JP2007100961A - Foaming polyethylene coated metallic pipe - Google Patents
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本発明は、発泡ポリエチレン被覆金属管に関する。更に詳しくは、金属腐蝕を起こさず、かつ断熱性、衝撃吸収性に富んだ金属管被覆用発泡性ポリエチレン樹脂組成物を用いて得られる発泡ポリエチレン被覆金属管に関する。 The present invention relates to a foamed polyethylene-coated metal tube. More specifically, the present invention relates to a foamed polyethylene-coated metal tube that is obtained by using a foamable polyethylene resin composition for coating a metal tube that does not cause metal corrosion and is excellent in heat insulation and shock absorption.
鉄、ステンレス、銅、亜鉛、アルミニウム、チタン、錫、銀等の金属からなる金属管の表面にポリエチレン発泡体を被覆して製造される発泡ポリエチレン被覆金属管は、断熱性と衝撃吸収性に富むため、水、湯、温泉水、各種化学物質等の輸送用や、電線、光ファイバー等の保護用として数多く用いられている。これらの発泡ポリエチレン被覆金属管は、通常次のような方法で製造される。すなわち、１つの方法は、まずポリエチレン系樹脂と化学発泡剤を該樹脂の融点以上でかつ化学発泡剤の分解温度以下の温度下、バンバリーミキサー、押出機等でもって加熱混練し、化学発泡剤を該樹脂中に均一に分散させて発泡性ポリエチレン樹脂組成物を調製し、次いでこれを予熱された金属管の表面に押出機より該化学発泡剤の分解温度を超える温度（通常は１３５〜２００℃）で押出被覆し、金属管の表面にポリエチレン発泡体を形成させる。別の方法は、まず上記発泡性ポリエチレン樹脂組成物を押出機より上記化学発泡剤の分解温度を超える温度で発泡シートとして押出し、次いで該発泡シートを金属管の外周とほぼ同じ幅に切断したのち円筒状に丸めて金属管に被覆し、その両側面を対峠させた状態で熱融着させるか、又は熱融着させない場合は、外部を粘着テープや針金で巻きつけるかして、ほどけないような状態にし、金属管の表面にポリエチレン発泡体を形成させる。 A foamed polyethylene-coated metal tube manufactured by coating a polyethylene foam on the surface of a metal tube made of metal such as iron, stainless steel, copper, zinc, aluminum, titanium, tin, silver, etc. is rich in heat insulation and shock absorption. Therefore, it is widely used for transporting water, hot water, hot spring water, various chemical substances, etc., and for protecting electric wires, optical fibers and the like. These foamed polyethylene-coated metal tubes are usually produced by the following method. That is, one method is to first heat-knead a polyethylene resin and a chemical foaming agent with a Banbury mixer, an extruder, etc. at a temperature not lower than the melting point of the resin and not higher than the decomposition temperature of the chemical foaming agent. A foamable polyethylene resin composition is prepared by uniformly dispersing in the resin, and then the temperature is higher than the decomposition temperature of the chemical foaming agent from an extruder on the surface of a preheated metal tube (usually 135 to 200 ° C). ) To form a polyethylene foam on the surface of the metal tube. Another method is to first extrude the expandable polyethylene resin composition from an extruder as a foam sheet at a temperature exceeding the decomposition temperature of the chemical foaming agent, and then cut the foam sheet to approximately the same width as the outer periphery of the metal tube. If it is rolled into a cylindrical shape and covered with a metal tube and both sides are opposed to each other, or heat fusion is not performed, the outside cannot be unwound by wrapping with adhesive tape or wire. In such a state, a polyethylene foam is formed on the surface of the metal tube.
しかしながら、近年になって、こうした発泡ポリエチレン被覆金属管の表面が腐食して金属管に穴があき、その結果として、内部の流体が漏れたり、内部の流体が汚染されたり、金属管自体が折れたりする等の事故が発生し、問題となっている。現在のところ、この原因としては、化学発泡剤中に残存するハロゲン又はハロゲン含有化合物からなる不純物が金属腐蝕を起こさせているものと考えられる。したがって、上述した従来の発泡ポリエチレン被覆金属管のもつ問題点を解消するため、金属腐蝕を起こさず、かつ断熱性、衝撃吸収性に富んだ金属管被覆用発泡性ポリエチレン樹脂組成物及びこれを用いて得られる発泡ポリエチレン被覆金属管の出現が望まれている。 However, in recent years, the surface of such foamed polyethylene-coated metal tubes corroded and the metal tubes are perforated. As a result, the internal fluid leaks, the internal fluid is contaminated, or the metal tube itself is broken. Accidents such as accidents occur, which is a problem. At present, it is considered that this is caused by metal corrosion caused by halogens or halogen-containing compounds remaining in the chemical foaming agent. Therefore, in order to eliminate the problems of the above-mentioned conventional foamed polyethylene-coated metal pipes, a foamable polyethylene resin composition for coating metal pipes that does not cause metal corrosion and has excellent heat insulation properties and shock absorption properties, and the use thereof are used. The appearance of a foamed polyethylene-coated metal tube obtained in this way is desired.
本発明の目的は、金属腐蝕を起こさず、かつ断熱性、衝撃吸収性に富んだ金属管被覆用発泡性ポリエチレン樹脂組成物を用いて得られる発泡ポリエチレン被覆金属管を提供することにある。 An object of the present invention is to provide a foamed polyethylene-coated metal tube obtained by using a foamable polyethylene resin composition for coating a metal tube, which does not cause metal corrosion and is excellent in heat insulation and shock absorption.
本発明者らは、前記した従来の発泡ポリエチレン被覆金属管のもつ問題点を克服するために鋭意研究した結果、一定量の不純物捕集剤を配合した金属管被覆用発泡性ポリエチレン樹脂組成物を用いて得られる発泡ポリエチレン被覆金属管により、上記目的を達成できることを見いだした。
本発明は、これらの知見に基づいて完成に至ったものである。
As a result of diligent research to overcome the problems of the above-described conventional foamed polyethylene-coated metal pipes, the present inventors have obtained a foamable polyethylene resin composition for coating metal pipes that contains a certain amount of an impurity scavenger. It has been found that the above object can be achieved by using a foamed polyethylene-coated metal tube obtained by use.
The present invention has been completed based on these findings.
