed by discovering that a resin composition for pipes having excellent drawdown properties and free of wrinkles can be obtained by adding a specific additive to.
すなわち、本発明の樹脂パイプの成形法は、樹脂を外径
サイジング成形法に付して肉厚が３mm以上のパイプを成
形する方法において、樹脂としてＭＦＲが０．０５〜２
ｇ／１０分かつ１９０℃における溶融張力が３ｇ以上で
ある直鎖状エチレン重合体に、フォスファイトおよび／
またはフォスフォナイトを０．０２〜１重量％配合した
組成物を用いること、を特徴とするものである。That is, the resin pipe molding method of the present invention is a method for molding a pipe having a wall thickness of 3 mm or more by subjecting a resin to an outer diameter sizing molding method, and having a resin MFR of 0.05 to 2
g / 10 min and a linear ethylene polymer having a melt tension at 190 ° C. of 3 g or more, phosphite and /
Alternatively, a composition containing 0.02 to 1% by weight of phosphonite is used.
＜効 果＞ 本発明の樹脂パイプの成形法によれば、特定のエチレン
系重合体に特定の添加剤を配合すると、前記した従来技
術でのパイプの内面に皺が発生するといった問題が解決
される。<Effect> According to the resin pipe molding method of the present invention, when a specific additive is added to a specific ethylene polymer, the problem of wrinkles occurring on the inner surface of the pipe in the above-mentioned prior art is solved. It
さらに、従来二次酸化防止剤として用いられていた特定
のリン系化合物を用いることによってドローダウン性に
優れ、パイプ内面の皺発生の問題が解決されるというこ
とは、全く思いがけなかったことである。Furthermore, it is completely unexpected that the drawdown property is excellent and the problem of wrinkling on the inner surface of the pipe is solved by using a specific phosphorus compound that has been conventionally used as a secondary antioxidant. .
従って、本発明の樹脂パイプの成形法は、厚肉サイズの
パイプが必要とされる分野へ実用性の高い成形法として
活用することができる。Therefore, the resin pipe molding method of the present invention can be utilized as a highly practical molding method in the field where thick-walled pipes are required.
〔Ｉ〕組成物 (1)構成成分 (a)エチレン重合体 本発明の樹脂パイプの成形法で用いるエチレン重合体
は、イオン重合触媒を用いて製造した直鎖状重合体であ
り、気相法、溶液法、スラリー法、高圧法等いずれの製
造法によるものでも適用でき、エチレンの単独重合体も
しくは、主成分のエチレンとエチレン以外のコモノマー
の一種または、二種以上を共重合させて得られた共重合
体である。[I] Composition (1) Constituent Components (a) Ethylene Polymer The ethylene polymer used in the method for molding the resin pipe of the present invention is a linear polymer produced using an ionic polymerization catalyst, and is a gas phase method. It can be applied by any manufacturing method such as a solution method, a slurry method, a high pressure method, etc., and is obtained by homopolymerizing ethylene or by copolymerizing ethylene as a main component with one or more comonomers other than ethylene. It is a copolymer.
このエチレン重合体は、分子量の目安となるＭＦＲ（Ｊ
ＩＳ−Ｋ６７６０、荷重２．１６kg）が０．０５〜２ｇ
／１０分のものが適用でき、特に０．１〜１ｇ／１０分
のものが好ましい。これらの中でもＭＦＲの低い方の重
合体はドローダウン性、強度等に優れるが、過度に低く
て、例えばＭＦＲが０．０５未満のものは成形時の流動
性等の成形性が悪くなる。またＭＦＲが２超過のものは
ドローダウン性、強度等が劣る。This ethylene polymer has a MFR (J
IS-K6760, load 2.16kg) is 0.05-2g
Those of / 10 minutes can be applied, and those of 0.1 to 1 g / 10 minutes are particularly preferable. Among them, the polymer having a lower MFR is excellent in drawdown property, strength and the like, but is excessively low, and for example, a polymer having an MFR of less than 0.05 deteriorates moldability such as fluidity during molding. If the MFR exceeds 2, drawdown property and strength are poor.
