JPS601176B2 - Manufacturing method for anti-corrosion metal pipes - Google Patents
Manufacturing method for anti-corrosion metal pipesInfo
- Publication number
- JPS601176B2 JPS601176B2 JP54104276A JP10427679A JPS601176B2 JP S601176 B2 JPS601176 B2 JP S601176B2 JP 54104276 A JP54104276 A JP 54104276A JP 10427679 A JP10427679 A JP 10427679A JP S601176 B2 JPS601176 B2 JP S601176B2
- Authority
- JP
- Japan
- Prior art keywords
- silyl
- corrosion
- modified polymer
- manufacturing
- metal pipe
- 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
Links
- 238000005260 corrosion Methods 0.000 title claims description 21
- 239000002184 metal Substances 0.000 title claims description 21
- 229910052751 metal Inorganic materials 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000003707 silyl modified polymer Substances 0.000 claims description 17
- 229910000831 Steel Inorganic materials 0.000 claims description 13
- 239000010959 steel Substances 0.000 claims description 13
- 230000007797 corrosion Effects 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 238000007747 plating Methods 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 18
- 239000000126 substance Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Processes Specially Adapted For Manufacturing Cables (AREA)
- Laminated Bodies (AREA)
Description
【発明の詳細な説明】
本発明は、管表面へ防食被覆層を形成させた防食金属管
の製法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a corrosion-resistant metal pipe in which a corrosion-resistant coating layer is formed on the surface of the pipe.
従来から、上下水道や化学工場等の液体輸送用Ｚの金属
管として、機械的強度の大きい鋼管が知られている。BACKGROUND ART Steel pipes with high mechanical strength have been known as metal pipes for transporting liquids in water and sewage facilities, chemical factories, and the like.
しかしながら、このような鋼管も塩分や酸に対しては抵
抗性に乏しく長年使用した場合には相当腐食されるとい
う欠点があった。However, such steel pipes also have the disadvantage that they have poor resistance to salt and acids and are subject to considerable corrosion when used for many years.
このため鋼管の内外表面に合成樹脂、特に耐酸、耐薬品
性に優れた塩化ビニル樹脂やポリエチレンによる防食被
覆層を形成することが行なわれていた。しかしながら、
ポリエチレンは、無極性のポリマーであるため金属との
接着性に乏しく、従来接着剤を使用して密着させていた
が、適当な接着剤がないため、防食層に損傷を受けたよ
うな場合、水が防食層の裏側へ浸透して短期間で防食層
が剥離してしまうと共に使用時の熱的条件で接着剤が劣
化してしまい防食層が剥離してしまうという難点があっ
た。For this reason, anti-corrosion coating layers of synthetic resins, particularly vinyl chloride resins and polyethylene, which have excellent acid and chemical resistance, have been formed on the inner and outer surfaces of steel pipes. however,
Since polyethylene is a non-polar polymer, it has poor adhesion to metals, and conventionally adhesives have been used to bond them, but as there is no suitable adhesive, if the anti-corrosion layer is damaged, Water penetrates into the back side of the anti-corrosion layer and the anti-corrosion layer peels off in a short period of time, and the adhesive deteriorates due to the thermal conditions during use, causing the anti-corrosion layer to peel off.
また、かかる防食層に使用されるポリエチレンは未架橋
のポリエチレンであるため、耐油性や耐薬品性に乏しく
、このような用途へは使用できないという難点もあった
。Furthermore, since the polyethylene used in such anti-corrosion layers is uncrosslinked polyethylene, it has poor oil resistance and chemical resistance, and therefore cannot be used for such purposes.
更に、ポリエチレンに極性基であるシリル基を導入して
成るシリル変性ポリマーを押出被覆することも考えられ
るが、かかる方法によっても必ずしも充分な剥離強度が
得られていない。Furthermore, extrusion coating with a silyl-modified polymer obtained by introducing a silyl group, which is a polar group, into polyethylene may be considered, but such a method does not necessarily provide sufficient peel strength.
