WO2004067803A1 - Steel pipe with multilayer protective coating - Google Patents

Steel pipe with multilayer protective coating Download PDF

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Publication number
WO2004067803A1
WO2004067803A1 PCT/JP2003/016888 JP0316888W WO2004067803A1 WO 2004067803 A1 WO2004067803 A1 WO 2004067803A1 JP 0316888 W JP0316888 W JP 0316888W WO 2004067803 A1 WO2004067803 A1 WO 2004067803A1
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Prior art keywords
steel pipe
layer
zinc
multilayer protective
coating layer
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PCT/JP2003/016888
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French (fr)
Japanese (ja)
Inventor
Takanori Kon
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Sanoh Industrial Co., Ltd.
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Publication of WO2004067803A1 publication Critical patent/WO2004067803A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/36—Phosphatising
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L58/00—Protection of pipes or pipe fittings against corrosion or incrustation
    • F16L58/02—Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
    • F16L58/04—Coatings characterised by the materials used
    • F16L58/08—Coatings characterised by the materials used by metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/146—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies to metallic pipes or tubes

Definitions

  • the present invention relates to a multi-layer protective coated steel pipe, and more particularly to a multi-layer protective coated steel pipe used for piping outside a vehicle body that forms a brake system and a lubrication system of an automobile or the like.
  • steel pipes are frequently used for various pipes used in automobiles and the like, for example, brake pipes, fuel pipes, and the like.
  • a multi-layer protective coating layer is formed for the purpose of protection from the like.
  • this multilayer protective coating layer for example, first, a zinc plating layer is formed on the outer peripheral surface of a steel pipe, and a chromate coating layer having a good surface property is formed above the zinc plating layer, and a primer or a primer is interposed as the upper layer.
  • a fluororesin layer or a nylon resin layer is formed, and further, for example, a layer formed by applying a vinyl chloride resin layer as an upper layer, or a layer formed by heat shrinking a polyolefin resin layer, Is formed by extruding a polyethylene resin layer or a polypropylene resin layer.
  • an object of the present invention is to form a multilayer protective coating layer on the surface of a steel pipe without using harmful hexavalent chromium, etc., and to achieve excellent high adhesion and corrosion resistance equivalent to or higher than conventional chromate films. It is an object of the present invention to provide a multi-layer protective coated steel pipe provided with a surface coating layer having a property. Disclosure of the invention
  • the present inventors have conducted intensive research to achieve the above-mentioned object.
  • the zinc phosphate film layer was formed by electrolytic treatment on the zinc plating layer. It has been found that a multi-layer protective coated steel pipe provided with a surface coating layer having excellent adhesion and corrosion resistance equal to or higher than that of a conventional chromatographic coating can be economically provided when formed as a conventional coating. Completed.
  • the present invention provides a zinc-based plating layer formed on the outer peripheral surface of a steel pipe, a zinc phosphate coating layer formed on the zinc-based plating layer, and a synthetic coating formed on the zinc phosphate coating layer.
  • a multilayer protective coated steel pipe having a resin layer.
  • a single-wound steel pipe or a double-wound steel pipe formed from a steel plate can be used as the above-mentioned steel pipe, and it may have a copper plating layer of several m on the outer peripheral surface.
  • ERW steel pipes, drawn steel pipes, and the like can also be used.
  • the outer diameter and thickness of these steel pipes are not particularly limited, but the outer diameter is 4.776 to 20 mm, and the thickness is 0.5 to 1
  • a thin-walled thin steel pipe of mm is preferable for various pipes used in automobiles and the like.
  • Examples of the zinc plating layer formed on the outer peripheral surface of the steel pipe include Zn plating, Zn—Ni alloy plating, and Zn—A1 alloy plating.
  • the same type or different types may be formed as a multi-layer zinc-based plating layer in which two or more types are plated.
  • the zinc A known method such as an electrolysis method and a melting method may be used as a method for forming the system plating layer.
  • the electrolysis method is preferred because a uniform and smooth thin zinc-based plating layer can be economically formed.
  • the thickness of the zinc-based plating layer is preferably 3 to 40 from the viewpoint of corrosion resistance and economy.