本発明によれば、ポリエチレン系樹脂１００重量部に、ハロゲン及びハロゲン系化合物からなる残留の不純物を含む化学発泡剤０．１〜１０重量部と、ハイドロタルサイト、ステアリン酸カルシウム、酸化カリウム、水酸化マグネシウム、水酸化カルシウム、有機スズ化合物及びリン酸カルシウムからなる群より選ばれる少なくとも１種の化合物０．０１〜１重量部とを配合させ、上記残留の不純物を捕集することにより製造された金属管被覆用発泡性ポリエチレン樹脂組成物を、予熱された金属管の表面に押出機により押出し被覆し製造されることを特徴とする金属腐食を起こさず、断熱性、衝撃吸収性に富んだ発泡ポリエチレン被覆金属管が提供される。 According to the present invention, 0.1 to 10 parts by weight of a chemical foaming agent containing residual impurities composed of halogen and a halogen compound, 100 parts by weight of a polyethylene resin, hydrotalcite, calcium stearate, potassium oxide, hydroxylation Metal tube coating produced by blending 0.01 to 1 part by weight of at least one compound selected from the group consisting of magnesium, calcium hydroxide, organotin compounds and calcium phosphate, and collecting the remaining impurities A foamed polyethylene-coated metal with excellent heat insulation and shock absorption characteristics, which is produced by extruding and coating a foamable polyethylene resin composition for the surface of a preheated metal tube with an extruder. A tube is provided.
また、本発明によれば、ポリエチレン系樹脂１００重量部に、ハロゲン及びハロゲン系化合物からなる残留の不純物を含む化学発泡剤０．１〜１０重量部と、ハイドロタルサイト、ステアリン酸カルシウム、酸化カリウム、水酸化マグネシウム、水酸化カルシウム、有機スズ化合物及びリン酸カルシウムからなる群より選ばれる少なくとも１種の化合物０．０１〜１重量部とを配合させ、上記残留の不純物を捕集することにより製造された金属管被覆用発泡性ポリエチレン樹脂組成物を、押出機よりシート状に押出して発泡シートとし、該発泡シートを金属管の外周と同じ長さに切断したのち円筒状に丸めて金属管に被覆し製造されることを特徴とする金属腐食を起こさず、断熱性、衝撃吸収性に富んだ発泡ポリエチレン被覆金属管が提供される。 Further, according to the present invention, 0.1 to 10 parts by weight of a chemical foaming agent containing residual impurities consisting of halogen and a halogen compound, 100 parts by weight of a polyethylene resin, hydrotalcite, calcium stearate, potassium oxide, Metal produced by mixing 0.01 to 1 part by weight of at least one compound selected from the group consisting of magnesium hydroxide, calcium hydroxide, organotin compounds and calcium phosphate, and collecting the remaining impurities A foamable polyethylene resin composition for tube coating is extruded into a sheet from an extruder to form a foamed sheet. The foamed sheet is cut to the same length as the outer circumference of the metal tube, and then rolled into a cylindrical shape to coat the metal tube. A foamed polyethylene-coated metal tube that does not cause metal corrosion and has excellent heat insulation and shock absorption is provided. That.
本発明は、上述した如く、一定量の不純物捕集剤を配合した金属管被覆用発泡性ポリエチレン樹脂組成物を用いて得られる発泡ポリエチレン被覆金属管に係わるものであるが、その好ましい態様としては、次のものが包含される。 As described above, the present invention relates to a foamed polyethylene-coated metal tube obtained by using a foamable polyethylene resin composition for coating a metal tube containing a certain amount of an impurity scavenger. The following are included:
（１）ポリエチレン系樹脂１００重量部に、ハロゲン又はハロゲン系化合物からなる残留の不純物を含む化学発泡剤０．１〜１０重量部、及び不純物捕集剤０．０１〜１重量部を配合させ、上記残留の不純物を捕集することにより製造された金属管被覆用発泡性ポリエチレン樹脂組成物を、予熱された金属管の表面に押出機により押出し被覆し製造された、金属腐食を起こさず、断熱性、衝撃吸収性に富んだ発泡ポリエチレン被覆金属管において、該不純物捕集剤がハイドロタルサイト、ステアリン酸カルシウム、酸化カリウム、水酸化マグネシウム、水酸化カルシウム、有機スズ化合物及びリン酸カルシウムからなる群から選ばれる少なくとも１種の化合物であることを特徴とする発泡性ポリエチレン被覆金属管。
（２）ポリエチレン系樹脂１００重量部に、ハロゲン又はハロゲン系化合物からなる残留の不純物を含む化学発泡剤０．１〜１０重量部、及び不純物捕集剤０．０１〜１重量部を配合させ、上記残留の不純物を捕集することにより製造された金属管被覆用発泡性ポリエチレン樹脂組成物を、予熱された金属管の表面に押出機により押出し被覆し製造された、金属腐食を起こさず、断熱性、衝撃吸収性に富んだ発泡ポリエチレン被覆金属管において、該化学発泡剤がアゾ化合物、スルホヒドラジド化合物及びニトロソ化合物からなる群から選ばれる少なくとも１種の化合物であることを特徴とする発泡性ポリエチレン被覆金属管。
（３）ポリエチレン系樹脂１００重量部に、ハロゲン又はハロゲン系化合物からなる残留の不純物を含む化学発泡剤０．１〜１０重量部、及び不純物捕集剤０．０１〜１重量部を配合させ、上記残留の不純物を捕集することにより製造された金属管被覆用発泡性ポリエチレン樹脂組成物を、押出機よりシート状に押出して発泡シートとし、該発泡シートを金属管の外周と同じ長さに切断したのち円筒状に丸めて金属管に被覆し製造された、金属腐食を起こさず、断熱性、衝撃吸収性に富んだ発泡ポリエチレン被覆金属管において、該不純物捕集剤がハイドロタルサイト、ステアリン酸カルシウム、酸化カリウム、水酸化マグネシウム、水酸化カルシウム、有機スズ化合物及びリン酸カルシウムからなる群から選ばれる少なくとも１種の化合物であることを特徴とする発泡性ポリエチレン被覆金属管。
（４）ポリエチレン系樹脂１００重量部に、ハロゲン又はハロゲン系化合物からなる残留の不純物を含む化学発泡剤０．１〜１０重量部、及び不純物捕集剤０．０１〜１重量部を配合させ、上記残留の不純物を捕集することにより製造された金属管被覆用発泡性ポリエチレン樹脂組成物を、押出機よりシート状に押出して発泡シートとし、該発泡シートを金属管の外周と同じ長さに切断したのち円筒状に丸めて金属管に被覆し製造された、金属腐食を起こさず、断熱性、衝撃吸収性に富んだ発泡ポリエチレン被覆金属管において、該化学発泡剤がアゾ化合物、スルホヒドラジド化合物及びニトロソ化合物からなる群から選ばれる少なくとも１種の化合物であることを特徴とする発泡性ポリエチレン被覆金属管。
(1) To 100 parts by weight of a polyethylene-based resin, 0.1 to 10 parts by weight of a chemical foaming agent containing residual impurities composed of halogen or a halogen-based compound, and 0.01 to 1 part by weight of an impurity scavenger are blended, The foamable polyethylene resin composition for coating metal pipes produced by collecting the residual impurities is extruded and coated on the surface of a preheated metal pipe by an extruder, and is insulated without causing metal corrosion. In the foamed polyethylene-coated metal tube rich in heat resistance and shock absorption, the impurity scavenger is selected from the group consisting of hydrotalcite, calcium stearate, potassium oxide, magnesium hydroxide, calcium hydroxide, organotin compounds and calcium phosphate A foamable polyethylene-coated metal tube, which is at least one compound.