また、このエチレン重合体の溶融張力は、これをＪＩＳ
−Ｋ６７６０のＭＦＲ測定法にて使用する炉及びノズル
から１９０℃の温度でシリンダー押出棒を１０mm／分の
速度で押出し、４ｍ／分の速度で引っ張ったときの溶融
張力が３ｇ以上のものが適用でき、特にドローダウン性
の観点より４ｇ以上のものが好ましい。Also, the melt tension of this ethylene polymer is
-A cylinder extrusion rod is extruded at a speed of 10 mm / min from a furnace and a nozzle used in the MFR measurement method of K6760 at a temperature of 190 ° C, and a melt tension of 3 g or more when pulled at a speed of 4 m / min is applied. It is possible, and particularly preferably 4 g or more from the viewpoint of drawdown property.
エチレン重合体として、酸化クロムをシリカ・アルミナ
等無機担体等に担持させたもの、すなわち酸化クロム系
フィリップス型触媒を用いて気相法、溶液法、スラリー
法、あるいは圧力５００kg／cm2以上および温度１００
〜３５０℃の条件下での高圧イオン重合法等の製造プロ
セスを適用して、エチレンを単独で重合もしくは主成分
のエチレンとα−オレフィンを共重合することで得られ
るものは、特に本発明の効果が大きく奏される。As an ethylene polymer, chromium oxide supported on an inorganic carrier such as silica / alumina, that is, using a chromium oxide type Phillips catalyst, a gas phase method, a solution method, a slurry method, or a pressure of 500 kg / cm 2 or more and a temperature. 100
Those obtained by polymerizing ethylene alone or copolymerizing ethylene as a main component and α-olefin by applying a manufacturing process such as a high pressure ionic polymerization method under the condition of ˜350 ° C. The effect is great.
エチレンと共重合させる場合のα−オレフィンとして
は、炭素数３〜１２程度のα−オレフィンたとえばプロ
ピレン、ブテン−１、ペンテン−１、ヘキセン−１、４
−メチルペンテン−１、オクテン−１等が挙げられる。
特に好ましいα−オレフィンは、炭素数４〜８のもの、
特にブテン−１、ヘキセン−１、４−メチルペンテン−
１およびオクテン−１、である。これらα−オレフィン
は二種以上併用することができる。共重合体中のα−オ
レフィン含量は、０．５〜２０重量％、好ましくは１〜
１５重量％である。When the α-olefin is copolymerized with ethylene, the α-olefin has about 3 to 12 carbon atoms, for example, propylene, butene-1, pentene-1, hexene-1, 4
-Methylpentene-1, octene-1 and the like.
Particularly preferred α-olefins have 4 to 8 carbon atoms,
Especially butene-1, hexene-1,4-methylpentene-
1 and octene-1. Two or more kinds of these α-olefins can be used in combination. The α-olefin content in the copolymer is 0.5 to 20% by weight, preferably 1 to
It is 15% by weight.
中でも、エチレン・α−オレフィン共重合体の密度（Ｊ
ＩＳ−Ｋ６７６０の試験法による）が０．９１５〜０．
９３０ｇ／cm3、特に０．９２０〜０．９２５ｇ／cm3の
ものが耐圧強度、長尺間巻の点で好ましい。これら共重
合体の密度は共重合させたα−オレフィンの種類および
（または）含量によって変化する。Above all, the density of the ethylene / α-olefin copolymer (J
IS-K6760) is 0.915-0.
930 g / cm 3, particularly compression strength ones 0.920~0.925g / cm 3, preferably in terms of long Shakuma winding. The density of these copolymers varies depending on the type and / or content of the copolymerized α-olefin.
この重合体は、また分子量分布の目安となるＦＲ（荷重
１０kg時のＭＦＲと上記荷重２．１６kg時のＭＦＲとの
比）が１３〜２５のもの、特に１４〜２０のもの、が好
ましい。ＦＲの低い方の重合体は衝撃強度等に優れる
が、成形時の流動性等の成形性が低下する傾向がある。
また、ＦＲが高いほど衝撃強度等が劣る傾向にある。こ
のようなエチレン重合体は市販のものの中から適宜選ん
で用いることができる。This polymer preferably has a FR (ratio of MFR at a load of 10 kg to MFR at a load of 2.16 kg) of 13 to 25, particularly 14 to 20, which is a measure of the molecular weight distribution. A polymer having a lower FR has excellent impact strength and the like, but the moldability such as fluidity during molding tends to be lowered.