  • the zinc phosphate coating layer formed on the zinc plating layer is not particularly limited as long as it contains zinc phosphate as a main component.
  • the thickness of the zinc phosphate coating layer is preferably 0.01 to 2 m. This is because if the thickness of the zinc phosphate coating layer formed on the zinc-based plating layer is less than 0.01 im, the function and effect of improving the corrosion resistance of the steel pipe do not appear. Conversely, if a zinc phosphate coating layer with a thickness of more than 2 is formed, the formed zinc phosphate coating layer may be cracked and peeled off during bending of the steel pipe after surface treatment. This is because there is.
  • the zinc phosphate coating layer having the above film thickness for example, phosphate ions, nitrate ions, and zinc ions are contained, and if necessary, nickel ions, manganese ions, magnesium ions, etc. It is preferably formed by electrolytic treatment using an aqueous solution containing another metal.
  • the current density in this case, especially not limited, short period of time in order to economically form the skin layer of the film thickness control current density 5 to 1 5 AZ dm 2 of within range Is preferred.
  • the steel pipe on which the zinc phosphate coating layer is formed may be subjected to a primer treatment, if desired.
  • This primer treatment has been used as a surface treatment method that can enhance the adhesion to a synthetic resin layer formed later.
  • This is a known treatment, and the specific method thereof is not particularly limited. Usually, a method of immersing a steel pipe in a primer treatment agent, a method of spraying a primer treatment agent onto a steel pipe, or the like is employed.
  • examples of the primer treatment agent include various known organic primer treatment agents such as an epoxy resin dissolved in an organic solvent or a chlorinated rubber, and known various primers such as chromium oxide-colloidal silica. Inorganic primer treatment agents can be used.
  • the zinc phosphate coating layer, or the synthetic resin layer formed as an upper layer of the primer formed on the zinc phosphate coating layer if desired, may be a single layer formed by a method such as coating or extrusion molding, or It can be a multi-layer synthetic resin layer in which the same or different kinds are laminated, and the resin material forming the synthetic resin layer is PVF (polyvinyl fluoride), PVDF (polyvinyldene fluoride), PP ( Synthetic resins such as polypropylene), PE (polyethylene), PA11 (polyamide 11), and PA12 (polyamide 12).
  • PVF polyvinyl fluoride
  • PVDF polyvinyldene fluoride
  • PP Synthetic resins such as polypropylene
  • PE polyethylene
  • PA11 polyamide 11
  • PA12 polyamide 12
  • the above synthetic resin layer is formed for the purpose of countermeasures against impact from hopping stones, countermeasures for interference between pipes that follow complicated paths, or pipes and the vehicle body and other parts, and also measures for heat insulation.
  • the layer thickness is preferably from 10 to 1500 m.
  • PVF polyvinyl fluoride
  • PVDF polyvinyldene fluoride
  • thermoplastic resin such as PP (polypropylene) or PA11 (polyamide 11) is sent in a longitudinal direction using a known extruder.
  • a synthetic resin layer firmly adhered to the surface of the steel pipe can be formed.
  • a steel pipe having a multilayer protective coating layer having excellent corrosion resistance and adhesion can be formed without forming a chromate film using harmful hexavalent chromium or the like.
  • the outer peripheral surface of the steel pipe was subjected to a primer treatment by baking coating, and a fluorine resin layer having a thickness of about 20 im was formed thereon by baking coating to obtain a multilayer protective coated steel pipe.
  • a PP (polypropylene) resin layer having a layer thickness of about 100 m is formed by extrusion molding on the multilayer protective coated steel pipe of Example 1 above, and the outermost synthetic resin layer is made of a different kind of synthetic resin. This was a two-layer multi-layer protective coated steel pipe.
  • Example 4 Instead of the fluororesin layer obtained by baking the multi-layer protective coated steel pipe of Example 1 above, a PA11 (polyamide 11) resin layer having a layer thickness of about 150 m was pressed. A multilayer protective coated steel pipe formed on the primer by extrusion molding. (Example 4)
  • a PP (polypropylene) resin layer having a layer thickness of about 100 im is formed by extrusion molding on the multilayer protective coated steel pipe of Example 3 above, and the outermost synthetic resin layer is made of a different kind of synthetic resin. This was a two-layer multi-layer protective coated steel pipe.
