JP2017071218A - Stainless steel sheet-carbon composite material and method for producing the same - Google Patents

Stainless steel sheet-carbon composite material and method for producing the same Download PDF

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JP2017071218A
JP2017071218A JP2016195626A JP2016195626A JP2017071218A JP 2017071218 A JP2017071218 A JP 2017071218A JP 2016195626 A JP2016195626 A JP 2016195626A JP 2016195626 A JP2016195626 A JP 2016195626A JP 2017071218 A JP2017071218 A JP 2017071218A
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resin
stainless steel
carbon
plate
powder
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JP6970495B2 (en
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村上　信吉
Shinkichi Murakami
信吉 村上
琢 香川
Taku Kagawa
琢 香川
禰宜　教之
Noriyuki Negi
教之 禰宜
淳子 今村
Junko Imamura
淳子 今村
快朗 萩原
Yoshiaki Hagiwara
快朗 萩原
雅史 臼井
Masafumi Usui
雅史 臼井
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel and Sumikin Materials Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E60/50—Fuel cells

Abstract

PROBLEM TO BE SOLVED: To provide a stainless steel sheet-carbon composite material excellent in all of conductivity, corrosion resistance, and flexibility, and a method for producing the same.SOLUTION: In the stainless steel sheet-carbon composite material, a carbon layer containing a carbon powder and a resin powder composed of a thermoplastic resin or a thermosetting resin is laminated on at least one surface of a tabular substrate made of stainless steel. The carbon layer contains the carbon powder (C) and the resin powder (R) at a volume ratio (C/R) of 6/4 to 9/1 and is laminated via an oxide film formed on the surface of the tabular substrate. The element ratio (O/Fe) of oxygen (O) to iron (Fe) in the oxide film is within a range of 0.07 to 0.26 as measured by EDS elemental analysis.SELECTED DRAWING: None

Description

この発明は、ステンレス鋼板カーボン複合材及びその製造方法に係り、特にステンレス鋼製の板状基材の表面に炭素粉末及び樹脂粉末を含むカーボン層が積層されていることにより、例えば、固体高分子形燃料電池用等の燃料電池用セパレータを始めとして、レドックスフロー型２次電池用の集電板や、石油精製用、石油化学用等のガスケットやパッキン等においても使用可能な、導電性、耐食性及び可撓性等に優れたステンレス鋼板カーボン複合材及びその製造方法に関する。   The present invention relates to a stainless steel plate carbon composite material and a method for producing the same, and in particular, by laminating a carbon layer containing carbon powder and resin powder on the surface of a stainless steel plate-like substrate, for example, a solid polymer Conductivity and corrosion resistance that can be used for separators for fuel cells such as fuel cells, redox flow type secondary battery current collectors, and oil refining and petrochemical gaskets and packings In addition, the present invention relates to a stainless steel plate carbon composite material excellent in flexibility and a manufacturing method thereof.

近年、固体高分子形燃料電池が注目されている。斯かる燃料電池及び燃料電池用セパレータの一例を図５及び図６（ａ）、（ｂ）に示す。
ここで、図５は、燃料電池１６を構成する単位セルの構成を示す分解図であり、図６は、図５に示す燃料電池用セパレータ５の構成を示す図である。図６（ａ）は、平面図であり、図６（ｂ）は、図６（ａ）の線Ｘ−Ｙにとった断面図である。 In recent years, polymer electrolyte fuel cells have attracted attention. An example of such a fuel cell and a fuel cell separator is shown in FIGS. 5 and 6A and 6B.
Here, FIG. 5 is an exploded view showing the configuration of the unit cells constituting the fuel cell 16, and FIG. 6 is a diagram showing the configuration of the fuel cell separator 5 shown in FIG. 6A is a plan view, and FIG. 6B is a cross-sectional view taken along line XY in FIG. 6A.

固体高分子形燃料電池１６は、固体高分子電解質膜６とアノード（燃料電極）７とカソード（酸化剤電極）８とからなるＭＥＡ（ｍｅｍｂｒａｎｅ ｅｌｅｃｔｒｏｄｅ ａｓｓｅｍｂｌｙ：膜／電極接合体）を２枚の燃料電池用セパレータ５によって、ガスケット９を介して挟持した構成１０を単位セルとして、これを数十個〜数百個積層し、アノード７に流体である燃料ガス（水素ガス）を、カソード８に流体である酸化ガス（酸素ガス）を供給することにより、外部回路から電流を取り出す構成となっている。そして、燃料電池用セパレータ５は、図６（ａ）、（ｂ）に示すように、薄肉の板状体の片面又は両面に複数個のガス供給排出用溝１１と、ガス供給排出用溝１１に燃料ガス又は酸化ガスを供給する開口部１２と、ＭＥＡを並設するための固定穴１３とを有する形状であり、燃料電池内を流れる燃料ガスと酸化ガスとが混合しないように分離する働きを有すると共に、ＭＥＡで発電した電気エネルギーを外部へ伝達したり、ＭＥＡで生じた熱を外部へ放熱したりするという重要な役割を担っている。   The polymer electrolyte fuel cell 16 is composed of a membrane / electrode assembly (MEA) composed of a solid polymer electrolyte membrane 6, an anode (fuel electrode) 7, and a cathode (oxidant electrode) 8. The structure 10 sandwiched by the battery separator 5 via the gasket 9 is used as a unit cell, and several tens to several hundreds of the unit cells are stacked. A fuel gas (hydrogen gas) as a fluid is supplied to the anode 7 and a fluid is supplied to the cathode 8. By supplying an oxidizing gas (oxygen gas), current is extracted from an external circuit. As shown in FIGS. 6A and 6B, the fuel cell separator 5 includes a plurality of gas supply / discharge grooves 11 and gas supply / discharge grooves 11 on one surface or both surfaces of a thin plate-like body. Is provided with an opening 12 for supplying fuel gas or oxidant gas and a fixing hole 13 for arranging the MEAs in parallel, and the fuel gas and oxidant gas flowing in the fuel cell are separated so as not to be mixed. And plays an important role of transmitting the electric energy generated by the MEA to the outside and radiating the heat generated by the MEA to the outside.

そのため、固体高分子形燃料電池用セパレータに求められる特性としては、特に、組立時におけるボルト締め付けや自動車などの振動に対しても割れない強度やフレキシブル性（可撓性）があること、燃料電池内の使用環境（高温、腐食性、低ｐＨ等）下における長期の耐久性（耐食性）があること、発電ロスを少なくするために電気抵抗を小さくて導電性に優れること、及び燃料ガスと酸化ガスをその両面で完全に分離して電極に供給するためのガス不透過性などの特性が求められている。   Therefore, the characteristics required of a polymer electrolyte fuel cell separator are, in particular, strength and flexibility (flexibility) that do not break even with bolt tightening during assembly or vibration of automobiles, etc. Have long-term durability (corrosion resistance) under the usage environment (high temperature, corrosiveness, low pH, etc.), low electrical resistance to reduce power generation loss, excellent electrical conductivity, and fuel gas and oxidation There is a demand for characteristics such as gas impermeability for completely separating the gas on both sides and supplying the gas to the electrode.

そして、このような要請に応えるために、以下に示すような様々な取り組みが行われている。
すなわち、固体高分子形燃料電池用セパレータとしては、ガラス状カーボンを中心としたカーボン製セパレータが従来から検討されていたが、このようなカーボン製のセパレータは、非常に割れやすく、可撓性・柔軟性が乏しく、また、車載用の燃料電池等としての用途を考えると、ガスバリア性・気密性に乏しく、更には、小型化が困難で加工コストも高い等といった問題もあることから、実用性に問題があるとされている。 In order to respond to such a request, various approaches as described below are being carried out.
That is, as a separator for a polymer electrolyte fuel cell, a carbon separator centered on glassy carbon has been conventionally studied. However, such a carbon separator is very fragile, flexible, Insufficient flexibility, and considering its use as an in-vehicle fuel cell, it has poor gas barrier properties and airtightness, and further, there are problems such as difficulty in miniaturization and high processing costs. There is a problem.

そのため、カーボン製セパレータに替えて、金属素材を適用する試みがなされ、特に、機械的強度、加工性、コストの点から、ステンレス鋼を素材とするセパレータが検討されているが、一般的にステンレス鋼表面にはその製造過程などに起因して形成された比較的厚い不動態皮膜を有しており、耐食性に優れるものの、この不動態皮膜は電気抵抗が大きくて導電性に乏しい。そのため、このようにステンレス鋼製のセパレータの導電性を向上（接触抵抗を低減）させる観点から、いくつかの報告がなされている。   Therefore, attempts have been made to apply metal materials instead of carbon separators. In particular, separators made of stainless steel have been studied from the viewpoint of mechanical strength, workability, and cost. Although the steel surface has a relatively thick passive film formed due to its manufacturing process and the like, and has excellent corrosion resistance, this passive film has high electrical resistance and poor electrical conductivity. Therefore, several reports have been made from the viewpoint of improving the conductivity of the stainless steel separator (reducing contact resistance).

例えば、特許文献１においては、フッ素イオンを含有した溶液にステンレス鋼を所定の溶解速度で浸漬し、表面の不動態被膜にフッ素を含有させて導電性を改善した(接触抵抗の低い)通電部品用ステンレス鋼が提案されているが、この通電部品用ステンレス鋼においては、フッ素イオンが不動態被膜中に存在するため、ステンレス鋼に劣化が起き易く、その結果として燃料電池の使用環境下で腐食し易く、使用途中での劣化が避けられない。   For example, in Patent Document 1, a conductive part in which stainless steel is immersed in a solution containing fluorine ions at a predetermined dissolution rate and fluorine is contained in a passive film on the surface to improve conductivity (low contact resistance). Stainless steel has been proposed, but in this stainless steel for current-carrying parts, fluorine ions are present in the passive film, so the stainless steel is prone to deterioration, and as a result, it corrodes in the fuel cell environment. It is easy to do and deterioration during use is inevitable.