Further, the higher the FR, the lower the impact strength and the like. Such an ethylene polymer can be appropriately selected and used from commercially available products.
(b)フォスファイトおよびフォスフォナイト本発明の樹
脂パイプの成形法において前記エチレン重合体に配合さ
れて樹脂組成物を形成する配合剤としてはフォスファイ
トまたはフォスフォナイトである。これらは併用して用
いることもできる。(b) Phosphite and Phosphonite The compounding agent that is mixed with the ethylene polymer to form a resin composition in the resin pipe molding method of the present invention is phosphite or phosphonite. These can be used in combination.
上記フォスファイトとしては、具体的にトリス（２，４
−ジ−ｔ−ブチルフェニル）フォスファイト、ビス
（２，６−ジ−ｔ−ブチル−４メチルフェニル）ペンタ
エリスリトール−ジ−フォスファイト、ビス（２，４−
ジ−ｔ−ブチルフェニル）ペンタエリスリトール−ジ−
フォスファイト等を挙げることができるが、水道管とし
て使用する場合は、加水分解によりパイプの耐塩素水性
を悪化さるので加水分解しにくいトリス（２，４−ジ−
ｔ−ブチルフェニル）フォスファイトを使用することが
特に好ましい。As the phosphite, specifically, Tris (2,4
-Di-t-butylphenyl) phosphite, bis (2,6-di-t-butyl-4methylphenyl) pentaerythritol-di-phosphite, bis (2,4-)
Di-t-butylphenyl) pentaerythritol-di-
Phosphite and the like can be mentioned, but when used as a water pipe, tris (2,4-di-), which is difficult to hydrolyze because it deteriorates the chlorine resistance of the pipe due to hydrolysis.
It is particularly preferred to use t-butylphenyl) phosphite.
このフォスファイトの配合量は、エチレン重合体に対し
て０．０２〜１重量％である。好ましくは０．０３〜
０．５重量％である。この配合量未満では皺発生防止効
果が小さく、一方、この配合量より多くなっても効果は
飽和してくると同時に製品のコスト高になり、また水道
管として使用する場合、ブリードによる水道水への流
出、耐塩素水性等の問題を発生する傾向があるので好ま
しくない。The amount of the phosphite compounded is 0.02 to 1% by weight based on the ethylene polymer. Preferably from 0.03
It is 0.5% by weight. If the amount is less than this amount, the effect of preventing wrinkles is small. On the other hand, if the amount is more than this amount, the effect is saturated and the cost of the product becomes high. Is not preferable because it tends to cause problems such as effluent of water and chlorine resistance.
また、上記フォスフォナイトとしては、例えばテトラキ
ス（２，４−ジ−ｔ−ブチルフェニル）−４，４′−ビ
フェニレン−ジ−フォスファイトを挙げることができ
る。Examples of the phosphonite include tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene-di-phosphite.
このフォスフォナイトの配合量は、エチレン重合体に対
して０．０２〜１重量％である。好ましくは０．０３〜
０．５重量％である。この配合量未満では皺発生防止効
果が小さく、一方、この配合量より多くなっても効果は
飽和してくると同時に製品のコスト高になり、また水道
管として使用する場合、ブリードによる水道水への流
出、耐塩素水性等の問題を生じる傾向になって好ましく
ない。The blending amount of this phosphonite is 0.02 to 1% by weight with respect to the ethylene polymer. Preferably from 0.03
It is 0.5% by weight. If the amount is less than this amount, the effect of preventing wrinkles is small. On the other hand, if the amount is more than this amount, the effect is saturated and the cost of the product becomes high. Of water and chlorine water resistance tend to cause problems.
(2)組成物の調製 上記構成成分を配合して組成物を製造する方法として
は、直接ロール、バンバリー、ニーダー、押出機等の混
練機で溶融混練する方法、配合剤の分散を良くするため
ヘンシェル型ミキサー等で予めエチレン重合体の粉体と
混合させた後、前述の混練機で溶融混練する方法、ある
いは一旦高濃度のマスターバッチを作った後に未配合の
エチレン重合体で希釈する方法等の種々の公知の方法を
適用することができる。(2) Preparation of composition As a method for producing a composition by blending the above-mentioned components, direct roll, Banbury, kneader, a method of melt-kneading with a kneader such as an extruder, to improve the dispersion of the compounding agent After mixing with ethylene polymer powder in advance with a Henschel type mixer, melt kneading with the above-mentioned kneader, or once preparing a high-concentration master batch and then diluting with unblended ethylene polymer, etc. Various known methods can be applied.