  • Each of the multilayer protective coated steel pipes of the present invention according to Examples 1 to 4 described above is a multilayer protective coated steel pipe having good adhesion between layers and high corrosion resistance, and subjected to various bending processes. It can be suitably used for various pipes used in automobiles and the like, such as brake pipes and fuel pipes. Industrial availability
  • the multilayer protective-coated steel pipe according to the present invention described above can provide a multilayer protective-coated steel pipe having excellent corrosion resistance and adhesion without forming a chromate film using harmful hexavalent chromium.
  • the multilayer protective coated steel pipe according to the present invention for various pipes used in automobiles, etc., the elution of hexavalent chromium, which is an environmentally hazardous substance, into the environment can be significantly reduced, and a great effect on environmental protection Demonstrate.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

A steel pipe with multilayer protective coating wherein in the formation of a multilayer protective coating layer on a steel pipe surface, a surface coating layer exhibiting high adhesion and high corrosion resistance identical with or superior to those of conventional chromate coatings is provided without the use of toxic hexavalent chromium, etc. In particular, a steel pipe with multilayer protective coating comprising a steel pipe and, superimposed on the circumferential surface thereof, a zinc electroplating layer, a 0.01 to 2 μm thick zinc phosphate coating layer formed on the zinc electroplating layer by electrolysis and a synthetic resin layer formed on the zinc phosphate coating layer by coating or extrusion.

Description

明 細 書 多層保護被覆鋼管 技術分野  Description Multi-layer protective coated steel pipe Technical field
本発明は、 多層保護被覆鋼管に関し、 特に自動車等のブレーキ系、 給 油系をなす車体外部の配管用に使用される多層保護被覆鋼管に関するも のである。 背景技術  The present invention relates to a multi-layer protective coated steel pipe, and more particularly to a multi-layer protective coated steel pipe used for piping outside a vehicle body that forms a brake system and a lubrication system of an automobile or the like. Background art
従来より、 自動車等に使用される各種配管、 例えばブレーキ用配管、 フユ一エル用配管等には鋼管が多用され、 これらの鋼管表面には、 自動 車走行中の跳ね石からの保護、 また腐蝕からの保護等を目的として、 多 層の保護被覆層が形成されている。  Conventionally, steel pipes are frequently used for various pipes used in automobiles and the like, for example, brake pipes, fuel pipes, and the like. A multi-layer protective coating layer is formed for the purpose of protection from the like.
この多層の保護被覆層としては、 例えば鋼管の外周表面に、 先ず亜鉛 メツキ層、 その上方に表面性状の良好なクロメート被膜層を形成し、 そ の上層として、 プライマーを介して、 或いはプライマーを介在させるこ となく、 フッ素樹脂層、 或いはナイロン樹脂層を形成し、 さらに、 その 上層として、 例えば塩化ビニール樹脂層を塗布により形成したもの、 或 いはポリオレフイン樹脂層を熱収縮により形成したもの、 更にはポリエ チレン樹脂層、 ポリプロピレン樹脂層を押出し成形により形成したもの がある。  As this multilayer protective coating layer, for example, first, a zinc plating layer is formed on the outer peripheral surface of a steel pipe, and a chromate coating layer having a good surface property is formed above the zinc plating layer, and a primer or a primer is interposed as the upper layer. Without forming, a fluororesin layer or a nylon resin layer is formed, and further, for example, a layer formed by applying a vinyl chloride resin layer as an upper layer, or a layer formed by heat shrinking a polyolefin resin layer, Is formed by extruding a polyethylene resin layer or a polypropylene resin layer.
しかしながら、 近年、 公害問題に対する関心が高まり、 従来のクロメ ート皮膜に用いられる六価クロム、 三価クロム等の有害性、 例えばァレ ルギーや生殖毒性、 発ガン性などがクローズアップされ、 環境保全の観 点から、 六価クロム等を使用しない表面処理の必要性が強く要望される 至った。 However, in recent years, interest in pollution problems has increased, and the harms of hexavalent chromium and trivalent chromium used in conventional chromate films, such as toxicity, reproductive toxicity, and carcinogenicity, have been highlighted. From the viewpoint of conservation, there is a strong demand for surface treatment that does not use hexavalent chromium, etc. Reached.