また、特許文献２においては、オーステナイト系ステンレス鋼の表面を、第１の酸と第２の酸とで処理することにより、表面にクロム酸化物組成比が大きい不導体被膜を形成して得られた固体高分子形燃料電池セパレータ用のステンレス部材が提案されており、耐食性に優れ、かつ、接触抵抗が低いとされているが、このステンレス部材においては、クロム酸化物組成比が大きくて不導体被膜の抵抗率が高いだけでなく、フッ化水素酸及び硝酸（以下、「フッ硝酸」等と表す場合がある。）溶液中の過多な硝酸に起因して表面の酸化が起き易く、このステンレス部材だけをセパレータとして用いると、経時的に接触抵抗が変化し易いという問題がある。   Moreover, in patent document 2, it is obtained by processing the surface of austenitic stainless steel with the 1st acid and the 2nd acid, and forming the non-conductive film with a large chromium oxide composition ratio on the surface. A stainless steel member for a polymer electrolyte fuel cell separator has been proposed, which is said to have excellent corrosion resistance and low contact resistance. However, this stainless steel member has a high chromium oxide composition ratio and is non-conductive. This stainless steel not only has high coating resistivity, but also tends to oxidize the surface due to excessive nitric acid in hydrofluoric acid and nitric acid (hereinafter sometimes referred to as “fluoric nitric acid”). When only a member is used as a separator, there is a problem that the contact resistance easily changes with time.

更に、特許文献３においては、16質量%のクロムを含有するステンレス鋼に対して、電解処理を施した後、フッ化水素酸やフッ硝酸などのフッ素を含有する溶液に浸漬することで、接触抵抗が低減され、且つ耐食性にも優れる燃料電池セパレータ用ステンレス鋼が提案されているが、このステンレス鋼についても、不動態皮膜を除去するための処理を行ったあとは、何らの処理も行なわれていないため表面の酸化が起き易く、このステンレス部材だけをセパレータとして用いると、燃料電池の使用環境下で経時的に接触抵抗が変化し易いという問題がある。   Furthermore, in Patent Document 3, after stainless steel containing 16% by mass of chromium is subjected to electrolytic treatment, it is immersed in a solution containing fluorine such as hydrofluoric acid or hydrofluoric acid, thereby contacting the steel. Although stainless steel for fuel cell separators with reduced resistance and excellent corrosion resistance has been proposed, this stainless steel is also subjected to any treatment after it has been treated to remove the passive film. Therefore, oxidation of the surface is likely to occur, and when only this stainless steel member is used as a separator, there is a problem that the contact resistance is likely to change over time under the usage environment of the fuel cell.

このように、ステンレス鋼製のセパレータについても、例えば、燃料電池の使用環境下においては、十分な導電性や耐食性を経時的に発揮させることは難しく、また、割れや亀裂などの発生がなく可撓性にも優れて、それらを満足するステンレス鋼製のセパレータはこれまでは見出されていない。
一方で、金属製の基材に対して、炭素粉末と樹脂粉末とを混合した混合粉末を含んだ塗料を塗布して、金属基材の表面に導電性塗膜を形成した塗装金属や、前記混合粉末を成型したカーボン板を金属製の基材に積層させた複合カーボン板を、燃料電池用のセパレータとして使用することもこれまで検討されている。 Thus, for a stainless steel separator, for example, in a fuel cell environment, it is difficult to exhibit sufficient conductivity and corrosion resistance over time, and cracks and cracks may not occur. A stainless steel separator that excels in flexibility and satisfies them has not been found so far.
On the other hand, a coating material containing a mixed powder obtained by mixing carbon powder and resin powder is applied to a metal base material, and a conductive metal film is formed on the surface of the metal base material. The use of a composite carbon plate obtained by laminating a carbon plate obtained by molding a mixed powder on a metal base material as a separator for a fuel cell has been studied.

例えば、特許文献４においては、酸洗したステンレス鋼板の基材表面に、グラファイト粉末及びカーボンブラックの混合粉末からなる導電剤とポリオレフィン樹脂とを含む水分散性塗料を塗布した表面塗装金属セパレータ材料が提案されており、塗膜欠陥がなく塗膜密着性や接触抵抗を向上させたものであるとされているが、この表面塗装金属セパレータ材料においては、ステンレス表面の不動態皮膜を酸洗により除去する方法を用いたものであるものの、具体的に使用されている塩酸洗浄では十分ではなく、導電材との間が接触し難くなり、所望の低い接触抵抗を達成できないという問題や、また、塗装部分の形成材料が黒鉛粒子、カーボンブラックという組合せでは可撓性に劣るといった問題がある。   For example, in Patent Document 4, there is a surface-coated metal separator material in which a water-dispersible paint containing a conductive agent and a polyolefin resin containing a mixed powder of graphite powder and carbon black is applied to the surface of a pickled stainless steel plate. It has been proposed to improve coating adhesion and contact resistance with no coating film defects, but in this surface-coated metal separator material, the passive film on the stainless steel surface is removed by pickling. However, the hydrochloric acid cleaning that is specifically used is not sufficient, and it becomes difficult to contact the conductive material, and the desired low contact resistance cannot be achieved. There is a problem that the combination of the part forming material of graphite particles and carbon black is inferior in flexibility.

同じく塗装金属を用いた特許文献５においては、ステンレス鋼板の表面に、カーボンブラック及びグラファイトの混合物からなる導電剤とエポキシ樹脂又はフェノール樹脂からなる熱硬化性樹脂とを含む導電性塗料を塗布した塗装ステンレス鋼板が提案されているが、この塗装ステンレス鋼板は、衝撃に対して比較的弱くて割れ易く、その結果、例えば自動車用等の固体高分子形燃料電池のセパレータとして使用中の震動等に起因して表面の塗膜に亀裂が入り、燃料電池の使用環境下において、腐食してステンレス鋼板と塗膜との間の接触抵抗が大きく悪化することが懸念される。   Similarly, in Patent Document 5 using a coated metal, the surface of a stainless steel plate is coated with a conductive paint containing a conductive agent made of a mixture of carbon black and graphite and a thermosetting resin made of epoxy resin or phenol resin. Stainless steel sheet has been proposed, but this coated stainless steel sheet is relatively weak against impact and easily cracked. As a result, it is caused by vibrations in use as a separator for polymer electrolyte fuel cells for automobiles, etc. Then, there is a concern that the coating film on the surface cracks and corrodes under the environment where the fuel cell is used, and the contact resistance between the stainless steel plate and the coating film is greatly deteriorated.

更に、特許文献６においては、炭素粉末として膨張黒鉛粉末と黒鉛粉末とを特定の割合で混合し、これにアンモニアを含まない特定量のフェノール樹脂とを共に圧縮成型したカーボン板を金属基材に積層した複合カーボン板が提案されているが、この複合カーボン板においては、使用されている金属基材であるステンレス鋼は何らの処理はなされていないことから、接触抵抗が比較的高くなる可能性があるといった問題がある。また、この特許文献６で使用されているカーボン板は、膨張黒鉛粉末の量が３０ｗｔ％以上と多く使用されているため、粒子内に空隙を多く持つ膨張黒鉛の中に樹脂が包埋してしまい、それによりカーボン板と金属箔との接着力が低下して接触抵抗が増加してしまうことが懸念される。   Further, in Patent Document 6, an expanded graphite powder and a graphite powder are mixed at a specific ratio as carbon powder, and a carbon plate compression-molded together with a specific amount of phenol resin not containing ammonia is used as a metal substrate. A laminated composite carbon plate has been proposed, but in this composite carbon plate, stainless steel, which is the metal substrate used, has not been treated at all, so the contact resistance may be relatively high. There is a problem that there is. Moreover, since the carbon plate used in this Patent Document 6 is used in an amount of 30 wt% or more of the expanded graphite powder, the resin is embedded in the expanded graphite having many voids in the particles. Therefore, there is a concern that the adhesive force between the carbon plate and the metal foil is reduced, thereby increasing the contact resistance.

特開2010-013684号公報JP 2010-013684 特開2013-129896号公報JP 2013-129896 WO 2012/098689号公報WO 2012/098689 Publication 特開平11-345618号公報Japanese Patent Laid-Open No. 11-345618 特開2010-248474号公報JP 2010-248474 A WO 2014/148649号公報WO 2014/148649

このように、燃料電池用のセパレータとして、カーボン製、金属（ステンレス鋼板）製、又はカーボンと金属とを積層させたものがそれぞれ提案されてきたものの、いずれも実用上で要求されるフレキシブル性（可撓性）、耐久性（耐食性）及び導電性などの特性を全て満足するものは見出されていなかった。
そこで、このような状況の下、本発明者らが鋭意検討した結果、ステンレス鋼製の板状基材の表面には、ＥＤＳ元素分析で測定された酸素(O)と鉄(Fe)との元素比(O/Fe)が所定の範囲である酸素欠損性の酸化皮膜を形成し、導電性が発現する酸素欠損性の酸化皮膜を介して板状基材の表面にカーボン層を積層することにより、導電性、耐食性及び可撓性が共に優れたステンレス鋼板カーボン複合材が得られることを見出し、本発明を完成した。 Thus, although carbon separators, metal (stainless steel plates), or carbon and metal laminates have been proposed as separators for fuel cells, respectively, the flexibility required in practice ( No one satisfying all the characteristics such as flexibility), durability (corrosion resistance) and conductivity has been found.
Thus, as a result of the intensive studies by the present inventors under such circumstances, the surface of the stainless steel plate-like base material has oxygen (O) and iron (Fe) measured by EDS elemental analysis. Forming an oxygen-deficient oxide film with an element ratio (O / Fe) in the specified range, and laminating a carbon layer on the surface of the plate-like substrate via an oxygen-deficient oxide film that exhibits conductivity Thus, the inventors have found that a stainless steel plate carbon composite having excellent conductivity, corrosion resistance and flexibility can be obtained, and the present invention has been completed.

従って、本発明の目的は、例えば、固体高分子形燃料電池用等の燃料電池用セパレータを始めとして、レドックスフロー型２次電池用の集電板や、石油精製用、石油化学用等のガスケットやパッキン等においても使用可能な、導電性、耐食性及び可撓性等が共に優れたステンレス鋼板カーボン複合材を提供することにある。
また、本発明の他の目的は、当該、導電性、耐食性及び可撓性等が共に優れたステンレス鋼板カーボン複合材の製造方法を提供することにある。 Accordingly, an object of the present invention is to collect a current collector plate for a redox flow type secondary battery, such as a separator for a fuel cell such as a polymer electrolyte fuel cell, and a gasket for oil refining or petrochemical. Another object of the present invention is to provide a stainless steel plate carbon composite material excellent in conductivity, corrosion resistance, flexibility, and the like that can be used in packing and packing.
Another object of the present invention is to provide a method for producing a stainless steel plate carbon composite having excellent conductivity, corrosion resistance, flexibility and the like.