(2) To 100 parts by weight of a polyethylene resin, 0.1 to 10 parts by weight of a chemical foaming agent containing residual impurities consisting of halogen or a halogen-based compound, and 0.01 to 1 part by weight of an impurity scavenger are blended, The foamable polyethylene resin composition for coating metal pipes produced by collecting the residual impurities is extruded and coated on the surface of a preheated metal pipe by an extruder, and is insulated without causing metal corrosion. Polyethylene foam-coated metal tube having excellent properties and shock absorption, wherein the chemical foaming agent is at least one compound selected from the group consisting of azo compounds, sulfohydrazide compounds and nitroso compounds. Coated metal tube.
(3) To 100 parts by weight of a polyethylene-based resin, 0.1 to 10 parts by weight of a chemical foaming agent containing residual impurities composed of halogen or a halogen-based compound, and 0.01 to 1 part by weight of an impurity scavenger are blended, The foamable polyethylene resin composition for covering metal pipes produced by collecting the remaining impurities is extruded into a sheet form from an extruder to form a foamed sheet, and the foamed sheet has the same length as the outer periphery of the metal pipe. After being cut and rolled into a cylindrical shape and coated on a metal tube, the metal scavenger-free foamed polyethylene-coated metal tube has excellent heat insulation and shock absorption. At least one compound selected from the group consisting of calcium phosphate, potassium oxide, magnesium hydroxide, calcium hydroxide, organotin compounds, and calcium phosphate Expandable polyethylene-coated metal tube, characterized in that.
(4) To 100 parts by weight of a polyethylene-based resin, 0.1 to 10 parts by weight of a chemical foaming agent containing residual impurities composed of halogen or a halogen-based compound, and 0.01 to 1 part by weight of an impurity scavenger are blended, The foamable polyethylene resin composition for covering metal pipes produced by collecting the remaining impurities is extruded into a sheet form from an extruder to form a foamed sheet, and the foamed sheet has the same length as the outer periphery of the metal pipe. In a foamed polyethylene-coated metal tube that is cut and then rolled into a cylindrical shape and coated onto a metal tube, which does not cause metal corrosion and has excellent heat insulation and shock absorption, the chemical foaming agent is an azo compound or a sulfohydrazide compound. And a foamable polyethylene-coated metal tube, which is at least one compound selected from the group consisting of nitroso compounds.
本発明により製造される発泡ポリエチレン被覆金属管は、従来の発泡ポリエチレン被覆金属管とは違い、通常市販されているハロゲン又はハロゲン化合物を不純物として含む化学発泡剤を使用しても、発錆や金属腐蝕を起こさず、かつ断熱性、衝撃吸収性にも富んだ高品質のものとなる。 Unlike the conventional foamed polyethylene-coated metal pipe, the foamed polyethylene-coated metal pipe produced according to the present invention is usually rusted or metalized even when a commercially available chemical foaming agent containing halogen or a halogen compound as an impurity is used. It does not cause corrosion, and is of high quality with excellent heat insulation and shock absorption.
以下、本発明の発泡ポリエチレン被覆金属管について詳細に説明する。 Hereinafter, the foamed polyethylene-coated metal tube of the present invention will be described in detail.
１．ポリエチレン系樹脂
本発明において用いられるポリエチレン系樹脂とは、低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン等のポリエチレン、直鎖状低密度エチレン−α−オレフィン共重合体、超低密度直鎖状エチレン−α−オレフィン共重合体、エチレン−酢酸ビニル共重合体、エチレン−エチルアクリレート共重合体等のエチレンと他のオレフィン又はビニルモノマーとの共重合体、又はメタロセン触媒によるポリエチレン等を意味する。通常は、これらポリエチレン系樹脂は、単独で用いられるが、必要に応じて、これらを組合せ、又は、これらを主体として、少量の他のオレフィン系ポリマー、スチレン系ポリマー等の熱可塑性エラストマーを配合してもよい。
1. Polyethylene resin The polyethylene resin used in the present invention is polyethylene such as low density polyethylene, medium density polyethylene, and high density polyethylene, linear low density ethylene-α-olefin copolymer, and ultra low density linear ethylene. It means a copolymer of ethylene and another olefin or vinyl monomer such as an α-olefin copolymer, an ethylene-vinyl acetate copolymer or an ethylene-ethyl acrylate copolymer, or a polyethylene based on a metallocene catalyst. Usually, these polyethylene resins are used alone, but if necessary, they are combined, or a small amount of other thermoplastic elastomers such as olefin polymers and styrene polymers are blended mainly. May be.