そこで、 本発明の目的は、 鋼管表面に多層の保護被覆層を形成するに 当たり、 有害な六価クロム等を用いず、 従来のクロメート皮膜と同等以 上の優れた高密着性、 及び高耐蝕性を有する表面皮膜層を備えた多層保 護被覆鋼管を提供することにある。 発明の開示  Therefore, an object of the present invention is to form a multilayer protective coating layer on the surface of a steel pipe without using harmful hexavalent chromium, etc., and to achieve excellent high adhesion and corrosion resistance equivalent to or higher than conventional chromate films. It is an object of the present invention to provide a multi-layer protective coated steel pipe provided with a surface coating layer having a property. Disclosure of the invention
本発明者らは、 上記した目的を達成すべく鋭意研究を進めた結果、 有 害な六価クロム等を使用するクロメート処理に代えて、 リン酸亜鉛皮膜 層を電解処理により亜鉛メツキ層の上層として形成した場合、 従来のク ロメ一卜皮膜と同等以上の優れた高密着性、 及び高耐蝕性を有する表面 皮膜層を備えた多層保護被覆鋼管を経済的に提供できることを見出し、 本発明を完成させた。  The present inventors have conducted intensive research to achieve the above-mentioned object. As a result, instead of chromate treatment using harmful hexavalent chromium or the like, the zinc phosphate film layer was formed by electrolytic treatment on the zinc plating layer. It has been found that a multi-layer protective coated steel pipe provided with a surface coating layer having excellent adhesion and corrosion resistance equal to or higher than that of a conventional chromatographic coating can be economically provided when formed as a conventional coating. Completed.
即ち、 本発明は、 鋼管の外周面上に形成された亜鉛系メツキ層と、 該 亜鉛系メツキ層上に形成されたリン酸亜鉛皮膜層と、 該リン酸亜鉛皮膜 層上に形成された合成樹脂層とを有する多層保護被覆鋼管とした。  That is, the present invention provides a zinc-based plating layer formed on the outer peripheral surface of a steel pipe, a zinc phosphate coating layer formed on the zinc-based plating layer, and a synthetic coating formed on the zinc phosphate coating layer. A multilayer protective coated steel pipe having a resin layer.
ここで、 上記鋼管としては、 鋼板から造管した一重卷鋼管、 或いは二 重巻鋼管が使用でき、 また数^ mの銅メツキ層を外周面に有するもので あっても良い。 また、 その他、 電縫鋼管、 引抜鋼管等も使用でき、 これ らの鋼管の外径及び厚みは、 特には限定されないが、 外径 4 . 7 6〜2 0 mm、 厚さ 0 . 5〜 1 mmの細径薄肉鋼管が、 自動車等に使用される 各種配管には好ましい。  Here, a single-wound steel pipe or a double-wound steel pipe formed from a steel plate can be used as the above-mentioned steel pipe, and it may have a copper plating layer of several m on the outer peripheral surface. In addition, ERW steel pipes, drawn steel pipes, and the like can also be used. The outer diameter and thickness of these steel pipes are not particularly limited, but the outer diameter is 4.776 to 20 mm, and the thickness is 0.5 to 1 A thin-walled thin steel pipe of mm is preferable for various pipes used in automobiles and the like.