すなわち、本発明の要旨は、以下の通りである。
(1) ステンレス鋼製の板状基材の少なくとも片面に、炭素粉末と熱可塑性樹脂又は熱硬化性樹脂からなる樹脂粉末とを含むカーボン層が積層されたステンレス鋼板カーボン複合材であり、前記カーボン層は、前記炭素粉末(C)と樹脂粉末(R)とを体積比(C/R)で６／４〜９／１の割合で含み、且つ前記板状基材の表面に形成された酸化皮膜を介して積層されており、また、前記酸化皮膜はＥＤＳ元素分析で測定された酸素(O)と鉄(Fe)との元素比(O/Fe)が０．０７〜０．２６の範囲内であることを特徴とするステンレス鋼板カーボン複合材。
(2) 前記板状基材が、オーステナイト系ステンレス鋼又はフェライト系ステンレス鋼であることを特徴とする前記(1)に記載のステンレス鋼板カーボン複合材。
(3) 前記熱可塑性樹脂からなる樹脂粉末が、ポリプロピレン樹脂、ポリエチレン樹脂、ポリアミド樹脂、ポリフェニレンスルフィド樹脂、ポリメチルペンテン樹脂、ポリエーテルエーテルケトン樹脂、ポリフェニレンエーテル樹脂、液晶ポリマー樹脂、ポリアミドイミド樹脂、ポリスルホン樹脂、ポリエチレンテレフタレート樹脂及びポリブチレンテレフタレート樹脂からなる群から選ばれたいずれか１種か又は２種以上の混合物からなる樹脂粉末であることを特徴とする前記(1)又は(2)に記載のステンレス鋼板カーボン複合材。
(4) 前記熱硬化性樹脂からなる樹脂粉末が、フェノール樹脂及びエポキシ樹脂からなる群から選ばれたいずれか１種か又は２種以上の混合物からなる樹脂粉末であることを特徴とする前記(1)又は(2)に記載のステンレス鋼板カーボン複合材。
(5) 前記板状基材の表面とこの表面に積層されるカーボン層との間が、接着剤層を介して接合されていることを特徴とする前記(1)〜(4)のいずれかに記載のステンレス鋼板カーボン複合材。
(6) ステンレス鋼製の板状基材の少なくとも片面に、炭素粉末と熱可塑性樹脂又は熱硬化性樹脂からなる樹脂粉末とを含むカーボン層を積層してステンレス鋼板カーボン複合材を製造する方法であり、
前記板状基材の少なくとも片面に、表面処理液として、１〜８質量%のフッ化水素酸水溶液、又は、フッ化水素酸(HF)と硝酸(HNO3)との濃度比(HF/HNO3)が２以上であってＨＦ濃度が２質量%以上のフッ化水素酸・硝酸混合水溶液を接触させる表面処理工程と、
この表面処理後の板状基材の表面に前記炭素粉末(C)と樹脂粉末(R)との体積比(C/R)が６／４〜９／１の割合であるカーボン層を積層する積層工程とを有することを特徴とするステンレス鋼板カーボン複合材の製造方法。
(7) 前記表面処理工程に先駆けて、前記板状基材の少なくとも片面に、前処理液として、酸濃度２５質量%以上及び塩化鉄濃度２０質量%以上の塩化鉄含有酸水溶液を接触させる前処理工程を有することを特徴とする前記(6)に記載のステンレス鋼板カーボン複合材の製造方法。
(8) 前記積層工程では、前記炭素粉末と樹脂粉末とを含む粉末混合物をホットプレスしてカーボン層を形成し、得られたカーボン層を表面処理後の板状基材の表面にホットプレスして積層することを特徴とする前記(6)又は(7)に記載のステンレス鋼板カーボン複合材の製造方法。
(9) 前記積層工程に先駆けて、表面処理後の板状基材の表面に接着剤組成物を塗布して接着剤層を形成する接着剤層形成工程を有し、積層工程ではこの接着剤層を介して表面処理後の板状基材の表面にカーボン層が積層されることを特徴とする前記(6)〜(8)のいずれかに記載のステンレス鋼板カーボン複合材の製造方法。
(10) 前記熱可塑性樹脂からなる樹脂粉末が、ポリプロピレン樹脂、ポリエチレン樹脂、ポリアミド樹脂、ポリフェニレンスルフィド樹脂、ポリメチルペンテン樹脂、ポリエーテルエーテルケトン樹脂、ポリフェニレンエーテル樹脂、液晶ポリマー樹脂、ポリアミドイミド樹脂、ポリスルホン樹脂、ポリエチレンテレフタレート樹脂及びポリブチレンテレフタレート樹脂からなる群から選ばれたいずれか１種か又は２種以上の混合物からなる樹脂粉末であることを特徴とする前記(6)〜(9)のいずれかに記載のステンレス鋼板カーボン複合材の製造方法。
(11) 前記熱硬化性樹脂からなる樹脂粉末が、フェノール樹脂及びエポキシ樹脂からなる群から選ばれたいずれか１種か又は２種以上の混合物からなる樹脂粉末であることを特徴とする前記(6)〜(9)のいずれかに記載のステンレス鋼板カーボン複合材の製造方法。
(12) 前記板状基材が、オーステナイト系ステンレス鋼又はフェライト系ステンレス鋼であることを特徴とする前記(6)〜(11)のいずれかに記載のステンレス鋼板カーボン複合材の製造方法。 That is, the gist of the present invention is as follows.
(1) A stainless steel plate carbon composite in which a carbon layer containing carbon powder and a resin powder made of a thermoplastic resin or a thermosetting resin is laminated on at least one surface of a plate-like substrate made of stainless steel, the carbon The layer includes the carbon powder (C) and the resin powder (R) at a volume ratio (C / R) of 6/4 to 9/1, and an oxidation formed on the surface of the plate-like substrate. The oxide film is in the range of the element ratio (O / Fe) of oxygen (O) and iron (Fe) measured by EDS elemental analysis in the range of 0.07 to 0.26. A stainless steel plate carbon composite material characterized by being within.
(2) The stainless steel plate carbon composite material according to (1), wherein the plate-like base material is austenitic stainless steel or ferritic stainless steel.
(3) The resin powder comprising the thermoplastic resin is polypropylene resin, polyethylene resin, polyamide resin, polyphenylene sulfide resin, polymethylpentene resin, polyether ether ketone resin, polyphenylene ether resin, liquid crystal polymer resin, polyamideimide resin, polysulfone. The resin powder according to (1) or (2) above, which is a resin powder made of any one selected from the group consisting of a resin, a polyethylene terephthalate resin and a polybutylene terephthalate resin, or a mixture of two or more. Stainless steel plate carbon composite material.
(4) The resin powder comprising the thermosetting resin is a resin powder comprising any one kind or a mixture of two or more kinds selected from the group consisting of a phenol resin and an epoxy resin. The stainless steel plate carbon composite material according to 1) or (2).
(5) Any one of the above (1) to (4), wherein the surface of the plate-like substrate and the carbon layer laminated on the surface are bonded via an adhesive layer The stainless steel plate carbon composite material described in 1.
(6) A method for producing a stainless steel plate carbon composite by laminating a carbon layer containing carbon powder and a resin powder made of a thermoplastic resin or a thermosetting resin on at least one surface of a stainless steel plate-like substrate. Yes,
On at least one surface of the plate-like substrate, as a surface treatment liquid, a 1 to 8 mass% hydrofluoric acid aqueous solution, or a concentration ratio of hydrofluoric acid (HF) and nitric acid (HNO 3 ) (HF / HNO 3 ) a surface treatment step in which a hydrofluoric acid / nitric acid mixed aqueous solution having 2 or more and an HF concentration of 2% by mass or more is brought into contact;
A carbon layer having a volume ratio (C / R) of the carbon powder (C) to the resin powder (R) of 6/4 to 9/1 is laminated on the surface of the plate-like substrate after the surface treatment. A method for producing a carbon composite material of a stainless steel plate, comprising a lamination step.
(7) Before contacting the surface treatment step, at least one surface of the plate-shaped substrate is brought into contact with an aqueous iron chloride-containing acid solution having an acid concentration of 25% by mass or more and an iron chloride concentration of 20% by mass or more as a pretreatment liquid. The method for producing a stainless steel plate carbon composite material according to (6), further comprising a treatment step.
(8) In the laminating step, a powder mixture containing the carbon powder and the resin powder is hot pressed to form a carbon layer, and the obtained carbon layer is hot pressed onto the surface of the plate-like substrate after the surface treatment. The method for producing a carbon composite material for a stainless steel plate according to the above (6) or (7), wherein the carbon composite material is laminated.
(9) Prior to the laminating step, an adhesive layer forming step of forming an adhesive layer by applying an adhesive composition to the surface of the plate-like substrate after the surface treatment is provided. The method for producing a stainless steel plate carbon composite according to any one of (6) to (8), wherein a carbon layer is laminated on the surface of the plate-like substrate after the surface treatment via the layer.
(10) The resin powder made of the thermoplastic resin is polypropylene resin, polyethylene resin, polyamide resin, polyphenylene sulfide resin, polymethylpentene resin, polyether ether ketone resin, polyphenylene ether resin, liquid crystal polymer resin, polyamideimide resin, polysulfone. Any one of the above (6) to (9), which is a resin powder made of any one or a mixture of two or more selected from the group consisting of a resin, a polyethylene terephthalate resin and a polybutylene terephthalate resin The manufacturing method of the stainless steel plate carbon composite material of description.
(11) The resin powder composed of the thermosetting resin is a resin powder composed of any one kind or a mixture of two or more kinds selected from the group consisting of a phenol resin and an epoxy resin. A method for producing a stainless steel plate carbon composite material according to any one of 6) to (9).
(12) The method for producing a stainless steel plate carbon composite according to any one of (6) to (11), wherein the plate-like base material is austenitic stainless steel or ferritic stainless steel.

本発明によれば、導電性、耐食性及び可撓性が共に優れたステンレス鋼板カーボン複合材を提供することができる。
また、本発明によれば、導電性、耐食性及び可撓性が共に優れたステンレス鋼板カーボン複合材の製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the stainless steel plate carbon composite material which was excellent in electroconductivity, corrosion resistance, and flexibility can be provided.
Moreover, according to this invention, the manufacturing method of the stainless steel plate carbon composite material which was excellent in electroconductivity, corrosion resistance, and flexibility can be provided.