本発明者等は、かかる難点を解消すべく鋭意研究をした
結果金属管に錫その他の錫系めつきを施して、その上へ
シリル変性ポリマーを被覆して架橋すると、錫とシリル
変性ポリマーが強固に接着することを見出した。The inventors of the present invention have conducted extensive research to solve this problem. As a result, the metal tube is plated with tin or other tin-based plating, and a silyl-modified polymer is coated thereon for cross-linking. It was discovered that it adheres strongly.
本発明は、かかる知見に塞いてなされたもので、金属管
表面へ、錫系めつき層を形成し、前記錫系めつき層へ、
未架橋のシリル変性ポリマーを熔融状態にして被覆する
と共に、前記シリル変性ポリマーを水と反応させて架橋
することを特徴とする防食金属管の製法を提供すること
を目的とする。The present invention was made based on this knowledge, and includes forming a tin-based plating layer on the surface of a metal tube, and forming a tin-based plating layer on the tin-based plating layer.
It is an object of the present invention to provide a method for manufacturing a corrosion-resistant metal pipe, characterized in that an uncrosslinked silyl-modified polymer is coated in a molten state, and the silyl-modified polymer is cross-linked by reacting with water.
本発明に使用する未架橋のシリル変性ポリマ−は、特公
昭４８−１７１１号公報に記載されているように、例え
ば、高密度、中密度あるいは低密度のポリエチレンまた
はエチレンを主体とするエチレン共重合体と、ピニルト
リメトキシシラン（ＶＴＭＯＳ）のような加水分解可能
な有機基とビニル基とを有するシランモノマーと、ジグ
ミルパーオキサィド（ＤＣＰ）のような有機過酸化物と
を押出機のホッパ一に供給して加熱反応することにより
得られる。The uncrosslinked silyl-modified polymer used in the present invention is, for example, a high-density, medium-density or low-density polyethylene or an ethylene copolymer mainly composed of ethylene, as described in Japanese Patent Publication No. 48-1711. A silane monomer having a hydrolyzable organic group and a vinyl group, such as pinyltrimethoxysilane (VTMOS), and an organic peroxide, such as digumyl peroxide (DCP), are combined in an extruder. It is obtained by feeding it into a hopper and subjecting it to a heating reaction.
このようにして得られたシリル変性ポリマーは、ジブチ
ル錫ジラウレート（ＤＢＴＤＬ）のようなシラノール縮
合触媒の存在下で、常温でも水分と反応して架橋するが
、加熱水蒸気雰囲気下または温水中で急速に架橋する。The silyl-modified polymer thus obtained reacts with moisture and crosslinks even at room temperature in the presence of a silanol condensation catalyst such as dibutyltin dilaurate (DBTDL), but rapidly under a heated steam atmosphere or in hot water. crosslink.
而して、このシリル変性ポリマーは、分子の主鎖へシリ
ル基が結合する結果接着性が非常に改善されており「こ
れを錫めつき面へ融着させた場合優れた接着性を発揮す
る。なお、シラノール縮合触媒は、マスターバッチにし
て、シリル変性ポリマーと混合して押出してもよく、ま
たシリル変性ポリマーを金属管表面へ融着させた後その
表面へ塗布するようにしてもよい。This silyl-modified polymer has greatly improved adhesion as a result of the silyl group bonding to the main chain of the molecule, and ``when it is fused to a tin-plated surface, it exhibits excellent adhesion. The silanol condensation catalyst may be made into a masterbatch, mixed with the silyl-modified polymer and extruded, or the silyl-modified polymer may be fused to the surface of the metal tube and then applied to the surface.