２．化学発泡剤
本発明において用いられる化学発泡剤とは、ベンゼンスルホヒドラジド、ベンゼン−１，３−ジスルホヒドラジド、ジフェニルスルホン−３−３’−ジスルホヒドラジド、４，４’−オキシビス（ベンゼンスルホヒドラジド）（以下、ＯＢＳＨと略することもある）等のスルホヒドラジド化合物や、アゾジカルボンアミド（以下、ＡＤＣＡと略することもある）、２，２’−アゾイソブチロニトリル、アゾヘキサヒドロベンゾニトリル、ジアゾアミノベンゼン等のアゾ化合物や、Ｎ，Ｎ’−ジニトロソペンタメチレンテトラミン（以下、ＤＮＰＴと略することもある）、Ｎ，Ｎ’−ジニトロソ−Ｎ，Ｎ’−ジメチルテレフタルアミド等のニトロソ化合物を意味する。これらの化合物は、製造時にハロゲン含有化合物を原料として使用するため、精製工程で未反応の原料や副生成物等の不純物を除去するべく濾別しても、どうしてもこれらの不純物が生成物と共に通過し、生成物中に微量の不純物が残留することになる。この残留するハロゲン又はハロゲン系化合物からなる不純物が原因となって金属管の表面を発錆させ、金属管の腐蝕を進行させる結果となる。そのため、これらの化学発泡剤を単独で用いた従来の発泡ポリエチレン被覆金属管の場合は、品質の良好な金属管を得ることは不可能である。本発明においては、上記したハロゲン又はハロゲン系化合物からなる不純物による発錆作用を抑制するために、不純物捕集剤を併用し、上記の弊害を防止することができる。本発明おいては、発泡剤として上記の化学発泡剤単独でもよいが、化学発泡剤同志を併用することもでき、しかも場合によっては、化学発泡剤に併用して、窒素ガス、炭酸ガス、アルゴンガス、キセノンガス、ブタン、ペンタン、ヘプタン等の気体を使用してもよい。発泡ポリエチレン被覆金属管の場合、通常はポリエチレン系樹脂を１０〜３０倍に発泡させるのが一般的である。そのため、化学発泡剤の使用量は、ポリエチレン系樹脂１００重量部に対して０．１〜１０重量部であることが好ましい。化学発泡剤の使用量が０．１重量部未満であると、発泡度が低すぎ、結果として所定の断熱性、衝撃吸収性が得られず、良好な品質の発泡体被覆金属管が得られない。一方、化学発泡剤の使用量が１０重量部を越えると、過発泡がおき、均一な発泡体が得られず、結果として発泡体の表面も不均一となり、良好な品質の発泡体被覆金属管が得られない。
2. Chemical foaming agent The chemical foaming agent used in the present invention is benzenesulfohydrazide, benzene-1,3-disulfohydrazide, diphenylsulfone-3-3'-disulfohydrazide, 4,4'-oxybis (benzenesulfohydrazide). ) (Hereinafter also abbreviated as OBSH) and the like, azodicarbonamide (hereinafter also abbreviated as ADCA), 2,2′-azoisobutyronitrile, azohexahydrobenzonitrile Azo compounds such as diazoaminobenzene, nitroso such as N, N′-dinitrosopentamethylenetetramine (hereinafter sometimes abbreviated as DNPT), N, N′-dinitroso-N, N′-dimethylterephthalamide, etc. Means a compound. Since these compounds use halogen-containing compounds as raw materials at the time of production, even if they are filtered to remove impurities such as unreacted raw materials and by-products in the purification process, these impurities always pass along with the products. Trace amounts of impurities will remain in the product. This residual impurity of halogen or a halogen-based compound causes the surface of the metal tube to rust, resulting in the corrosion of the metal tube. Therefore, in the case of a conventional foamed polyethylene-coated metal tube using these chemical foaming agents alone, it is impossible to obtain a metal tube with good quality. In the present invention, in order to suppress the rusting action caused by impurities composed of the halogen or the halogen-based compound described above, an impurity scavenger can be used in combination to prevent the above-described adverse effects. In the present invention, the above-mentioned chemical foaming agent alone may be used as the foaming agent, but chemical foaming agents may be used in combination, and in some cases, combined with the chemical foaming agent, nitrogen gas, carbon dioxide gas, argon Gases such as gas, xenon gas, butane, pentane and heptane may be used. In the case of a foamed polyethylene-coated metal tube, it is common to foam a polyethylene resin 10 to 30 times. Therefore, it is preferable that the usage-amount of a chemical foaming agent is 0.1-10 weight part with respect to 100 weight part of polyethylene-type resin. When the amount of the chemical foaming agent used is less than 0.1 parts by weight, the foaming degree is too low, and as a result, the predetermined heat insulating property and shock absorbing property cannot be obtained, and a good quality foam-coated metal tube is obtained. Absent. On the other hand, when the amount of the chemical foaming agent used exceeds 10 parts by weight, overfoaming occurs and a uniform foam cannot be obtained. As a result, the surface of the foam becomes non-uniform, resulting in a good quality foam-coated metal tube. Cannot be obtained.
３．不純物捕集剤
本発明において用いられる不純物捕集剤とは、化学発泡剤中に残存するハロゲン又はハロゲン系化合物からなる不純物を物理的及び／又は化学的に吸着及び／又は化学反応により捕集する化合物を意味する。本発明では、この不純物捕集剤を用いることにより、ハロゲン又はハロゲン系化合物からなる不純物によって発現される発錆や腐蝕が抑制されるだけでなく、その上不純物によるポリエチレン系樹脂の発泡阻害をもなくする効果が生ずる。これらの不純物捕集剤としては、具体的には、ハイドロタルサイト、ステアリン酸カルシウム、酸化カリウム、水酸化マグネシウム、水酸化カルシウム、有機スズ化合物、リン酸カルシウム等の化合物が挙げられるが、そのうち、ハイドロタルサイトが特に望ましい。
上記のハイドロタルサイトは、マグネシウムとアルミニウムの含水塩基性炭酸塩を意味し、これらは、天然物であっても合成物であってもいずれでもよい。天然物は、Ｍｇ５Ａｌ２（ＯＨ）１６ＣＯ３・４Ｈ２Ｏの構造を有し、一方、合成物は、ＭｇとＡｌとの比が異なったもの、例えば、
Ｍｇ４Ａｌ２（ＯＨ）１２ＣＯ３・３Ｈ２Ｏ、
Ｍｇ５Ａｌ２（ＯＨ）１４ＣＯ３・４Ｈ２Ｏ、
Ｍｇ１０Ａｌ２（ＯＨ）２２ＣＯ３・４Ｈ２Ｏ、
Ｍｇ８Ａｌ２（ＯＨ）２０ＣＯ３・５Ｈ２Ｏ
等が挙げられる。
これらの不純物捕集剤を本発泡性ポリエチレン樹脂組成物に配合する場合は、上記化合物を単独で使用しても、また２種以上を併用してもよい。
不純物捕集剤の使用量は、化学発泡剤の１〜１０％の範囲、すなわち、ポリエチレン系樹脂１００重量部に対して０．０１〜１．０重量部である。不純物捕集剤の使用量が０．０１重量部未満であると、金属腐蝕防止効果（防錆効果）が発現しなく、また一方、不純物捕集剤の使用量が１．０重量部を越えると、押出ダイ付近に目やにが発生し、その結果、生産性が悪くなったり、均一な発泡体が得られなかったり等の問題が生じ、望ましくない。
3. Impurity trapping agent The impurity trapping agent used in the present invention traps impurities consisting of halogen or halogen-based compounds remaining in the chemical foaming agent physically and / or chemically by adsorption and / or chemical reaction. Means a compound. In the present invention, by using this impurity scavenger, not only rusting and corrosion expressed by impurities composed of halogen or a halogen-based compound is suppressed, but also foaming inhibition of the polyethylene-based resin due to impurities is suppressed. The effect to lose occurs. Specific examples of these impurity scavengers include hydrotalcite, calcium stearate, potassium oxide, magnesium hydroxide, calcium hydroxide, organotin compounds, and calcium phosphate compounds. Among them, hydrotalcite Is particularly desirable.