図１は、ステンレス鋼製板状基材及びその表面に形成された酸化皮膜のＴＥＭ観察断面を示す説明図（写真）である。FIG. 1 is an explanatory view (photograph) showing a TEM observation cross section of a stainless steel plate-like substrate and an oxide film formed on the surface thereof. 図２はカーボン層又はステンレス鋼板カーボン複合材を製造するための成型方法の概略説明図である。FIG. 2 is a schematic explanatory diagram of a molding method for producing a carbon layer or a stainless steel plate carbon composite material. 図３は、本発明のステンレス鋼板カーボン複合材の製造におけるカーボン層、接着剤層及びステンレス鋼製の板状基材の積層方法の概略説明図である。FIG. 3 is a schematic explanatory view of a method for laminating a carbon layer, an adhesive layer and a stainless steel plate-like substrate in the production of the stainless steel plate carbon composite of the present invention. 図４は、接触抵抗を測定する方法の概略説明図である。FIG. 4 is a schematic explanatory diagram of a method for measuring contact resistance. 図５は、燃料電池を構成する単位セルの構成を示す分解図である。FIG. 5 is an exploded view showing a configuration of a unit cell constituting the fuel cell. 図６(a)は燃料電池用セパレータの一例を示す平面図であり、図６(b)は図６(a)の線Ｘ−Ｙ断面を示す断面図である。6 (a) is a plan view showing an example of a fuel cell separator, and FIG. 6 (b) is a cross-sectional view taken along line XY of FIG. 6 (a).

以下、本発明のステンレス鋼板カーボン複合材及びその製造方法について、詳細に説明する。
本発明のステンレス鋼板カーボン複合材は、ステンレス鋼製の板状基材の少なくとも片面に、炭素粉末と熱可塑性樹脂又は熱硬化性樹脂からなる樹脂粉末とを含むカーボン層が積層されたステンレス鋼板カーボン複合材であって、前記カーボン層は、前記炭素粉末(C)と樹脂粉末(R)とを体積比(C/R)で６／４〜９／１の割合で含み、且つ板状基材の表面に形成された酸化皮膜を介して積層されており、また、前記酸化皮膜はＥＤＳ元素分析で測定された酸素(O)と鉄(Fe)との元素比(O/Fe)が０．０７〜０．２６の範囲内であることにその特徴を有する。 Hereinafter, the stainless steel plate carbon composite material of the present invention and the manufacturing method thereof will be described in detail.
The stainless steel plate carbon composite material of the present invention is a stainless steel plate carbon in which a carbon layer containing carbon powder and a resin powder made of a thermoplastic resin or a thermosetting resin is laminated on at least one surface of a stainless steel plate-like substrate. It is a composite material, and the carbon layer includes the carbon powder (C) and the resin powder (R) at a volume ratio (C / R) of 6/4 to 9/1, and a plate-like base material In addition, the oxide film has an element ratio (O / Fe) of oxygen (O) and iron (Fe) measured by EDS elemental analysis of 0. It is characterized by being in the range of 07 to 0.26.

本発明において、板状基材を構成するステンレス鋼については、特に制限されるものではないが、好ましくは、オーステナイト系ステンレス鋼又はフェライト系ステンレス鋼であるのがよい。オーステナイト系ステンレス鋼については、例えばSUS316Lは質量%割合でＣ：０．０１５、Ｓi：０．５６、Ｍn：０．８４、Ｐ：０．０２７、Ｓ：０．００１、Ｃr：１７．１４、Ｎi：１２．１１、Ｍo：２．０３、及び、残部：Ｆe及び微量の不可避的不純物からなる組成を有し、また、フェライト系ステンレス鋼については、例えばSUS430は質量%割合でＣ：０．０８、Ｓi：０．２８、Ｍn：０．６４、Ｐ：０．０２４、Ｓ：０．００１、Ｃr：１６．２６、Ｎi：０．０９、及び、残部：Ｆe及び微量の不可避的不純物からなる組成を有し、SUS444は質量%割合でＣ：０．０４、Ｓi：０．１３、Ｍn：０．１３、Ｐ：０．０２８、Ｓ：０．００１、Ｃr：１９．１、Ｍo：１．８、Ｎb：０．１８、Ｔi：０．１４、Ｎ：０．０１２、及び、残部：Ｆe及び微量の不可避的不純物からなる組成を有する。なお、このようなステンレス鋼製の板状基材の表面に形成された酸化皮膜は、素材のステンレス鋼に含有される元素と酸素(O)とから構成されるが、このうち含有比率の最も多いのがＦeとＯとからなる鉄酸化物であり、酸化皮膜の性質は、実質的にこの鉄酸化物の性質に依存するものと考えられる。非酸化性の酸を過多に含む溶液で処理したステンレスは大気中での酸化皮膜形成の際に、酸素分子の拡散律速により酸素欠損性の酸化皮膜が形成され易くなるため、時間経過のなかでも導電性が劣化しない。一方、酸化性の酸が過多に含む溶液で処理すると、金属の溶解と同時に酸化皮膜が表面に形成されるため、比較的薄く緻密な酸素欠損の少ない酸化皮膜が形成されやすい。この酸化皮膜は緻密であるため時間経過に伴う酸化皮膜厚みの増加は非常に小さいが、酸化皮膜の少しの成長でも導電性の悪化程度は大きくなってしまう。   In the present invention, the stainless steel constituting the plate-like substrate is not particularly limited, but is preferably austenitic stainless steel or ferritic stainless steel. As for austenitic stainless steel, for example, SUS316L is C: 0.015, Si: 0.56, Mn: 0.84, P: 0.027, S: 0.001, Cr: 17.14 in mass percentages. Ni: 12.11, Mo: 2.03, and the balance: Fe and a small amount of unavoidable impurities, and for ferritic stainless steel, for example, SUS430 is in a mass% ratio of C: 0.00. 08, Si: 0.28, Mn: 0.64, P: 0.024, S: 0.001, Cr: 16.26, Ni: 0.09, and the balance: Fe and trace amounts of inevitable impurities SUS444 has the following composition: C: 0.04, Si: 0.13, Mn: 0.13, P: 0.028, S: 0.001, Cr: 19.1, Mo: 1.8, Nb: 0.18, Ti: 0.14, N: 0.012, and the balance: Fe and trace amounts It has a composition consisting of inevitable impurities. The oxide film formed on the surface of such a stainless steel plate-like substrate is composed of elements and oxygen (O) contained in the material stainless steel, of which the content ratio is the most. Many of them are iron oxides composed of Fe and O, and the properties of the oxide film are considered to substantially depend on the properties of the iron oxides. Stainless steel treated with a solution containing an excessive amount of non-oxidizing acid tends to form an oxygen-deficient oxide film due to the diffusion-controlled diffusion of oxygen molecules when forming an oxide film in the atmosphere. Conductivity does not deteriorate. On the other hand, when the treatment is performed with a solution containing an excessive amount of an oxidizing acid, an oxide film is formed on the surface simultaneously with the dissolution of the metal, so that a relatively thin and dense oxide film with little oxygen deficiency is easily formed. Since this oxide film is dense, the increase in the oxide film thickness with the passage of time is very small. However, even if the oxide film grows a little, the degree of deterioration of conductivity increases.

そして、前記板状基材の表面に形成される酸化皮膜については、ＥＤＳ元素分析で測定されたその酸素(O)と鉄(Fe)との元素比(O/Fe)が０．０７以上０．２６以下であり、好ましくは０．０７以上０．２０以下であるのがよい。また、この酸化皮膜の厚さについては、通常６μm以上２５μm以下である。この元素比(O/Fe)が０．０７より小さいと酸化皮膜の耐食性が低下し、その結果導電性も劣化する問題がある。また、この元素比(O/Fe)が０．２６を超えて高くなると板状基材の表面に形成された酸化皮膜の導電性が低下し、得られたステンレス鋼板カーボン複合材の接触抵抗が１０mΩ・cm2を超えて高くなる虞がある。また、この元素比(O/Fe)が０．２０以下になると、酸化皮膜は更にその導電性が向上し、得られたステンレス鋼板カーボン複合材の接触抵抗が９mΩ・cm2よりも小さくなるという利点が生じる。また、酸化皮膜の厚さが、６μmよりも小さくなると燃料電池作動環境中の腐食性液に対する耐久性が低下するという虞があり、反対に、２５μmを超えて大きくなると接触抵抗が１０mΩ・cm2よりも高くなるという虞がある。 And about the oxide film formed in the surface of the said plate-shaped base material, the element ratio (O / Fe) of the oxygen (O) and iron (Fe) measured by EDS elemental analysis is 0.07 or more and 0 .26 or less, preferably 0.07 or more and 0.20 or less. The thickness of the oxide film is usually 6 μm or more and 25 μm or less. If this element ratio (O / Fe) is smaller than 0.07, the corrosion resistance of the oxide film is lowered, and as a result, there is a problem that the conductivity is deteriorated. Moreover, when this element ratio (O / Fe) becomes higher than 0.26, the conductivity of the oxide film formed on the surface of the plate-like substrate is lowered, and the contact resistance of the obtained stainless steel plate carbon composite is reduced. There is a risk that it will become higher than 10 mΩ · cm 2 . Further, when the element ratio (O / Fe) is 0.20 or less, the oxide film is further improved in conductivity, and the contact resistance of the obtained stainless steel plate carbon composite is less than 9 mΩ · cm 2. Benefits arise. In addition, if the thickness of the oxide film is smaller than 6 μm, the durability against the corrosive liquid in the operating environment of the fuel cell may be reduced. Conversely, if the thickness exceeds 25 μm, the contact resistance becomes 10 mΩ · cm 2. There is a risk that it will be higher.