更に、必要に応じて、触媒を含む全成分を混合して押出
機のホッパ−へ供給し、押出機中でシリル変性しながら
押出すようにしてもよい。次にＬ図面に基づき本発明の
一実施例を詳述する。第１図において、表面へ防食層を
形成すべき金属管も例えば鋼管１は、サンドブラスト加
工、アルカリ脱脂等の機械的、化学的な方法で鋼管表面
の酸化物「油脂などを除去した上で、めつき糟に子入れ
られて、表面に錫めつき層２を形成する。Furthermore, if necessary, all components including the catalyst may be mixed and supplied to the hopper of an extruder, and extruded while being silyl-modified in the extruder. Next, one embodiment of the present invention will be described in detail based on drawing L. In FIG. 1, a metal pipe on which an anti-corrosion layer is to be formed is, for example, a steel pipe 1. After removing oxides, oils, etc. from the surface of the steel pipe by mechanical or chemical methods such as sandblasting or alkaline degreasing, They are placed in a plating pot to form a tinned layer 2 on the surface.
続いて、錫めつきを施された鋼管１の錫めつき層２表面
に、押出機より押出された未架橋のシリル変性ポリマー
を適当な流動性を持たせて押出被覆する。適当な流動性
を持たせるためには、高密度のポリエチレンを使用した
場合には１８０〜２５０℃、低密度のポリエチレンを使
用した場合には、１５０〜２２０ｑｏの温度であるのが
よい。シリル変性ポリマーを被覆された鋼管は、速やか
に、温水中又は水蒸気雰囲気中で水架橋されて、架橋シ
リル変性ポリマーから成る防食層３を形成させて、防食
鋼管が製造される。なお、鋼管が大口径である場合は、
Ｔダィでテープ状に押出されたシリル変性ポリマーを巻
回した後に、加熱加圧の下で水架橋して被覆するとよい
。Subsequently, the surface of the tin-plated layer 2 of the tin-plated steel pipe 1 is coated with an uncrosslinked silyl-modified polymer extruded from an extruder with appropriate fluidity. In order to have appropriate fluidity, the temperature is preferably 180 to 250°C when high density polyethylene is used, and 150 to 220 qo when low density polyethylene is used. The steel pipe coated with the silyl-modified polymer is immediately water-crosslinked in hot water or in a steam atmosphere to form a corrosion-protective layer 3 made of the cross-linked silyl-modified polymer, thereby producing a corrosion-resistant steel pipe. In addition, if the steel pipe has a large diameter,
It is preferable to wind the silyl-modified polymer extruded into a tape shape using a T-die, and then cross-link it with water under heat and pressure for coating.
而して、架橋後冷却された防食層は、線膨張の体積収縮
のため、鋼管を締め付けるように収縮して鋼管と密着す
る。The anticorrosive layer cooled after crosslinking contracts to tighten the steel pipe due to volumetric contraction due to linear expansion, and comes into close contact with the steel pipe.
なお、冷却過程で更に加圧して密着を促すようにしても
よい。上記のように製造された防食金属管の防食層３を
第２図に示すように１伽幅で長さ方向に切れ目を入れ、
長さ方向と直角の方向（図の矢印の方向）にショッパ一
引張試験機により引張り剥離強度を試験した。Note that pressure may be further applied during the cooling process to promote close contact. The anti-corrosion layer 3 of the anti-corrosion metal pipe manufactured as described above is cut in the length direction by 1 tog width as shown in Fig. 2.
The tensile peel strength was tested using a Schopper tensile tester in the direction perpendicular to the length direction (in the direction of the arrow in the figure).
結果を第１表に示す。第１表
（比較例は、鋼管に錫めつき層を形成させずに、シリル
変性ポリマーを被覆したものである。The results are shown in Table 1. Table 1 (Comparative example is a steel pipe coated with a silyl-modified polymer without forming a tinned layer.
）なお、使用したシリル変性ポリエチレンおよび触媒マ
スターバッチは次の配合により製造したものである。) The silyl-modified polyethylene and catalyst masterbatch used were manufactured using the following formulation.