The above hydrotalcite means a water-containing basic carbonate of magnesium and aluminum, and these may be natural products or synthetic products. Natural products have the structure Mg 5 Al 2 (OH) 16 CO 3 .4H 2 O, while synthetic products have different ratios of Mg and Al, eg
Mg 4 Al 2 (OH) 12 CO 3 · 3H 2 O,
Mg 5 Al 2 (OH) 14 CO 3 .4H 2 O,
Mg 10 Al 2 (OH) 22 CO 3 .4H 2 O,
Mg 8 Al 2 (OH) 20 CO 3 · 5H 2 O
Etc.
When blending these impurity scavengers in the foamable polyethylene resin composition, the above compounds may be used alone or in combination of two or more.
The amount of the impurity scavenger used is in the range of 1 to 10% of the chemical foaming agent, that is, 0.01 to 1.0 part by weight with respect to 100 parts by weight of the polyethylene resin. If the amount of the impurity scavenger used is less than 0.01 parts by weight, the metal corrosion prevention effect (rust prevention effect) does not appear, while the amount of the impurity scavenger used exceeds 1.0 parts by weight. In this case, eyes are formed near the extrusion die. As a result, problems such as poor productivity and a uniform foam cannot be obtained.
４．発泡性ポリエチレン樹脂組成物
本発明の発泡ポリエチレン被覆金属管を製造するのに用いられる発泡性ポリエチレン樹脂組成物は、前記した如く、所定の配合比で配合されたポリエチレン系樹脂、化学発泡剤、不純物捕集剤及び所望に応じて添加する他の添加剤からなる混合物を、例えばバンバリーミキサー等の好適な混練手段によって混練することによって製造される。特に好ましい混練法によれば、ポリエチレン系樹脂、所定量の不純物捕集剤及び他の添加剤（酸化防止剤など）は、バンバリーミキサー内で、まずポリエチレン系樹脂の融点以上の温度に加熱され混練され、次いでこの混練物に所定量の化学発泡剤が添加され、化学発泡剤の分解温度（１３５〜２００℃）よりも低い温度で混練された後に冷却され、シート状物にされる。この発泡工程は、一段であっても予備発泡を含む二段であってもよく、適宜選びうるが、均一な発泡体を得るためには、後者の手段が好ましい。予備発泡を含む二段にする場合には、シート状物は、更に切断され、ペレットにされたのち、再び所定の形状に発泡成形される。
本発明において用いられる発泡性ポリエチレン樹脂組成物には、他の添加剤として、発泡助剤、発泡均一剤、着色剤、酸化防止剤、成核剤、銅害防止剤、金属腐食防止剤、加工助剤、目やに発生防止剤等を配合してもよい。
4). Expandable polyethylene resin composition The expandable polyethylene resin composition used for producing the expanded polyethylene-coated metal tube of the present invention comprises, as described above, a polyethylene-based resin, a chemical foaming agent, and impurities mixed at a predetermined mixing ratio. It is produced by kneading a mixture comprising a collecting agent and other additives to be added as desired by a suitable kneading means such as a Banbury mixer. According to a particularly preferred kneading method, a polyethylene resin, a predetermined amount of an impurity scavenger and other additives (antioxidants, etc.) are first heated and kneaded in a Banbury mixer at a temperature equal to or higher than the melting point of the polyethylene resin. Then, a predetermined amount of a chemical foaming agent is added to the kneaded product, and after being kneaded at a temperature lower than the decomposition temperature (135 to 200 ° C.) of the chemical foaming agent, it is cooled to form a sheet. This foaming step may be one step or two steps including pre-foaming, and can be selected as appropriate. However, the latter means is preferable in order to obtain a uniform foam. In the case of two stages including preliminary foaming, the sheet-like product is further cut and pelletized, and then foam-molded into a predetermined shape again.
In the foamable polyethylene resin composition used in the present invention, as other additives, foaming aids, foaming uniform agents, colorants, antioxidants, nucleating agents, copper damage inhibitors, metal corrosion inhibitors, processing You may mix | blend an auxiliary agent, a generation | occurrence | production prevention agent, etc. with eyes.