また、 上記鋼管の外周面上に形成された亜鉛系メツキ層としては、 例 えば Z nメツキ、 Z n— N i合金メッキ、 Z n— A 1合金メッキ等を挙 げることができ、 これらのメツキ層のうち同種又は異種のものを 2種以 上メツキした複層の亜鉛系メツキ層とすることもできる。 また、 該亜鉛 系メツキ層の形成方法としては、 電解法、 溶融法等の公知の方法によれ ば良いが、 電解法は、 均一且つ平滑な薄い亜鉛系メツキ層を、 経済的に 形成できるために好ましい。 また、 この亜鉛系メツキ層の膜厚は、 耐蝕 性及び経済性等の観点から、 3〜 4 0 とすることが好ましい。 Examples of the zinc plating layer formed on the outer peripheral surface of the steel pipe include Zn plating, Zn—Ni alloy plating, and Zn—A1 alloy plating. Of the above-mentioned plating layers, the same type or different types may be formed as a multi-layer zinc-based plating layer in which two or more types are plated. The zinc A known method such as an electrolysis method and a melting method may be used as a method for forming the system plating layer. The electrolysis method is preferred because a uniform and smooth thin zinc-based plating layer can be economically formed. Further, the thickness of the zinc-based plating layer is preferably 3 to 40 from the viewpoint of corrosion resistance and economy.
上記亜鉛系メツキ層上に形成されたリン酸亜鉛皮膜層としては、 リン 酸亜鉛を主成分として含有しているものであれば、 特には制限されるも のではなく、 より優れた耐蝕性、 密着性等を必要とする場合、 Z n以外 の成分として N i 、 M n、 M g等の中から選ばれる 1種又は 2種以上の 金属を含有したものとすることが好ましい。  The zinc phosphate coating layer formed on the zinc plating layer is not particularly limited as long as it contains zinc phosphate as a main component. When adhesion or the like is required, it is preferable to contain one or more metals selected from Ni, Mn, Mg and the like as components other than Zn.
上記リン酸亜鉛皮膜層の膜厚としては、 0 . 0 1〜 2 mとすること が好ましい。 これは、 亜鉛系メツキ層上に形成されたリン酸亜鉛皮膜層 の膜厚が、 0 . 0 1 i mに満たないものである場合には、 鋼管の耐蝕性 を向上させる作用 ·効果が現れないためであり、 逆に 2 を越える膜 厚のリン酸亜鉛皮膜層を形成した場合には、 表面処理後の鋼管の曲げ加 ェ等に際して、 形成したリン酸亜鉛皮膜層が割れ、 剥離する憂いがある ためである。  The thickness of the zinc phosphate coating layer is preferably 0.01 to 2 m. This is because if the thickness of the zinc phosphate coating layer formed on the zinc-based plating layer is less than 0.01 im, the function and effect of improving the corrosion resistance of the steel pipe do not appear. Conversely, if a zinc phosphate coating layer with a thickness of more than 2 is formed, the formed zinc phosphate coating layer may be cracked and peeled off during bending of the steel pipe after surface treatment. This is because there is.
上記膜厚のリン酸亜鉛皮膜層を均一且つ経済的に形成する方法として は、 例えばリン酸イオン、 硝酸イオン、 亜鉛イオンを含有し、 必要に応 じてニッケルイオン、 マンガンイオン、 マグネシウムイオン等の他の金 属を含有する水溶液を用いた電解処理により形成することが好ましい。 この場合の電流密度には、 特には制限はないが、 短時間で上記膜厚の皮 膜層を経済的に形成するためには、 電流密度を 5〜 1 5 A Z d m2の範 囲内にコントロールすることが好ましい。 As a method for uniformly and economically forming the zinc phosphate coating layer having the above film thickness, for example, phosphate ions, nitrate ions, and zinc ions are contained, and if necessary, nickel ions, manganese ions, magnesium ions, etc. It is preferably formed by electrolytic treatment using an aqueous solution containing another metal. The current density in this case, especially not limited, short period of time in order to economically form the skin layer of the film thickness control current density 5 to 1 5 AZ dm 2 of within range Is preferred.
上記リン酸亜鉛皮膜層が形成された鋼管に対して、 所望によりプライ マー処理を施しても良い。 このプライマー処理は、 後に形成される合成 樹脂層との密着性を高めることができる表面処理方法として、 従来から 知られた処理であり、 その具体的な方法は、 特には限定されないが、 通 常、 プライマー処理剤に鋼管を浸漬する、 或いはプライマー処理剤を鋼 管にスプレーする方法などが採用される。 The steel pipe on which the zinc phosphate coating layer is formed may be subjected to a primer treatment, if desired. This primer treatment has been used as a surface treatment method that can enhance the adhesion to a synthetic resin layer formed later. This is a known treatment, and the specific method thereof is not particularly limited. Usually, a method of immersing a steel pipe in a primer treatment agent, a method of spraying a primer treatment agent onto a steel pipe, or the like is employed.