ここで、本発明において、ＥＤＳ元素分析による板状基材表面の酸化皮膜における酸素(O)と鉄(Fe)との元素比(O/Fe)は、例えば、以下のように測定することができる。すなわち、集束イオンビーム（ＦＩＢ）法等の方法を用いて作製したＴＥＭ観察用の薄膜断面試料を観察し、エネルギー分散形Ｘ線分析装置（ＥＤＳ）により、酸化皮膜の領域を点分析し、ステンレス表面の酸化皮膜における酸素(O)のＫα線のカウントピーク面積と、ＦｅのＬα線のカウントピーク面積との面積比から算出する。測定点については、ＴＥＭ観察断面（図１）において、ＥＤＳ元素分析のＦｅのＫα線とＣｒのＫα線とのカウントピーク面積比が母材（ステンレス）のＦｅとＣｒとの組成比（モル比）になる層は図１中の基材(2)であるため、その基材の表面に形成されている皮膜層を酸化皮膜層〔図１中の(1)〕とし、その酸化皮膜層における任意の測定点を測定して平均値を求めることで元素比(O/Fe)として算出することができる。   Here, in the present invention, the element ratio (O / Fe) of oxygen (O) and iron (Fe) in the oxide film on the surface of the plate-like substrate by EDS elemental analysis can be measured, for example, as follows. it can. That is, a thin film cross-sectional sample for TEM observation produced using a method such as a focused ion beam (FIB) method is observed, and an oxide film region is point-analyzed by an energy dispersive X-ray analyzer (EDS), and stainless steel is obtained. It is calculated from the area ratio between the count peak area of the Kα line of oxygen (O) in the oxide film on the surface and the count peak area of the Lα line of Fe. Regarding the measurement point, in the TEM observation cross section (FIG. 1), the count peak area ratio between the Fe Kα line and the Cr Kα line in the EDS elemental analysis is the composition ratio (molar ratio) of Fe and Cr in the base material (stainless steel). 1) is the base material (2) in FIG. 1, and the film layer formed on the surface of the base material is the oxide film layer ((1) in FIG. 1). The element ratio (O / Fe) can be calculated by measuring an arbitrary measurement point and obtaining an average value.

なお、表面酸化皮膜厚みの測定方法については、例えば、電解放出型透過電子顕微鏡を用いて前記と同様にＴＥＭ観察断面（図１）から酸化皮膜(1)の厚みを任意に３か所以上測定し、その平均値を求めることにより、ステンレス表面の酸化皮膜厚みとする。   As for the method of measuring the thickness of the surface oxide film, for example, the thickness of the oxide film (1) is arbitrarily measured at three or more locations from the TEM observation cross section (FIG. 1) in the same manner as described above using a field emission type transmission electron microscope. And by calculating | requiring the average value, it is set as the oxide film thickness of the stainless steel surface.

本発明においては、前記板状基材がこのような表面状態を有するものであることから、好ましくはその接触抵抗が１０mΩ・cm2以下であることがよく、より好ましくは８mΩ・cm2以下、さらに好ましくは５mΩ・cm2以下、さらにより好ましくは３mΩ・cm2以下であり、尚且つ、その接触抵抗が３０日経過後においても実質的に変化しないことが好ましい。 In the present invention, since the plate-like substrate has such a surface state, the contact resistance is preferably 10 mΩ · cm 2 or less, more preferably 8 mΩ · cm 2 or less. More preferably, it is 5 mΩ · cm 2 or less, still more preferably 3 mΩ · cm 2 or less, and it is preferable that the contact resistance does not substantially change even after 30 days.

そして、このステンレス鋼製の板状基材の厚さについては、ステンレス鋼板カーボン複合材の用途によっても異なるので特に制限されるものではないが、通常１０μm以上１５０μm以下、好ましくは２０μm以上７０μm以下であるのがよく、この板状基材の厚さが１０μm未満であると機械的強度が低下する虞があり、反対に、１５０μmを超えて厚くなると柔軟性や可撓性の点で問題が生じる虞がある。   The thickness of the stainless steel plate-like substrate is not particularly limited because it varies depending on the use of the stainless steel plate carbon composite material, but is usually 10 μm or more and 150 μm or less, preferably 20 μm or more and 70 μm or less. If the thickness of the plate-like base material is less than 10 μm, the mechanical strength may be lowered. On the other hand, if the thickness exceeds 150 μm, a problem arises in terms of flexibility and flexibility. There is a fear.

また、上記の板状基材の表面に積層されるカーボン層については、炭素粉末と熱可塑性樹脂又は熱硬化性樹脂からなる樹脂粉末とを含むものであり、炭素粉末(C)と樹脂粉末(R)とを体積比(C/R)で６／４〜９／１、好ましくは７／３〜８／２の割合で含み、また、その厚さが０．０５mm以上２．０mm以下、好ましくは０．１mm以上１．０mm以下である。この炭素粉末(C)と樹脂粉末(R)との体積比(C/R)については、６／４より小さくなって炭素粉末の比率が低下すると導電性が低下する虞があり、反対に、９／１より大きくなると熱可塑性樹脂又は熱硬化性樹脂の比率が低いために柔軟性、可撓性および耐食性に劣る虞がある。また、カーボン層の厚さについては、０．０５mmより薄くなるとカーボン層の僅かなクラックから腐食が始まる可能性があり、反対に、２．０mmより厚くなると可撓性に悪影響を及ぼす可能性がある。   Further, the carbon layer laminated on the surface of the plate-shaped substrate includes carbon powder and a resin powder made of a thermoplastic resin or a thermosetting resin, and the carbon powder (C) and the resin powder ( R) in a volume ratio (C / R) of 6/4 to 9/1, preferably 7/3 to 8/2, and the thickness is 0.05 mm to 2.0 mm, preferably Is from 0.1 mm to 1.0 mm. Regarding the volume ratio (C / R) between the carbon powder (C) and the resin powder (R), if the ratio of the carbon powder is decreased to be smaller than 6/4, the conductivity may be decreased. If the ratio is larger than 9/1, the ratio of the thermoplastic resin or the thermosetting resin is low, so that the flexibility, flexibility, and corrosion resistance may be inferior. Also, regarding the thickness of the carbon layer, if it is thinner than 0.05 mm, corrosion may start from slight cracks in the carbon layer. Conversely, if it is thicker than 2.0 mm, flexibility may be adversely affected. is there.

ここで、前記カーボン層を形成する炭素粉末については、例えば、天然黒鉛粉末、人造黒鉛粉末、膨張黒鉛粉末、膨張化黒鉛粉末、鱗片状黒鉛粉末、球状黒鉛粉末などの粉末等から選ばれたいずれか１種か、又は２種以上の混合物を挙げることができ、好ましくは、可撓性及び導電性の点から、少なくとも膨張黒鉛粉末及び／又は膨張化黒鉛粉末を含む方が良い。その場合、当該膨張黒鉛粉末及び／又は膨張化黒鉛粉末の含有量は、炭素粉末と樹脂粉末との混合粉末中４体積％以上５１体積％未満が好ましく、５体積％以上２１体積％未満がより好ましい。４体積％未満の場合、可撓性が低くなる虞があり、一方、５１体積％以上の場合、本来、粒子同士、又は粒子と金属板との接着に寄与する樹脂がうまく機能することができずに、接触抵抗が大きくなる虞がある。なお、この範囲において炭素粉末中の膨張黒鉛粉末及び／又は膨張化黒鉛粉末の質量含有量としては、膨張黒鉛粉末及び／又は膨張化黒鉛粉末の真比重を他の黒鉛粉末と同じ２．２ｇ/ｃｍ３として計算することができ、５質量％以上７３質量％未満が好ましく、７質量％以上３０質量％未満がより好ましい。
そして、この炭素粉末の粒子径については、レーザー回折式粒度分布測定装置（例えば、Malvern社製商品名「Mastersizer2000」等）を用いて測定されるＤ50（累積５０体積%径）の値（平均粒子径）が、通常４μm以上２００μm以下、好ましくは10μm以上30μm以下であるのがよく、４μmより小さいと比表面積が大きいため樹脂が粒子同士またはSUS板との接着に使用されにくく可撓性に劣る虞があり、反対に、２００μmより大きくなるとカーボン層を形成する際に平滑な面が得られにくく不良率が大きくなる虞がある。 Here, the carbon powder forming the carbon layer may be any one selected from natural graphite powder, artificial graphite powder, expanded graphite powder, expanded graphite powder, scaly graphite powder, spherical graphite powder, and the like. 1 type, or 2 or more types of mixtures can be mentioned, Preferably, it is better to contain at least expanded graphite powder and / or expanded graphite powder from the viewpoint of flexibility and conductivity. In that case, the content of the expanded graphite powder and / or the expanded graphite powder is preferably 4% by volume or more and less than 51% by volume in the mixed powder of the carbon powder and the resin powder, and more preferably 5% by volume or more and less than 21% by volume. preferable. If it is less than 4% by volume, flexibility may be lowered. On the other hand, if it is 51% by volume or more, the resin that contributes to the adhesion between particles or between the particles and the metal plate can function properly. Otherwise, the contact resistance may increase. In this range, the mass content of the expanded graphite powder and / or the expanded graphite powder in the carbon powder is the same as the other graphite powders in terms of the true specific gravity of the expanded graphite powder and / or the expanded graphite powder of 2.2 g / It can be calculated as cm 3 and is preferably 5% by mass or more and less than 73% by mass, and more preferably 7% by mass or more and less than 30% by mass.
Then, the particle size of the carbon powder, a laser diffraction type particle size distribution measuring device (e.g., Malvern trade name "Mastersizer2000", etc.) the value of D 50 (cumulative 50% by volume diameter) as measured using the (average The particle diameter) is usually 4 μm or more and 200 μm or less, preferably 10 μm or more and 30 μm or less. If it is smaller than 4 μm, the specific surface area is large, and the resin is difficult to be used for adhesion between particles or SUS plate. On the other hand, when the thickness is larger than 200 μm, it is difficult to obtain a smooth surface when forming the carbon layer, and the defect rate may be increased.

また、前記カーボン層を形成する樹脂粉末については、熱可塑性樹脂であっても、また、熱硬化性樹脂であってもよく、前記熱可塑性樹脂としては、用途に応じて選択できるものであって特に制限されるものではないが、好ましくはポリプロピレン樹脂(PP)、ポリエチレン樹脂(PE)、ポリアミド樹脂(PA)、ポリフェニレンスルフィド樹脂(PPS)及びポリメチルペンテン樹脂(PMP)、ポリエーテルエーテルケトン樹脂(PEEK)、ポリフェニレンエーテル樹脂(PPE)、液晶ポリマー樹脂(LCP)、ポリアミドイミド樹脂(PAI)、ポリスルホン樹脂(PSU)、ポリエチレンテレフタレート樹脂(PET)及びポリブチレンテレフタレート樹脂(PBT)からなる群から選ばれたいずれか１種か又は２種以上の混合物を挙げることができ、また、前記熱硬化性樹脂についても、用途に応じて選択できるものであって特に制限されるものではないが、好ましくはフェノール樹脂及びエポキシ樹脂からなる群から選ばれたいずれか１種か又は２種以上の混合物を挙げることができる。   The resin powder forming the carbon layer may be a thermoplastic resin or a thermosetting resin, and the thermoplastic resin can be selected depending on the application. Although not particularly limited, preferably polypropylene resin (PP), polyethylene resin (PE), polyamide resin (PA), polyphenylene sulfide resin (PPS) and polymethylpentene resin (PMP), polyether ether ketone resin ( PEEK), polyphenylene ether resin (PPE), liquid crystal polymer resin (LCP), polyamideimide resin (PAI), polysulfone resin (PSU), polyethylene terephthalate resin (PET), and polybutylene terephthalate resin (PBT). Any one kind or a mixture of two or more kinds can be mentioned, and the thermosetting resin can also be selected depending on the application. Although it can be made and is not particularly limited, any one or a mixture of two or more selected from the group consisting of a phenol resin and an epoxy resin can be preferably mentioned.