なお以上の実施例では、金属管表面として鋼管の外面に
防食層を形成する場合について説明したが、本発明にお
ける金属管表面はこれらに限られるものでなく、薬液輸
送用の金属管にあっては、薬液との接触面となる金属管
内面にも同様の防食層を形成する。In addition, in the above embodiment, a case was explained in which an anticorrosion layer is formed on the outer surface of the steel pipe as the metal pipe surface, but the metal pipe surface in the present invention is not limited to this, and can be applied to a metal pipe for transporting chemical liquids. A similar anti-corrosion layer is also formed on the inner surface of the metal tube, which is the surface that comes into contact with the chemical solution.
以上説明したように本発明によれば、耐酸性、耐薬品性
の良好な剥離強度の大なる防食金属管を提供することが
できる。As explained above, according to the present invention, it is possible to provide a corrosion-resistant metal pipe with good acid resistance, chemical resistance, and high peel strength.
第１図は「本発明による防食金属管の断面を示す説明図
、第２図は剥離強度試験の説明図である。
１・・…・鋼管、２……錫めつき層、３…・・・防食層
。
孝１図
多２図Fig. 1 is an explanatory diagram showing a cross section of a corrosion-resistant metal pipe according to the present invention, and Fig. 2 is an explanatory diagram of a peel strength test. 1... Steel pipe, 2... Tin plating layer, 3...・Anti-corrosion layer.
Claims (1)
つき層へ、未架橋のシリル変性ポリマーを溶融状態にし
て被覆すると共に、前記シリル変性ポリマーを水と反応
させて架橋することを特徴とする防食金属管の製法。 ２ 金属管は鋼管である特許請求の範囲第１項記載の防
食金属管の製法。 ３ シリル変性ポリマーは、シリル変性ポリエチレンで
ある特許請求の範囲第１項又は第２項記載の防食金属管
の製法。[Scope of Claims] 1. Forming a tin-based plating layer on the surface of a metal tube, coating the tin-based plating layer with an uncrosslinked silyl-modified polymer in a molten state, and immersing the silyl-modified polymer in water. A method for manufacturing a corrosion-resistant metal pipe characterized by crosslinking by reacting with. 2. The method for manufacturing a corrosion-resistant metal pipe according to claim 1, wherein the metal pipe is a steel pipe. 3. The method for producing a corrosion-resistant metal pipe according to claim 1 or 2, wherein the silyl-modified polymer is silyl-modified polyethylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP54104276A JPS601176B2 (en) | 1979-08-15 | 1979-08-15 | Manufacturing method for anti-corrosion metal pipes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP54104276A JPS601176B2 (en) | 1979-08-15 | 1979-08-15 | Manufacturing method for anti-corrosion metal pipes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5627339A JPS5627339A (en) | 1981-03-17 |
| JPS601176B2 true JPS601176B2 (en) | 1985-01-12 |
Family
ID=14376395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP54104276A Expired JPS601176B2 (en) | 1979-08-15 | 1979-08-15 | Manufacturing method for anti-corrosion metal pipes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS601176B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03207646A (en) * | 1990-01-09 | 1991-09-10 | Sekisui Chem Co Ltd | Manufacture of polyethylene covered metallic body |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5240571A (en) * | 1975-09-26 | 1977-03-29 | British Insulated Callenders | Method of producing extruded product and insulated electric cable produced thereby |
| JPS53120638A (en) * | 1977-03-31 | 1978-10-21 | Sumitomo Metal Ind Ltd | Outside plating method for steel tube |
-
1979
- 1979-08-15 JP JP54104276A patent/JPS601176B2/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5240571A (en) * | 1975-09-26 | 1977-03-29 | British Insulated Callenders | Method of producing extruded product and insulated electric cable produced thereby |
| JPS53120638A (en) * | 1977-03-31 | 1978-10-21 | Sumitomo Metal Ind Ltd | Outside plating method for steel tube |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5627339A (en) | 1981-03-17 |
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