ここで、 プライマー処理剤としては、 例えば、 エポキシ系樹脂を有機 溶剤に溶解させたものや塩化ゴム系などの公知の各種有機物系プライマ 一処理剤、 及び酸化クロム—コロイダルシリカ系等の公知の各種無機物 系プライマー処理剤を用いることができる。  Here, examples of the primer treatment agent include various known organic primer treatment agents such as an epoxy resin dissolved in an organic solvent or a chlorinated rubber, and known various primers such as chromium oxide-colloidal silica. Inorganic primer treatment agents can be used.
上記リン酸亜鉛皮膜層、 或いは所望によりリン酸亜鉛皮膜層上に形成 された上記プライマーの上層として形成された合成樹脂層としては、 塗 装、 押出し成形等の方法で形成された単層、 或いは同種又は異種のもの を積層した複層の合成樹脂層とすることができ、 該合成樹脂層を形成す る樹脂材料としては、 P V F (ポリフッ化ビニル） 、 P V D F (ポリフ ッ化ビニルデン） 、 P P (ポリプロピレン） 、 P E (ポリエチレン） 、 P A 1 1 (ポリアミ ド 1 1 ) 、 P A 1 2 (ポリアミド 1 2 ) 等の合成樹 脂が挙げられる。  The zinc phosphate coating layer, or the synthetic resin layer formed as an upper layer of the primer formed on the zinc phosphate coating layer if desired, may be a single layer formed by a method such as coating or extrusion molding, or It can be a multi-layer synthetic resin layer in which the same or different kinds are laminated, and the resin material forming the synthetic resin layer is PVF (polyvinyl fluoride), PVDF (polyvinyldene fluoride), PP ( Synthetic resins such as polypropylene), PE (polyethylene), PA11 (polyamide 11), and PA12 (polyamide 12).
上記合成樹脂層は、 跳ね石からの衝撃対策、 複雑な経路をたどる配管 同士、 或いは配管と車両本体や他部品との干渉対策、 更には断熱対策等 も目的として形成されたものであることから、 その層厚は、 1 0〜1 5 0 0 mとすることが好ましい。  The above synthetic resin layer is formed for the purpose of countermeasures against impact from hopping stones, countermeasures for interference between pipes that follow complicated paths, or pipes and the vehicle body and other parts, and also measures for heat insulation. The layer thickness is preferably from 10 to 1500 m.
上記層厚の合成樹脂層を塗装により形成する方法としは、 例えば P V F (ポリフッ化ビニル） 、 P V D F (ポリフッ化ビニルデン） 等をジェ チルフタレートのような溶剤中に分散させ、 その中に鋼管を浸漬して塗 布し、 その後加熱処理する焼付け塗装により行うことができる。  As a method of forming a synthetic resin layer having the above-mentioned thickness by painting, for example, PVF (polyvinyl fluoride), PVDF (polyvinyldene fluoride), etc. are dispersed in a solvent such as methyl phthalate, and a steel pipe is immersed therein. Then, it can be applied by baking coating, which is followed by heat treatment.
また、 合成樹脂層を押出し成形により形成する方法としは、 例えば P P (ポリプロピレン） 、 P A 1 1 (ポリアミド 1 1 ) 等の熱可塑性樹脂 を、 公知の押出機を用いて長手方向に送られてくる鋼管の外周表面上に 筒状に押し出し、 該押し出された合成樹脂を鋼管上において冷却させる ことにより、 鋼管表面上に強固に密着した合成樹脂層を形成することが できる。 In addition, as a method of forming a synthetic resin layer by extrusion molding, for example, a thermoplastic resin such as PP (polypropylene) or PA11 (polyamide 11) is sent in a longitudinal direction using a known extruder. On the outer surface of the steel pipe By extruding the synthetic resin into a cylindrical shape and cooling the extruded synthetic resin on the steel pipe, a synthetic resin layer firmly adhered to the surface of the steel pipe can be formed.