ここで、前記PP、PE、PMPなどのポリオレフィン樹脂については、不飽和カルボン酸又はその誘導体の一部又は全部が当該ポリオレフィン樹脂にグラフトされて変性された変性ポリオレフィン樹脂を使用することも可能である。このような変性ポリオレフィン樹脂を使用することにより、カーボン層やそれを備えたステンレス鋼板カーボン複合材としての可撓性の向上や、ＳＵＳとの密着性及び炭素粒子との密着性が向上することが期待され、それにより接触抵抗が低下するため好ましい。そして、変性ポリオレフィン樹脂全体に占めるグラフト量（グラフト率）としては通常、０．０５〜１５質量％であることが好ましく、より好ましくは０．１〜１０質量％、さらに好ましくは０．１〜３質量％とされる。変性前のポリオレフィン樹脂にグラフトするために使用される前記不飽和カルボン酸又はその誘導体の具体的なものとしては、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、シトラコン酸、メサコン酸、無水マレイン酸、無水ハイミック酸、４−メチルシクロヘキセ−４−エン−１，２−ジカルボン酸無水物、α−エチルアクリル酸、フマール酸、テトラヒドロフタル酸、メチルテトラヒドロフタル酸、エンドシス−ビシクロ〔２，２，１〕ヘプト−５−エン−２，３−ジカルボン酸（ナジック酸〔商標〕）、ビシクロ［２．２．２］オクト−５−エン−２，３−ジカルボン酸無水物、１，２，３，４，５，８，９，１０−オクタヒドロナフタレン−２，３−ジカルボン酸無水物、２−オクタ−１，３−ジケトスピロ［４．４］ノン−７−エン、ビシクロ［２．２．１］ヘプト−５−エン−２，３−ジカルボン酸無水物、マレオピマル酸、テトラヒドロフタル酸無水物、ｘ−メチル−ビシクロ［２．２．１］ヘプト−５−エン−２，３−ジカルボン酸無水物、ｘ−メチル−ノルボルネン−５−エン−２，３−ジカルボン酸無水物（ｘはメチル基の置換位置を示す）、及びノルボルン−５−エン−２，３−ジカルボン酸無水物などを使用することができる。また、上記不飽和カルボン酸の酸ハライド、アミド、イミド、エステル等の誘導体なども使用可能である。これらの中では不飽和ジカルボン酸又はその酸無水物が好ましく、特に無水マレイン酸又は無水ハイミック酸が好ましい。このような不飽和カルボン酸又はその誘導体を１種単独で使用することもできるし、２種以上を組み合せて使用することもできる。ハロゲン基としては、塩素或いは臭素を好適に使用することができる。   Here, for the polyolefin resin such as PP, PE, PMP, it is also possible to use a modified polyolefin resin in which a part or all of the unsaturated carboxylic acid or its derivative is grafted on the polyolefin resin. . By using such a modified polyolefin resin, it is possible to improve the flexibility of the carbon layer and the stainless steel plate carbon composite provided with the carbon layer, and to improve the adhesion with SUS and the adhesion with carbon particles. It is preferred because it is expected and thereby reduces contact resistance. And as graft amount (graft ratio) to the whole modified polyolefin resin, it is usually preferable that it is 0.05-15 mass%, More preferably, it is 0.1-10 mass%, More preferably, it is 0.1-3. Mass%. Specific examples of the unsaturated carboxylic acid or derivative thereof used for grafting to the polyolefin resin before modification include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride , Hymic anhydride, 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride, α-ethylacrylic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endocis-bicyclo [2,2, 1] hept-5-ene-2,3-dicarboxylic acid (nadic acid [trademark]), bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride, 1,2,3 , 4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic anhydride, 2-octa-1,3-diketospiro [4.4] non 7-ene, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride, maleopimaric acid, tetrahydrophthalic anhydride, x-methyl-bicyclo [2.2.1] hept- 5-ene-2,3-dicarboxylic acid anhydride, x-methyl-norbornene-5-ene-2,3-dicarboxylic acid anhydride (x represents the substitution position of the methyl group), and norborn-5-ene- 2,3-dicarboxylic acid anhydride and the like can be used. In addition, derivatives of the above unsaturated carboxylic acids such as acid halides, amides, imides, and esters can also be used. In these, unsaturated dicarboxylic acid or its acid anhydride is preferable, and especially maleic anhydride or a hymic anhydride is preferable. Such unsaturated carboxylic acid or its derivative can also be used individually by 1 type, and can also be used in combination of 2 or more type. As the halogen group, chlorine or bromine can be preferably used.

そして、前記した樹脂粉末については、その平均粒子径が通常5μm以上300μm以下、好ましくは20μm以上200μm以下であるのがよく、5μmより小さいと樹脂粒子の凝集が起きる虞があり、反対に、300μmより大きくなると温間圧縮成型（ホットプレス）中の樹脂流れが悪くなりカーボン層の形成に問題が起きる虞がある。平均粒子径については、前記炭素粉末の場合と同様に定義される。   For the resin powder described above, the average particle size is usually 5 μm or more and 300 μm or less, preferably 20 μm or more and 200 μm or less, and if it is less than 5 μm, there is a risk of aggregation of the resin particles, on the contrary, 300 μm If it is larger, the resin flow during warm compression molding (hot pressing) becomes worse, which may cause a problem in the formation of the carbon layer. About an average particle diameter, it defines similarly to the case of the said carbon powder.

本発明においては、ステンレス鋼製の板状基材の表面とこの表面に積層されるカーボン層との間が、通常０．１μm以上１０μm以下の接着剤層を介して接合されていてもよい。このような接着剤層を形成するための接着剤組成物については、特に制限されるものではないが、好ましくは不飽和カルボン酸若しくはその誘導体の一部又は全部がポリオレフィン樹脂にグラフトした変性ポリオレフィン樹脂を含むもの（例えば、特開2005-146,178号公報参照）であるのがよく、具体的には、接着性ポリオレフィン樹脂を含む接着剤組成物（三井化学株式会社製商品名：アドマー）、不飽和カルボン酸によりグラフト変性された変性ポリオレフィン樹脂を含む接着剤組成物（三井化学株式会社製商品名：ユニストール）等が挙げられる。なお、ハロゲンによりグラフト変性された変性ポリオレフィン樹脂を含む接着剤組成物（東洋紡株式会社製商品名：トーヨータック）等も使用することができ、また、5wt%-フェノール樹脂接着剤組成物（溶媒：イソプロピルアルコール、フェノール樹脂：リグナイト株式会社製商品名：ＡＨ-１１４８）やエポキシ樹脂接着剤組成物（新日鉄住金化学株式会社製商品名：YSLV-80XY）等も使用することができる。この接着剤層の層厚が０．１μm未満だと接着強度が低下する虞があり、反対に、１０μmを超えると作製されたステンレス鋼板カーボン複合材の導電性が低下する虞がある。   In the present invention, the surface of the stainless steel plate-like base material and the carbon layer laminated on the surface may be joined usually via an adhesive layer of 0.1 μm or more and 10 μm or less. The adhesive composition for forming such an adhesive layer is not particularly limited, but is preferably a modified polyolefin resin in which a part or all of an unsaturated carboxylic acid or derivative thereof is grafted to the polyolefin resin. (For example, refer to JP-A-2005-146,178), and specifically, an adhesive composition containing an adhesive polyolefin resin (trade name: Admer, manufactured by Mitsui Chemicals, Inc.), unsaturated Examples thereof include an adhesive composition containing a modified polyolefin resin graft-modified with carboxylic acid (trade name: Unistor, manufactured by Mitsui Chemicals, Inc.). Note that an adhesive composition containing a modified polyolefin resin graft-modified with halogen (Toyobo Co., Ltd., trade name: Toyotack) and the like can also be used, and a 5 wt% -phenol resin adhesive composition (solvent: Isopropyl alcohol, phenol resin: trade name: AH-1148 manufactured by Lignite Co., Ltd., epoxy resin adhesive composition (trade name: YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and the like can also be used. If the thickness of the adhesive layer is less than 0.1 μm, the adhesive strength may be reduced. Conversely, if the thickness exceeds 10 μm, the conductivity of the produced stainless steel plate carbon composite material may be reduced.

そして、本発明のステンレス鋼板カーボン複合材の製造方法については、ステンレス鋼製の板状基材の少なくとも片面に、炭素粉末と熱可塑性樹脂又は熱硬化性樹脂からなる樹脂粉末とを含むカーボン層を積層してステンレス鋼板カーボン複合材を製造するに際し、好ましくは、前記板状基材の少なくとも片面に、表面処理液として、１〜８質量%濃度のフッ化水素酸水溶液、又は、フッ化水素酸(HF)と硝酸(HNO3)との濃度比(HF/HNO3)が２以上であってＨＦ濃度が２質量%以上のフッ化水素酸・硝酸混合水溶液を接触させる表面処理工程と、この表面処理後の板状基材の表面に、前記炭素粉末(C)と樹脂粉末(R)との体積比(C/R)が６／４〜９／１の割合であるカーボン層を積層する積層工程とを有する方法であるのがよい。この際、更に、好ましくは、前記表面処理工程を行なうことに先駆けて、前記板状基材の少なくとも片面に、前処理液として、酸濃度２５質量%以上及び塩化鉄濃度２０質量%以上の塩化鉄含有酸水溶液を接触させる前処理工程を行なってもよい。 And about the manufacturing method of the stainless steel plate carbon composite material of this invention, the carbon layer containing carbon powder and the resin powder which consists of a thermoplastic resin or a thermosetting resin on the at least single side | surface of a stainless steel plate-shaped base material is provided. In producing a stainless steel plate carbon composite by laminating, preferably, at least one surface of the plate-like base material is a 1 to 8% by mass hydrofluoric acid aqueous solution or hydrofluoric acid as a surface treatment liquid. A surface treatment step of contacting a hydrofluoric acid / nitric acid mixed aqueous solution having a concentration ratio (HF / HNO 3 ) of (HF) and nitric acid (HNO 3 ) of 2 or more and an HF concentration of 2% by mass or more, A carbon layer having a volume ratio (C / R) of the carbon powder (C) and the resin powder (R) of 6/4 to 9/1 is laminated on the surface of the plate-like substrate after the surface treatment. Preferably, the method includes a lamination step. At this time, more preferably, prior to performing the surface treatment step, at least one surface of the plate-like substrate is preliminarily treated as a pretreatment liquid with an acid concentration of 25% by mass or more and an iron chloride concentration of 20% by mass or more. You may perform the pre-processing process which makes an iron-containing acid aqueous solution contact.