また、必要に応じて本発明の効果を著しく損なわない範
囲でポリプロピレン、分岐状ポリエチレン（高圧法ラジ
カル重合ポリエチレン）、エチレン・酢酸ビニル共重合
体等の混和可能な他の樹脂、あるいは他の酸化防止剤、
中和剤、滑剤、アンチブロッキング剤、帯電防止剤、紫
外線吸収剤、光安定剤、けい光増白剤等の添加剤、ある
いは有機系顔料、無機系顔料等の着色剤や充填剤等、を
直接または樹脂等のマスターバッチの形で添加すること
もできる。但し、これらを添加することによって皺発生
防止効果が低下する場合もあるので、種類および添加量
は注意しなければならない。If necessary, other miscible resins such as polypropylene, branched polyethylene (high-pressure radical polymerized polyethylene), ethylene / vinyl acetate copolymer, or other antioxidants may be used as long as the effects of the present invention are not significantly impaired. Agent,
Additives such as neutralizing agents, lubricants, anti-blocking agents, antistatic agents, ultraviolet absorbers, light stabilizers, fluorescent brighteners, or coloring agents such as organic pigments and inorganic pigments, fillers, etc. It can also be added directly or in the form of a masterbatch such as a resin. However, addition of these may reduce the wrinkle prevention effect, so care must be taken regarding the type and amount of addition.
〔II〕パイプ成形 本発明のパイプ成形法は汎用性があり、かつ外径寸法制
御に特徴を有する外径サイジング成形法であれば、成形
装置の大小、構造等に制限しない。[II] Pipe Molding The pipe molding method of the present invention is not limited to the size, structure, etc. of the molding apparatus as long as it is an outer diameter sizing molding method that is versatile and has a feature in controlling the outer diameter dimension.
但し、本発明の目的は肉厚が厚くてもパイプ内面の平滑
性を損なわない点にあり、これを達成するように改良さ
れた樹脂組成物を用いるため、パイプ肉厚は３mm以上、
好ましくは４mm以上、特に好ましくは６mm以上であるも
のが大きな効果を奏する。However, the object of the present invention is that even if the wall thickness is large, the smoothness of the inner surface of the pipe is not impaired, and since a resin composition improved to achieve this is used, the pipe wall thickness is 3 mm or more,
Those having a thickness of preferably 4 mm or more, particularly preferably 6 mm or more exhibit a great effect.
また、このパイプは必ずしも円形でなくてもよく、例え
ば長方形等異形押出成形に分類されるものも含む。な
お、この場合の肉厚とは最小肉厚箇所を意味する。さら
に、本発明の効果が奏される限り多層のパイプに成形す
ることもできる。Further, this pipe does not necessarily have to be circular, and includes pipes classified into irregular-shaped extrusion molding such as rectangular. The wall thickness in this case means the minimum wall thickness portion. Further, as long as the effects of the present invention are exhibited, it is possible to form a multilayer pipe.
実施例１〜５および比較例１ （イ）樹脂組成物の調製 気相法プロセスにて、微量酸素の存在下、二酸化けい素
に酸化クロムと酸化チタンを担持した通称フィリップス
型イオン重合触媒を用いてエチレンとブテン−１を共重
合させて、ＭＦＲ０．５ｇ／１０分、密度０．９２２ｇ
／cm3の直鎖状エチレン・ブテン−１共重合体を得た。
該共重合体に市販のフォスファイト、フォスフォナイ
ト、ステアリン酸亜鉛を第１表に示す配合量で配合した
後、ヘンシェル型ミキサーで混合し、スクリュー直径４
０mmの単軸押出機で溶融混練して樹脂組成物のペレット
を得た。Examples 1 to 5 and Comparative Example 1 (a) Preparation of Resin Composition In the vapor phase process, a so-called Phillips type ionic polymerization catalyst in which chromium oxide and titanium oxide are supported on silicon dioxide in the presence of a trace amount of oxygen is used. Copolymerize ethylene and butene-1, MFR 0.5g / 10min, density 0.922g
A linear ethylene / butene-1 copolymer having a density of / cm 3 was obtained.