上記した本発明にかかる多層保護被覆鋼管によれば、 有害な六価ク口 ム等を使用したクロメート皮膜を形成することなく、 耐蝕性及び密着性 の優れた多層の保護被覆層を有する鋼管を提供できる。 発明を実施するための最良の形態  According to the above-mentioned multilayer protective coated steel pipe according to the present invention, a steel pipe having a multilayer protective coating layer having excellent corrosion resistance and adhesion can be formed without forming a chromate film using harmful hexavalent chromium or the like. Can be provided. BEST MODE FOR CARRYING OUT THE INVENTION
以下、 上記した本発明に係る多層保護被覆鋼管の実施例を記載するが 、 本発明は、 何ら下記の実施例に限定されるものではない。  Hereinafter, examples of the above-described multilayer protective coated steel pipe according to the present invention will be described, but the present invention is not limited to the following examples.
〔実施例 1〕  (Example 1)
外径 6 . 3 5 mm, 厚さ 0 . 7 mmの一重巻鋼管、 或いは外径 4 . 7 6 mm、 厚さ 0 . 7 mmの二重巻鋼管の外周面に、 先ず、 膜厚 2 5 m 程度の電気亜鉛メツキ層を形成し、 その上方に、 膜厚 0 . 程度の 電解リン酸亜鉛皮膜層を形成した。  The outer surface of a single-walled steel pipe with an outer diameter of 6.35 mm and a thickness of 0.7 mm, or a double-walled steel pipe with an outer diameter of 4.76 mm and a thickness of 0.7 mm, first has a film thickness of 25 An approximately 0.5 m-thick electro-zinc plating layer was formed, and an electrolytic zinc phosphate coating layer having a thickness of approximately 0 was formed above the electro-zinc plating layer.
続いて、 上記鋼管の外周面に、 焼付け塗装によるプライマー処理を行 レ その上方に、 層厚 2 0 i m程度のフッ素樹脂層を焼付け塗装により 形成し、 多層保護被覆鋼管とした。  Subsequently, the outer peripheral surface of the steel pipe was subjected to a primer treatment by baking coating, and a fluorine resin layer having a thickness of about 20 im was formed thereon by baking coating to obtain a multilayer protective coated steel pipe.
〔実施例 2〕  (Example 2)
上記実施例 1の多層保護被覆鋼管の上方に、 更に層厚 1 0 0 0 m程 度の P P (ポリプロピレン） 樹脂層を押出し成形により形成し、 最外層 の合成樹脂層が、 異種の合成樹脂から成る二層の多層保護被覆鋼管とし た。  A PP (polypropylene) resin layer having a layer thickness of about 100 m is formed by extrusion molding on the multilayer protective coated steel pipe of Example 1 above, and the outermost synthetic resin layer is made of a different kind of synthetic resin. This was a two-layer multi-layer protective coated steel pipe.
〔実施例 3〕  (Example 3)
上記実施例 1の多層保護被覆鋼管の焼付け塗装によるフッ素樹脂層に 代えて、 層厚 1 5 0 m程度の P A 1 1 (ポリアミド 1 1 ) 樹脂層を押 出し成形によりプライマー上に形成した多層保護被覆鋼管とした。 〔実施例 4〕 Instead of the fluororesin layer obtained by baking the multi-layer protective coated steel pipe of Example 1 above, a PA11 (polyamide 11) resin layer having a layer thickness of about 150 m was pressed. A multilayer protective coated steel pipe formed on the primer by extrusion molding. (Example 4)
上記実施例 3の多層保護被覆鋼管の上方に、 更に層厚 1 0 0 0 i m程 度の P P (ポリプロピレン） 樹脂層を押出し成形により形成し、 最外層 の合成樹脂層が、 異種の合成樹脂から成る二層の多層保護被覆鋼管とし た。  A PP (polypropylene) resin layer having a layer thickness of about 100 im is formed by extrusion molding on the multilayer protective coated steel pipe of Example 3 above, and the outermost synthetic resin layer is made of a different kind of synthetic resin. This was a two-layer multi-layer protective coated steel pipe.