前記表面処理工程で表面処理液として用いるフッ化水素酸については、濃度１質量%以上８質量%以下、好ましくは３質量%以上８質量%以下のフッ化水素酸水溶液を用いる。ここで、表面処理液として用いるフッ化水素酸水溶液のフッ化水素酸濃度が1質量%より低いと、ステンレス表面の酸化皮膜中の前記O/Fe比を所定の範囲とすることができない虞があり、反対に、８質量%より高くなると、母材のステンレスの溶出が大きく、その表面に形成される酸化皮膜の厚みが厚くなり、接触抵抗が大きくなる虞がある。   With respect to hydrofluoric acid used as the surface treatment liquid in the surface treatment step, a hydrofluoric acid aqueous solution having a concentration of 1% by mass to 8% by mass, preferably 3% by mass to 8% by mass is used. Here, if the hydrofluoric acid concentration of the hydrofluoric acid aqueous solution used as the surface treatment liquid is lower than 1% by mass, the O / Fe ratio in the oxide film on the stainless steel surface may not be within a predetermined range. On the other hand, when the content is higher than 8% by mass, the elution of the base material stainless steel is large, and the thickness of the oxide film formed on the surface thereof is increased, which may increase the contact resistance.

また、表面処理液として、フッ化水素酸・硝酸の混合水溶液を用いる場合には、フッ化水素酸(HF)と硝酸(HNO3)との濃度比(HF/HNO3)が２以上、好ましくは、2.5以上とし、尚且つＨＦ濃度が２質量%以上、好ましくは３質量%以上とする。フッ化水素酸(HF)と硝酸(HNO3)との濃度比(HF/HNO3)が２未満であると、接触抵抗が10mΩ・cm2より大きくなる虞があり、また、ＨＦ濃度が２質量%未満の場合には、ステンレス表面の酸化皮膜中のO/Fe比が０．２６より大きくなり接触抵抗が10mΩ・cm2より大きくなる虞がある。混合水溶液として使用する場合においても、フッ化水素酸の上限濃度については、前記同様に、濃度８質量%以下とする。なお、処理温度については、温度３０℃以上６０℃以下及び時間１分以上２０分以下の処理条件で板状基材を浸漬し、その後に純水等で洗浄する。 Further, as the surface treatment solution, when using a mixed aqueous solution of hydrofluoric acid-nitric acid, hydrofluoric acid (HF) and nitric acid (HNO 3) concentration ratio of the (HF / HNO 3) is 2 or more, preferably Is 2.5 or more, and the HF concentration is 2 mass% or more, preferably 3 mass% or more. If the concentration ratio (HF / HNO 3 ) of hydrofluoric acid (HF) and nitric acid (HNO 3 ) is less than 2, the contact resistance may be greater than 10 mΩ · cm 2 , and the HF concentration is 2 If it is less than mass%, the O / Fe ratio in the oxide film on the stainless steel surface may be greater than 0.26 and the contact resistance may be greater than 10 mΩ · cm 2 . Even when used as a mixed aqueous solution, the upper limit concentration of hydrofluoric acid is 8% by mass or less as described above. In addition, about processing temperature, a plate-shaped base material is immersed on the processing conditions of temperature 30 degreeC or more and 60 degrees C or less and time 1 minute or more and 20 minutes or less, and it wash | cleans after that with pure water etc.

ここで、前記表面処理工程に先駆けて行なってもよい前処理工程では、前処理液としてＦeＣl3等の塩化鉄を塩酸やフッ化水素酸等の非酸化性の酸水溶液中に溶解させて得られた塩化鉄含有酸水溶液を用い、この塩化鉄含有酸水溶液中に板状基材を浸漬し、その後に純水等で洗浄する前処理が行われる。ここで、塩化鉄含有酸水溶液については、使用する酸の種類や塩化鉄の種類によっても異なるが、酸濃度が通常２５質量%以上、好ましくは３０質量%以上４０質量%以下であり、また、塩化鉄濃度が通常２０質量%以上、好ましくは２０質量%以上３０質量%以下であるものが用いられ、また、板状基材を塩化鉄含有酸水溶液中に浸漬する前処理条件については、通常温度３０℃以上６０℃以下及び時間３０秒以上３分以下の処理条件で行われる。この前処理により、ステンレス鋼の製造過程で行なわれる焼鈍工程でステンレス表面に形成された比較的厚い酸化皮膜に予め孔食を形成し、もしくは当該酸化皮膜を薄膜化させることで、その後の表面処理工程において、当該酸化皮膜の構造を制御することが容易となるため好ましい。 Here, in the pretreatment step that may be performed prior to the surface treatment step, iron chloride such as FeCl 3 is dissolved in a non-oxidizing acid aqueous solution such as hydrochloric acid or hydrofluoric acid as a pretreatment liquid. Using the iron chloride-containing acid aqueous solution thus obtained, a pretreatment is performed in which the plate-like substrate is immersed in the iron chloride-containing acid aqueous solution and then washed with pure water or the like. Here, the iron chloride-containing acid aqueous solution varies depending on the type of acid used and the type of iron chloride, but the acid concentration is usually 25% by mass or more, preferably 30% by mass to 40% by mass, The iron chloride concentration is usually 20% by mass or more, preferably 20% by mass or more and 30% by mass or less, and the pretreatment conditions for immersing the plate-like substrate in the iron chloride-containing acid aqueous solution are usually The treatment is performed at a temperature of 30 ° C. to 60 ° C. and a time of 30 seconds to 3 minutes. By this pretreatment, subsequent surface treatment is performed by forming pitting corrosion in the relatively thick oxide film formed on the stainless steel surface in the annealing process performed in the manufacturing process of stainless steel or by thinning the oxide film in advance. In the process, it is preferable because the structure of the oxide film can be easily controlled.

そして、表面処理後の板状基材の表面にカーボン層を積層する積層工程では、表面処理後の板状基材の表面に炭素粉末と樹脂粉末とを含むカーボン層が積層され、この際のカーボン層を積層する方法については、特に制限されるものではなく、例えば、表面処理後の板状基材の表面に炭素粉末と樹脂粉末とを含む粉末混合物を充填しホットプレスする方法、樹脂粉末と炭素粉末とを溶剤中に分散させたスラリーを、ドクターブレード等を使い表面処理後の板状基材の表面に塗布し、乾燥後にホットプレスする方法等が例示できるが、好ましくは、炭素粉末と樹脂粉末とを含む粉末混合物を温間圧縮成型（ホットプレス）して予めカーボン層を形成し、得られたカーボン層を表面処理後の板状基材の表面に再びホットプレスして積層させるホットプレス法で行うのがよい。このホットプレス法でカーボン層を形成し、また、積層することにより、連続的に炭素層を表面処理後の板状基材の表面に形成することができるという利点がある。   In the laminating step of laminating the carbon layer on the surface of the plate-like substrate after the surface treatment, a carbon layer containing carbon powder and resin powder is laminated on the surface of the plate-like substrate after the surface treatment. The method for laminating the carbon layer is not particularly limited. For example, a method of filling a powder mixture containing carbon powder and resin powder on the surface of a plate-like substrate after surface treatment and hot pressing, resin powder And a slurry in which a carbon powder and a carbon powder are dispersed in a solvent are applied to the surface of a plate-like substrate after a surface treatment using a doctor blade or the like, and hot-pressed after drying. A carbon mixture is formed in advance by hot compression molding (hot pressing) of a powder mixture containing the resin powder and the obtained carbon layer is hot pressed again on the surface of the plate-like substrate after the surface treatment and laminated. Relieved It may be carried out in the press method. By forming and laminating a carbon layer by this hot pressing method, there is an advantage that the carbon layer can be continuously formed on the surface of the plate-like substrate after the surface treatment.

本発明の製造方法においては、前記積層工程に先駆けて、表面処理後の板状基材の表面に前記接着剤組成物を塗布し、表面処理後の板状基材の表面に接着剤層を形成する接着剤層形成工程を実施してもよく、前記積層工程では、この接着剤層を介してカーボン層が積層される。積層工程に先駆けて接着剤層形成工程を実施することにより、板状基材とカーボン層との間の密着性が向上することや、板状基材のステンレス表面を接着層で被覆することから、例えば、固体高分子形燃料電池として使用する場合には腐食性環境に対する耐久性が向上するという利点がある。   In the production method of the present invention, prior to the laminating step, the adhesive composition is applied to the surface of the plate-like substrate after the surface treatment, and the adhesive layer is formed on the surface of the plate-like substrate after the surface treatment. An adhesive layer forming step to be formed may be carried out, and in the laminating step, a carbon layer is laminated via the adhesive layer. By performing the adhesive layer forming step prior to the lamination step, the adhesion between the plate-like substrate and the carbon layer is improved, and the stainless steel surface of the plate-like substrate is covered with the adhesive layer. For example, when used as a polymer electrolyte fuel cell, there is an advantage that durability against a corrosive environment is improved.