５．ポリエチレン発泡体被覆金属管
本発明において発泡性ポリエチレン樹脂組成物は、斯界で周知の発泡ポリエチレン被覆金属管の製法に従い、金属管の表面に被覆されたのち、発泡される。
この製法としては、種々のやり方が可能であるが、一つの方法によれば、まず上記のように準備した予備発泡ペレットを押出機に供給し、所定の温度に加熱溶融し、次いでこの得られた溶融発泡性樹脂組成物を予熱された金属管の表面に押出被覆して大気中で発泡させ、冷却させることにより、目的とするポリエチレン発泡体被覆金属管が得られる。この場合、最初の加熱溶融時の温度は、該ポリオレフィン系樹脂の融点以上でかつ化学発泡剤の分解温度以下の温度下であることが必要であり、また一方、次の被覆発泡時の温度は、該化学発泡剤の分解温度を超える温度（通常は１３５〜２００℃）であることが必要である。
また別の方法によれば、まず上記の予備発泡ペレットを押出機に供給し、所定の温度に加熱溶融し、得られた溶融発泡性樹脂組成物をダイよりシート状に押出して発泡シートとし、次いで該発泡シートを金属管の外周とほぼ同じ幅に切断したのち、円筒状に丸めて金属管に被覆し、該シートの両側面を対峠させた状態で熱融着させるか、又は熱融着させない場合は、外部を粘着テープや針金で巻きつけるかして、ほどけないような状態にし、目的とするポリエチレン発泡体被覆金属管が得られる。この場合においても、上記の第一の製法の場合と同様に、最初の加熱溶融時の温度は、該ポリオレフィン系樹脂の融点以上でかつ化学発泡剤の分解温度以下の温度下であることが必要であり、また一方、次のシート状に押出し時の温度は、該化学発泡剤の分解温度を超える温度（通常は１３５〜２００℃）であることが必要である。
後者の別の方法の場合、発泡シートの片面上でかつ金属管に対峠する面上に、長手方向に沿い平行に複数本のＶ形の溝を、カッターで切断したり又は加熱した金型でもって溶融押印したりすることで形成させておくと、円筒状の発泡シートがフラットな状態へ復元しようとする残留応力が極めて少なくなり、その結果、円筒状の形状維持が良好となる。
本発明において発泡性ポリエチレン樹脂組成物が適用される金属管は、通常、鉄、アルミニウム、銅、チタン、ステンレス、亜鉛、錫等の金属を主体として製造した管であるが、場合によっては、これらの金属以外にマグネシウム、クロム、ニッケル、ジルコニウム、炭素等を微量配合したものであってもよい。
5. Polyethylene foam-coated metal tube In the present invention, the foamable polyethylene resin composition is foamed after being coated on the surface of the metal tube in accordance with a well-known method for producing a foamed polyethylene-coated metal tube.
Various methods can be used for this production method. According to one method, first, the pre-foamed pellets prepared as described above are supplied to an extruder, heated and melted to a predetermined temperature, and then obtained. The melt-foamable resin composition thus obtained is extrusion-coated on the surface of a preheated metal tube, foamed in the air, and cooled to obtain the intended polyethylene foam-coated metal tube. In this case, the temperature at the first heating and melting needs to be not less than the melting point of the polyolefin resin and not more than the decomposition temperature of the chemical foaming agent, and the temperature at the next coating and foaming is The temperature must be higher than the decomposition temperature of the chemical foaming agent (usually 135 to 200 ° C.).
According to another method, the pre-foamed pellets are first supplied to an extruder, heated and melted to a predetermined temperature, and the resulting melt-foamable resin composition is extruded into a sheet form from a die to form a foam sheet, Next, the foamed sheet is cut to approximately the same width as the outer periphery of the metal tube, and then rolled into a cylindrical shape and covered with a metal tube, and heat-sealed with both sides of the sheet facing each other, or heat-fused. When not attached, the outside can be wound with an adhesive tape or a wire so that it cannot be unwound, and the desired polyethylene foam-coated metal tube can be obtained. In this case as well, as in the case of the first production method described above, the temperature at the first heating and melting must be not lower than the melting point of the polyolefin resin and not higher than the decomposition temperature of the chemical foaming agent. On the other hand, it is necessary that the temperature at the time of extrusion into the next sheet is a temperature exceeding the decomposition temperature of the chemical foaming agent (usually 135 to 200 ° C.).
In the case of the latter another method, a mold in which a plurality of V-shaped grooves are cut by a cutter or heated on one side of a foamed sheet and on a surface facing a metal tube in parallel along the longitudinal direction. Therefore, if it is formed by fusion stamping or the like, the residual stress that the cylindrical foam sheet tries to restore to a flat state is extremely reduced, and as a result, the cylindrical shape is maintained well.
In the present invention, the metal pipe to which the foamable polyethylene resin composition is applied is usually a pipe made mainly of metal such as iron, aluminum, copper, titanium, stainless steel, zinc, tin, etc. In addition to these metals, magnesium, chromium, nickel, zirconium, carbon, etc. may be blended in a trace amount.
本発明の発泡ポリエチレン被覆金属管は、従来の発泡ポリエチレン被覆金属管とは違い、金属腐蝕を起こさず、かつ断熱性、衝撃吸収性にも富んだものであるため、結湯管、結水管、ガス配管、温泉水配管、電線用配管、化学薬品配管、溶剤配管、熱媒体配管、原油配管、石油製品配管、排気ガス配管、冷媒配管、空気配管、工業用ガス配管、農薬配管、肥料配管等として幅広く利用される。 Unlike the conventional foamed polyethylene-coated metal pipe, the foamed polyethylene-coated metal pipe of the present invention does not cause metal corrosion, and is also excellent in heat insulation and shock absorption. Gas piping, hot spring water piping, electric wire piping, chemical piping, solvent piping, heat medium piping, crude oil piping, petroleum product piping, exhaust gas piping, refrigerant piping, air piping, industrial gas piping, agricultural chemical piping, fertilizer piping, etc. As widely used.
以下に、実施例を挙げて本発明を更に詳細に説明するが、本発明は、以下の実施例によって何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
実施例１（参考例）
メルトインデックスが２．３ｇ／１０分、密度が０．９１８ｇ／ｃｍ３、スウェリング比が６５％の高圧法低密度ポリエチレン１００重量部に対して、不純物１％を含有する市販の４，４’−オキシビスベンゼンスルホヒドラジド１．３重量部、ステアリン酸亜鉛０．１重量部、及び酸化防止剤（ブチル化ヒドロキシトルエン）０．１重量部を配合し、バンバリーミキサーで１０分間、１３０℃で混練して、シート状に押出し、予備発泡度４．４％のシートを得た。このシートをカッターで切断し、厚さ３ｍｍ、長さ５ｍｍ、幅４ｍｍのペレットを得た。
次いで、５０ｍｍφの押出機（Ｌ／Ｄ＝２４）に前記ペレットを供給し、供給領域のシリンダー温度を１３０℃、圧縮領域のシリンダー温度を１４０℃、計量領域のシリンダー温度を１４７℃としたのち、７０℃に予熱した３０ｍｍφの銅管の表面に速度２０ｍ／ｍｉｎで、厚さ３．０ｍｍとなるように押出被覆し、発泡ポリエチレン被覆銅管を得た。得られた発泡体は、発泡度５２％、気泡径５０〜１５０μを有し、外観は良好であった。
この発泡ポリエチレン被覆銅管の周囲に粘着テープを巻きつけ、温度５０℃、湿度１００％ＲＨの条件下で３００日間加湿処理したのち、目視により観察したところ、全く発錆は認められなかった。
Example 1 (reference example)
Commercially available 4,4 ′ containing 1% of impurities with respect to 100 parts by weight of high-pressure low-density polyethylene having a melt index of 2.3 g / 10 min, a density of 0.918 g / cm 3 , and a swelling ratio of 65%. -Mixing 1.3 parts by weight of oxybisbenzenesulfohydrazide, 0.1 part by weight of zinc stearate and 0.1 part by weight of antioxidant (butylated hydroxytoluene), kneading at 130 ° C for 10 minutes with a Banbury mixer Then, it was extruded into a sheet shape to obtain a sheet having a pre-foaming degree of 4.4%. This sheet was cut with a cutter to obtain a pellet having a thickness of 3 mm, a length of 5 mm, and a width of 4 mm.