〔実施例 1乃至実施例 4の効果〕  [Effects of Embodiments 1 to 4]
上記した実施例 1乃至実施例 4に係る本発明の多層保護被覆鋼管は、 いずれも各層間の密着性が良好で、 しかも耐蝕性の高い多層保護被覆鋼 管となり、 種々の曲げ加工が施される自動車等に使用される各種配管、 例えばブレーキ用配管、 フューエル用配管等に好適に使用できるもので めった。 産業の利用可能性  Each of the multilayer protective coated steel pipes of the present invention according to Examples 1 to 4 described above is a multilayer protective coated steel pipe having good adhesion between layers and high corrosion resistance, and subjected to various bending processes. It can be suitably used for various pipes used in automobiles and the like, such as brake pipes and fuel pipes. Industrial availability
以上、 説明した本発明に係る多層保護被覆鋼管は、 有害な六価クロム 等を使用したクロメート皮膜を形成することなく、 優れた耐蝕性及び密 着性を有する多層保護被覆鋼管を提供でき、 例えば、 自動車等に使用さ れる各種配管に本発明に係る多層保護被覆鋼管を用いることにより、 環 境負荷物質である六価クロムの環境への溶出を大幅に低減でき、 環境保 全に絶大な効果を発揮する。  The multilayer protective-coated steel pipe according to the present invention described above can provide a multilayer protective-coated steel pipe having excellent corrosion resistance and adhesion without forming a chromate film using harmful hexavalent chromium. By using the multilayer protective coated steel pipe according to the present invention for various pipes used in automobiles, etc., the elution of hexavalent chromium, which is an environmentally hazardous substance, into the environment can be significantly reduced, and a great effect on environmental protection Demonstrate.

Claims

請求の範囲 The scope of the claims
1 . 鋼管の外周面上に形成された亜鉛系メツキ層と、 該亜鉛系メツキ層 上に形成されたリン酸亜鉛皮膜層と、 該リン酸亜鉛皮膜層上に形成され た合成樹脂層とを有することを特徴とする多層保護被覆鋼管。 1. A zinc-based plating layer formed on the outer peripheral surface of the steel pipe, a zinc phosphate coating layer formed on the zinc-based plating layer, and a synthetic resin layer formed on the zinc phosphate coating layer. A multilayer protective coated steel pipe characterized by having:
2 . 上記リン酸亜鉛皮膜層が、 電解処理により形成された膜厚が 0 . 0 1〜 2 のリン酸亜鉛皮膜層であることを特徴とする、 請求の範囲第 1項記載の多層保護被覆鋼管。  2. The multilayer protective coating according to claim 1, wherein said zinc phosphate coating layer is a zinc phosphate coating layer having a thickness of 0.01 to 2 formed by electrolytic treatment. Steel pipe.
PCT/JP2003/016888 2003-01-29 2003-12-26 Steel pipe with multilayer protective coating WO2004067803A1 (en)

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JPWO2007052683A1 (en) * 2005-11-01 2009-04-30 三桜工業株式会社 Steel pipe for automobile piping
JP5225662B2 (en) * 2007-11-21 2013-07-03 三桜工業株式会社 Steel pipe for vehicle piping
CN107208828B (en) * 2015-02-13 2020-01-14 三樱工业株式会社 Coated metal pipe for piping of vehicle and method for manufacturing same
EP3940106A1 (en) * 2020-07-15 2022-01-19 TI Automotive Engineering Centre (Heidelberg) GmbH Pipeline and method for coating a pipeline

Citations (2)

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Publication number Priority date Publication date Assignee Title
JPH03126893A (en) * 1989-10-12 1991-05-30 Kawasaki Steel Corp Production of galvanized steel sheet having superior chemical convertibility
WO2001053566A1 (en) * 2000-01-19 2001-07-26 Itt Manufacturing Enterprises, Inc. Corrosion resistant metal tube and process for making the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03126893A (en) * 1989-10-12 1991-05-30 Kawasaki Steel Corp Production of galvanized steel sheet having superior chemical convertibility
WO2001053566A1 (en) * 2000-01-19 2001-07-26 Itt Manufacturing Enterprises, Inc. Corrosion resistant metal tube and process for making the same

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