Commercially available phosphite, phosphonite and zinc stearate were added to the copolymer in the amounts shown in Table 1, and then mixed with a Henschel mixer to obtain a screw diameter of 4
The pellets of the resin composition were obtained by melt-kneading with a 0 mm single screw extruder.
（ロ）パイプ成形 前記（イ）で得た樹脂組成物ペレットを外径３０mm、内
径２０mmのストレートダイスを有するスクリュー径４０
mmの単軸押出機にて１９０℃の樹脂温度にて、外径２７
mm、内径１５mm、肉厚が６mmの寸法になるように押出し
形成して、真空サイジング装置で外径を制御しながら水
槽でパイプ外面を冷却し単層パイプを得た。(B) Pipe molding The resin composition pellet obtained in (a) above was screw diameter 40 having a straight die with an outer diameter of 30 mm and an inner diameter of 20 mm.
mm single screw extruder, resin temperature of 190 ℃, outer diameter 27
mm, an inner diameter of 15 mm, and a wall thickness of 6 mm were extruded, and the outer surface was cooled in a water tank while controlling the outer diameter with a vacuum sizing device to obtain a single-layer pipe.
このような成形で得られたパイプ内面の皺発生度合を目
視にて観察して判定した。The degree of wrinkling on the inner surface of the pipe obtained by such molding was visually observed and judged.
これらの結果を第１表に示す。The results are shown in Table 1.
比較例２、３ 比較例２、３はパイプの内径を変えて肉厚を変えたこと
以外は比較例１と同様に行った。得られた結果を第２表
に示す。Comparative Examples 2 and 3 Comparative Examples 2 and 3 were performed in the same manner as Comparative Example 1 except that the inner diameter of the pipe was changed to change the wall thickness. The results obtained are shown in Table 2.
比較例４、５ 比較例４、５はエチレン系重合体を変えたこと以外は比
較例１と同様に行ったものである。得られた結果を第２
表に示す。Comparative Examples 4 and 5 Comparative Examples 4 and 5 were carried out in the same manner as Comparative Example 1 except that the ethylene polymer was changed. Second result obtained
Shown in the table.
───────────────────────────────────────────────────── 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 Office reference number FI technical display location B29L 23:22 4F
Claims (5)
が３ｍｍ以上のパイプを成形する方法において、樹脂と
してＭＦＲが０．０５〜２ｇ／１０分、かつ１９０℃に
おける溶融張力が３ｇ以上である直鎖状エチレン重合体
に、フォスファイトおよび／またはフォスフォナイトを
０．０２〜１重量％配合した組成物を用いることを特徴
とする、樹脂パイプの成形法。1. A method of molding a pipe having a wall thickness of 3 mm or more by subjecting a resin to an outer diameter sizing molding method, wherein the resin has an MFR of 0.05 to 2 g / 10 minutes and a melt tension at 190 ° C. of 3 g. A method for molding a resin pipe, characterized in that a composition in which 0.02 to 1% by weight of phosphite and / or phosphonite are mixed with the above linear ethylene polymer is used.
ス型触媒によって得られる直鎖状エチレン単独重合体も
しくは直鎖状エチレン・α−オレフィン共重合体であ
る、請求項１に記載の樹脂パイプの成形法。2. The resin pipe molding according to claim 1, wherein the ethylene polymer is a linear ethylene homopolymer or a linear ethylene / α-olefin copolymer obtained by a chromium oxide type Phillips type catalyst. Law.
３０ｇ／ｃｍ３のエチレン・α−オレフィン共重合体で
ある、請求項１または２に記載の樹脂パイプの成形法。3. The ethylene polymer has a density of 0.915 to 0.9.
The method for molding a resin pipe according to claim 1, which is a 30 g / cm 3 ethylene / α-olefin copolymer.
−ブチルフェニル）フォスファイトである、請求項１〜
３のいずれかに記載の樹脂パイプの成形法。4. Phosphite is tris (2,4-di-t)
-Butylphenyl) phosphite.