Next, the pellets were supplied to a 50 mmφ extruder (L / D = 24), the cylinder temperature in the supply area was 130 ° C., the cylinder temperature in the compression area was 140 ° C., and the cylinder temperature in the measurement area was 147 ° C. The surface of a 30 mmφ copper tube preheated to 70 ° C. was extrusion coated at a speed of 20 m / min to a thickness of 3.0 mm to obtain a foamed polyethylene-coated copper tube. The obtained foam had a foaming degree of 52%, a cell diameter of 50 to 150 μm, and a good appearance.
An adhesive tape was wound around the foamed polyethylene-coated copper tube, and after humidifying for 300 days under the conditions of a temperature of 50 ° C. and a humidity of 100% RH, no rusting was observed when observed visually.
比較例１
ステアリン酸亜鉛の配合量を０とした以外は、実施例１（参考例）と同様な実験を行ったところ、銅管表面に発錆が認められた。
Comparative Example 1
Rust was observed on the surface of the copper tube when the same experiment as in Example 1 (Reference Example) was conducted except that the amount of zinc stearate was changed to 0.
実施例２
融点が１３３℃、密度が０．９５８ｇ／ｃｍ３、スウェリング比が４７％、メルトインデックスが３．３ｇ／１０分の高密度ポリエチレン１００重量部に対して、メルトインデックスが２．４ｇ／１０分、密度が０．９２０ｇ／ｃｍ３、スウェリング比が５３％の高圧法で製造した長鎖分岐を有する低密度ポリエチレン６０重量部、融点が１５４℃、密度が０．９０ｇ／ｃｍ３，メルトフローレイトが２．８ｇ／１０分のポリプロピレン１０重量部、ポリシロキサン−ポリエーテルブロック共重合体１５重量部、ＡＤＣＡ（アゾジカルボンアミド）０．４重量部、ハイドロタルサイド（Ｍｇ４Ａｌ２（ＯＨ）１２ＣＯ３・３Ｈ２Ｏ）０．１重量部、タルク０．１重量部、及び酸化防止剤（ブチル化ヒドロキシトルエン）０．１重量部を配合し、バンバリーミキサーで１５分間、１６０℃で加熱混練して、シート状に押出した。このシート状物をカッターで切断し、厚さ３ｍｍ、長さ５ｍｍ、幅４ｍｍのペレットを得た。次いで６５ｍｍφの第一段の押出機（Ｌ／Ｄ＝２８）に前記ペレットを供給し、供給領域のシリンダー温度を１５２℃、圧縮領域のシリンダー温度を１８２℃、計量領域のシリンダー温度を１８８℃としながら、該圧縮領域において、前記ペレット１００重量部に対して１．８重量部の割合で窒素ガスを圧入し、引き続き、前記窒素ガスを圧入したペレットを第一段の押出機から６５ｍｍφの第二段の押出機（Ｌ／Ｄ＝２８）に供給し、供給領域のシリンダ温度を１７５℃、圧縮領域のシリンダ温度を１５７℃、計量領域のシリンダ温度を１３４℃として、前記ペレットと窒素を均一に混練し、各成分を均一に配合したのち、次いで第二段の押出機のクロスヘッドより８０℃に予熱した２０ｍｍφの鉄管の表面に、速度３０ｍ／ｍｉｎで、厚さ２．０ｍｍとなるように押出被覆し、発泡ポリエチレン被覆鉄管を得た。得られた発泡体は、発泡度８１％、気泡径２０〜９０μを有し、しかもその圧縮強度について測定したところ、１．８２ｋｇ／ｍｍ２であり、機械的強度も十分あった。この発泡ポリエチレン被覆鉄管の周囲にアルミテープを巻きつけ、温度５０℃、湿度１００％ＲＨの条件下で２００日間加湿処理したのち、目視により観察したところ、全く発錆は認められなかった。
Example 2
Melting point is 133 ° C., density is 0.958 g / cm 3 , swelling ratio is 47%, melt index is 3.3 g / 10 minutes, and 100 parts by weight of high density polyethylene is 2.4 g / 10 minutes. 60 parts by weight of low-density polyethylene having a long chain branch produced by a high pressure method having a density of 0.920 g / cm 3 and a swelling ratio of 53%, a melting point of 154 ° C., a density of 0.90 g / cm 3 , a melt flow 10 parts by weight of polypropylene at a rate of 2.8 g / 10 min, 15 parts by weight of polysiloxane-polyether block copolymer, 0.4 parts by weight of ADCA (azodicarbonamide), hydrotalcide (Mg 4 Al 2 (OH) 12 CO 3 · 3H 2 O) 0.1 parts by weight of talc, 0.1 part by weight and an antioxidant (butylated hydroxy toluene) 0.1 Blended for 15 minutes in a Banbury mixer, and heated and kneaded at 160 ° C., extruded into a sheet. This sheet was cut with a cutter to obtain a pellet having a thickness of 3 mm, a length of 5 mm, and a width of 4 mm. Next, the pellets were supplied to a 65 mmφ first stage extruder (L / D = 28), the cylinder temperature in the supply area was 152 ° C., the cylinder temperature in the compression area was 182 ° C., and the cylinder temperature in the metering area was 188 ° C. However, in the compression region, nitrogen gas was injected at a ratio of 1.8 parts by weight with respect to 100 parts by weight of the pellets. Subsequently, the pellets into which the nitrogen gas had been injected were put into a second 65 mmφ second pellet from the first stage extruder. Supply to the stage extruder (L / D = 28), the cylinder temperature in the supply area is 175 ° C., the cylinder temperature in the compression area is 157 ° C., the cylinder temperature in the metering area is 134 ° C., and the pellets and nitrogen are evenly distributed. After kneading and blending each component uniformly, the thickness of the steel tube of 20 mmφ preheated to 80 ° C. from the cross head of the second stage extruder is then increased at a speed of 30 m / min. Extrusion coated as a .0Mm, to obtain a foamed polyethylene-coated steel pipes. The obtained foam had a foaming degree of 81% and a bubble diameter of 20 to 90 μm, and when measured for its compressive strength, it was 1.82 kg / mm 2 and sufficient mechanical strength was obtained. An aluminum tape was wrapped around the foamed polyethylene-coated iron pipe, and after humidifying for 200 days under the conditions of a temperature of 50 ° C. and a humidity of 100% RH, no rusting was observed when visually observed.