4. The method for molding a resin pipe according to any one of 3 above.
ジ−ｔ−ブチルフェニル）−４，４′−ビフェニレン−
ジ−フォスフォナイトである、請求項１〜３のいずれか
に記載の樹脂パイプの成形法。5. The phosphonite is tetrakis (2,4-).
Di-t-butylphenyl) -4,4'-biphenylene-
The method for molding a resin pipe according to any one of claims 1 to 3, which is di-phosphonite.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1270907A JPH0637075B2 (en) | 1989-10-18 | 1989-10-18 | Molding method for resin pipes |
| JP5024330A JPH0739516B2 (en) | 1989-10-18 | 1993-02-12 | Ethylene copolymer composition |
| JP10252959A JPH11159666A (en) | 1989-10-18 | 1998-09-07 | Supply/discharge water pipe |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1270907A JPH0637075B2 (en) | 1989-10-18 | 1989-10-18 | Molding method for resin pipes |
| JP5024330A JPH0739516B2 (en) | 1989-10-18 | 1993-02-12 | Ethylene copolymer composition |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5024330A Division JPH0739516B2 (en) | 1989-10-18 | 1993-02-12 | Ethylene copolymer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03132327A JPH03132327A (en) | 1991-06-05 |
| JPH0637075B2 true JPH0637075B2 (en) | 1994-05-18 |
Family
ID=26361824
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1270907A Expired - Lifetime JPH0637075B2 (en) | 1989-10-18 | 1989-10-18 | Molding method for resin pipes |
| JP5024330A Expired - Lifetime JPH0739516B2 (en) | 1989-10-18 | 1993-02-12 | Ethylene copolymer composition |
| JP10252959A Pending JPH11159666A (en) | 1989-10-18 | 1998-09-07 | Supply/discharge water pipe |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5024330A Expired - Lifetime JPH0739516B2 (en) | 1989-10-18 | 1993-02-12 | Ethylene copolymer composition |
| JP10252959A Pending JPH11159666A (en) | 1989-10-18 | 1998-09-07 | Supply/discharge water pipe |
Country Status (1)
| Country | Link |
|---|---|
| JP (3) | JPH0637075B2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60163947A (en) * | 1984-02-06 | 1985-08-26 | Mitsubishi Petrochem Co Ltd | Polyethylene composition |
| JPH01203787A (en) * | 1988-02-05 | 1989-08-16 | Mitsubishi Petrochem Co Ltd | Supplied/discharged water transporting pipe |
| US4863983A (en) * | 1988-04-15 | 1989-09-05 | Minnesota Mining And Manufacturing Company | Extrudable thermoplastic hydrocarbon polymer composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5127462B2 (en) * | 1973-06-06 | 1976-08-12 | ||
| JPS6456747A (en) * | 1987-08-27 | 1989-03-03 | Mitsubishi Petrochemical Co | Pipe for plumbing system |
| JPS6487989A (en) * | 1987-09-29 | 1989-04-03 | Mitsubishi Petrochemical Co | Plumbing transfer pipe |
| JPS6487990A (en) * | 1987-09-29 | 1989-04-03 | Mitsubishi Petrochemical Co | Plumbing pipe |
| JPH0662817B2 (en) * | 1988-05-06 | 1994-08-17 | ユニオン・カーバイド・コーポレーション | VLDPE base material composition having excellent heat aging resistance |
-
1989
- 1989-10-18 JP JP1270907A patent/JPH0637075B2/en not_active Expired - Lifetime
-
1993
- 1993-02-12 JP JP5024330A patent/JPH0739516B2/en not_active Expired - Lifetime
-
1998
- 1998-09-07 JP JP10252959A patent/JPH11159666A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60163947A (en) * | 1984-02-06 | 1985-08-26 | Mitsubishi Petrochem Co Ltd | Polyethylene composition |
| JPH01203787A (en) * | 1988-02-05 | 1989-08-16 | Mitsubishi Petrochem Co Ltd | Supplied/discharged water transporting pipe |
| US4863983A (en) * | 1988-04-15 | 1989-09-05 | Minnesota Mining And Manufacturing Company | Extrudable thermoplastic hydrocarbon polymer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0739516B2 (en) | 1995-05-01 |
| JPH03132327A (en) | 1991-06-05 |
| JPH0673244A (en) | 1994-03-15 |
| JPH11159666A (en) | 1999-06-15 |
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