比較例２
ハイドロタルサイトの量を０とした以外は、実施例２と同様な実験を行ったところ、鉄管の表面に発錆が認められた。
Comparative Example 2
Except that the amount of hydrotalcite was set to 0, the same experiment as in Example 2 was performed, and rusting was observed on the surface of the iron pipe.
実施例３
メルトインデックスが３．５ｇ／１０分、密度が０．９３５ｇ／ｃｍ３、スウェリング比が５６％の高圧法で製造したエチレン−酢酸ビニル共重合体（酢酸ビニル含有量１５％）１００重量部に対して、アゾジカルボンアミド０．８重量部、酸化防止剤（ブチル化ヒドロキシトルエン）０．４重量部、及び水酸化マグネシウム０．２重量部を配合し、押出機に供給し、供給領域のシリンダー温度を１２５℃、圧縮領域のシリンダー温度を１３３℃、計量領域のシリンダー温度を１３９℃としたのち、Ｔダイより押出し、厚さが３ｍｍ、発泡度が４３％、気泡径が７０〜１３０μの発泡シートを得た。一方、直径３０ｍｍのアルミニウム管を用意し、上記発泡シートを切断し、アルミニウム管の外周に円筒状にまきつけ、その外部を粘着テープで３重にまきつけた。この発泡体被覆アルミニウム管を３００日間、屋外に設置したが、目視により観察したところ、全く発錆は認められなかった。
Example 3
100 parts by weight of ethylene-vinyl acetate copolymer (vinyl acetate content 15%) produced by a high pressure method having a melt index of 3.5 g / 10 min, a density of 0.935 g / cm 3 and a swelling ratio of 56% On the other hand, 0.8 part by weight of azodicarbonamide, 0.4 part by weight of antioxidant (butylated hydroxytoluene) and 0.2 part by weight of magnesium hydroxide are blended and supplied to the extruder, and the cylinder in the supply area After setting the temperature to 125 ° C, the cylinder temperature in the compression region to 133 ° C, and the cylinder temperature in the metering region to 139 ° C, extrusion from a T-die, foaming with a thickness of 3mm, a foaming degree of 43%, and a bubble diameter of 70-130μ A sheet was obtained. On the other hand, an aluminum tube having a diameter of 30 mm was prepared, the foam sheet was cut, and the outer periphery of the aluminum tube was cylindrically wound, and the outside was triple coated with an adhesive tape. This foam-coated aluminum tube was installed outdoors for 300 days. When visually observed, no rusting was observed.
比較例３
水酸化マグネシウムの量を０とした以外は、実施例３と同様な実験を行ったところ、アルミニウム管の表面に発錆が認められた。
Comparative Example 3
Except that the amount of magnesium hydroxide was changed to 0, an experiment similar to that of Example 3 was performed. As a result, rusting was observed on the surface of the aluminum tube.
実施例４
実施例１（参考例）においてステアリン酸亜鉛に代えて、ステアリン酸カルシウム、水酸化カルシウム、リン酸カルシウム、ジブチル錫ジラウレート、ジオクチル錫ジラウレートをそれぞれ使用した以外は、実施例１（参考例）と同様な実験を行った。発泡は、実施例１（参考例）と同様に正常に行われ、しかも銅管表面には、全く発錆が認められなかった。このことから、上記各化合物による不純物捕集剤としての効果が確認された。
Example 4
In Example 1 (Reference Example), the same experiment as Example 1 (Reference Example) was performed except that calcium stearate, calcium hydroxide, calcium phosphate, dibutyltin dilaurate, and dioctyltin dilaurate were used instead of zinc stearate. went. Foaming was performed normally in the same manner as in Example 1 (Reference Example), and no rusting was observed on the surface of the copper tube. From this, the effect as an impurity scavenger by each said compound was confirmed.
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| JP2006282242A JP4467553B2 (en) | 2006-10-17 | 2006-10-17 | Polyethylene foam coated metal tube |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009090576A (en) * | 2007-10-10 | 2009-04-30 | Mino Kogyo Kk | Molding member |
| WO2009148222A2 (en) * | 2008-06-06 | 2009-12-10 | 주식회사 아이에스테크 | Sheet for perforation for printed-circuit board |
| KR101822106B1 (en) * | 2015-10-20 | 2018-01-25 | 주식회사 하우솔 | Complex panel for outer wall or door of loaded vehicle and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009090576A (en) * | 2007-10-10 | 2009-04-30 | Mino Kogyo Kk | Molding member |
| WO2009148222A2 (en) * | 2008-06-06 | 2009-12-10 | 주식회사 아이에스테크 | Sheet for perforation for printed-circuit board |
| WO2009148222A3 (en) * | 2008-06-06 | 2010-01-28 | 주식회사 아이에스테크 | Sheet for perforation for printed-circuit board |
| CN102015286A (en) * | 2008-06-06 | 2011-04-13 | I.S科技股份有限公司 | Sheet for perforation for printed-circuit board |
| CN102015286B (en) * | 2008-06-06 | 2014-08-13 | I.S科技股份有限公司 | Sheet for perforation for printed-circuit board |
| KR101822106B1 (en) * | 2015-10-20 | 2018-01-25 | 주식회사 하우솔 | Complex panel for outer wall or door of loaded vehicle and manufacturing method thereof |
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