本発明の方法によって得られた本発明のステンレス鋼板カーボン複合材は、圧縮強度が３MPa以上であって、曲げ歪が０．８%以上で割れが無く、また、接触抵抗が１０mΩ・cm2以下であることが好ましく、より好ましくは８mΩ・cm2以下、さらに好ましくは５mΩ・cm2以下、さらにより好ましくは３mΩ・cm2以下であって、尚且つ、その接触抵抗が燃料電池の使用環境に相当する環境下（例えば、後述の実施例で示すようなフッ素イオンを含んだ酸溶液中に浸漬させる耐久試験）においても実質的に変化しないものであることが好ましい。
本発明のステンレス鋼板カーボン複合材は、柔軟性や可撓性、圧縮強度、成形性、気密性等において優れているだけでなく、導電性(低接触抵抗)と耐食性とが共に優れており、例えば、固体高分子形燃料電池用等の燃料電池用セパレータ、レドックスフロー型２次電池用の集電板、石油精製用、石油化学用等のガスケットやパッキン等の用途において好適に用いられる。 The carbon steel composite of the present invention obtained by the method of the present invention has a compressive strength of 3 MPa or more, a bending strain of 0.8% or more, no cracks, and a contact resistance of 10 mΩ · cm 2 or less. More preferably, it is 8 mΩ · cm 2 or less, more preferably 5 mΩ · cm 2 or less, and even more preferably 3 mΩ · cm 2 or less, and its contact resistance depends on the use environment of the fuel cell. It is preferable that the material does not substantially change even in a corresponding environment (for example, an endurance test immersed in an acid solution containing fluorine ions as shown in Examples described later).
The stainless steel plate carbon composite material of the present invention is excellent not only in flexibility and flexibility, compressive strength, formability, airtightness, etc., but also in both conductivity (low contact resistance) and corrosion resistance, For example, it is suitably used in applications such as a separator for a fuel cell such as a polymer electrolyte fuel cell, a current collecting plate for a redox flow type secondary battery, a gasket or packing for petroleum refining, petrochemical and the like.

以下、実施例及び比較例に基づいて、本発明のステンレス鋼板カーボン複合材、その製造方法、及び各性能評価について具体的に説明する。   Hereinafter, based on an Example and a comparative example, the stainless steel plate carbon composite material of this invention, its manufacturing method, and each performance evaluation are demonstrated concretely.

＜実施例１〜４＞
１．ステンレス鋼製の板状基材の調製
〔ステンレス鋼製の板状基材〕
以下の各実施例及び比較例においては、ＳＵＳ４３０ステンレス鋼板（以下、「Ｍ１」という。）、ＳＵＳ４４４ステンレス鋼板（以下、「Ｍ２」という。）、及びＳＵＳ３１６Ｌステンレス鋼板（以下、「Ｍ３」という。）から切り出された５０μm厚み×幅１００mm×長さ１００mmの大きさの板状基材(M1〜M3)を用いた。 <Examples 1-4>
1. Preparation of stainless steel plate-like substrate (stainless steel plate-like substrate)
In each of the following Examples and Comparative Examples, a SUS430 stainless steel plate (hereinafter referred to as “M1”), a SUS444 stainless steel plate (hereinafter referred to as “M2”), and a SUS316L stainless steel plate (hereinafter referred to as “M3”). A plate-like substrate (M1 to M3) having a size of 50 μm thickness × width 100 mm × length 100 mm cut out from the substrate was used.

〔板状基材の表面処理工程：酸化皮膜の形成〕
上で得られた板状基材(M1〜M3)について、それぞれ、表面処理液として表１に示すように４質量%のフッ化水素酸水溶液を用い、この表面処理液中に５０℃及び１０分間の処理条件で浸漬し、次いで超純水を用いて表面を洗浄し、板状基材の表面に酸化皮膜からなる表面層が形成された表面処理後の板状基材(M1〜M3)を調製した。 [Surface treatment of plate-like substrate: formation of oxide film]
For the plate-like substrates (M1 to M3) obtained above, a 4% by mass hydrofluoric acid aqueous solution was used as the surface treatment liquid as shown in Table 1, and 50 ° C. and 10 ° C. were used in this surface treatment liquid. Submerged plate-like substrate (M1 to M3) where the surface is washed with ultrapure water and then the surface is washed with a surface layer made of an oxide film formed on the surface of the plate-like substrate. Was prepared.

〔酸化皮膜の元素比(O/Fe)の測定と算出〕
表面処理後の板状基材(M1〜M3)について、集束イオンビーム加工装置（日立ハイテクサイエンス社製のSMI3050SE）を用い、メッシュとしてＭo製メッシュを使用し、また、表面保護膜としてカーボンデポ膜を使用し、FIB-マイクロサンプリング法にてＴＥＭ観察用の薄膜断面試料を作製した。
また、ＴＥＭ観察には電解放出型透過電子顕微鏡（日本電子株式会社製のJEM-2100F）を用いて、断面観察の加速電圧は２００kVとし、また、ＥＤＳ元素分析にはエネルギー分散形Ｘ線分析装置（日本電子株式会社製のＪＥＤ-2300Ｔ）を用いて、ＥＤＳ元素分析時には加速電圧２００kVで実施した。ＥＤＳ測定を実施する酸化皮膜は、ＴＥＭ観察断面（図１）において、ＥＤＳによる点分析のＦｅのＫα線とＣｒのＫα線とのカウントピーク面積比が母材（ステンレス）のＦｅとＣｒとの組成比（モル比）になる基材部分(2)の表面に形成されている酸化皮膜層(1)を対象とした。
そして、酸素Ｏと鉄Ｆeの元素比(O/Fe)は、ＥＤＳによる点分析の酸素(O)のＫα線及び鉄(Fe)のＬα線のカウントピーク面積比から算出した。なお、この面積の解析には日本電子株式会社製のAnalysis Programを使用した。
実際の測定及び算出に際しては、酸化皮膜の４ヶ所以上の点において、それぞれのＥＤＳのピーク比率を算出し、その平均値を求めた。なお、この測定は表面処理後大気中で３０日経過した試料を用いて測定した。 [Measurement and calculation of element ratio (O / Fe) of oxide film]
For the plate-like substrate (M1 to M3) after surface treatment, using a focused ion beam processing device (SMI3050SE manufactured by Hitachi High-Tech Science Co., Ltd.), using a mesh made of Mo as a mesh, and a carbon deposit film as a surface protective film A thin film cross-sectional sample for TEM observation was prepared by FIB-microsampling method.
In addition, an electron emission transmission electron microscope (JEM-2100F manufactured by JEOL Ltd.) is used for TEM observation, the acceleration voltage for cross-sectional observation is 200 kV, and an energy dispersive X-ray analyzer for EDS elemental analysis. (JED-2300T manufactured by JEOL Ltd.) was used at an acceleration voltage of 200 kV during EDS elemental analysis. In the TEM observation cross section (FIG. 1), the oxide film for performing EDS measurement has a count peak area ratio of Fe Kα ray and Cr Kα ray of point analysis by EDS between Fe and Cr of the base material (stainless steel). The target was the oxide film layer (1) formed on the surface of the base material portion (2) having a composition ratio (molar ratio).
The elemental ratio (O / Fe) of oxygen O to iron Fe was calculated from the ratio of the count peak areas of oxygen (O) Kα line and iron (Fe) Lα line in point analysis by EDS. In addition, the analysis program made by JEOL Ltd. was used for the analysis of this area.
In actual measurement and calculation, the peak ratio of each EDS was calculated at four or more points on the oxide film, and the average value was obtained. In addition, this measurement was performed using the sample which passed 30 days in air | atmosphere after surface treatment.

〔酸化皮膜の厚さ測定〕
表面処理後の板状基材(M1〜M3)について、集束イオンビーム加工装置（日立ハイテクサイエンス社製のSMI3050SE）を用い、メッシュとしてＭｏ製メッシュを使用し、また、表面保護膜としてカーボンデポ膜を使用し、FIB-マイクロサンプリング法にてＴＥＭ観察用の薄膜断面試料を作製した。
また、ＴＥＭ観察には電解放出型透過電子顕微鏡（日本電子株式会社製のJEM-2100F）を用い、１視野につき任意の３箇所の酸化皮膜の厚みを測定しその平均をすることで酸化皮膜の厚さを測定した。なお、上記同様にＴＥＭ観察断面において、ＥＤＳによる点分析のＦｅのＫα線とＣｒのＫα線とのカウントピーク面積比が母材（ステンレス）のＦｅとＣｒとの組成比（モル比）になる基材部分(2)の表面に形成されている酸化皮膜層(1)を対象とした。なお、上記同様、この測定についても表面処理後大気中で３０日経過した試料を用いて測定した。 [Measurement of oxide film thickness]
For the plate-like substrate (M1 to M3) after surface treatment, using a focused ion beam processing device (SMI3050SE manufactured by Hitachi High-Tech Science Co., Ltd.), using a mesh made of Mo as a mesh, and a carbon deposit film as a surface protective film A thin film cross-sectional sample for TEM observation was prepared by FIB-microsampling method.
In addition, using a field emission transmission electron microscope (JEM-2100F manufactured by JEOL Ltd.) for TEM observation, the thickness of the oxide film at any three locations per field of view was measured and averaged to determine the thickness of the oxide film. The thickness was measured. Similarly to the above, in the TEM observation cross section, the count peak area ratio of Fe Kα ray and Cr Kα ray of point analysis by EDS becomes the composition ratio (molar ratio) of Fe and Cr of the base material (stainless steel). The target was the oxide film layer (1) formed on the surface of the base material portion (2). As described above, this measurement was also performed using a sample that had passed 30 days in the atmosphere after the surface treatment.

２．カーボン層の積層工程
〔接着剤層形成工程〕
接着剤層を形成するための接着剤組成物としては、後述の実施例及び比較例の場合も含めて、樹脂粉末として熱可塑性樹脂〔ポリプロピレン樹脂(PP)、ポリエチレン樹脂(PE)、ポリアミド樹脂(PA)、ポリフェニレンスルフィド樹脂(PPS)、ポリメチルペンテン樹脂(PMP)、ポリエーテルエーテルケトン樹脂(PEEK)、ポリフェニレンエーテル樹脂(PPE)、液晶ポリマー樹脂(LCP)、ポリアミドイミド樹脂(PAI)、ポリスルホン樹脂(PSU)、ポリエチレンテレフタレート樹脂(PET)、ポリブチレンテレフタレート樹脂(PBT)〕を使用する場合には、変性ポリオレフィン樹脂接着剤（三井化学株式会社製、ユニストール）を用い、また、樹脂粉末として熱硬化性樹脂を使用する場合において、当該熱硬化性樹脂がフェノール樹脂(PF)の場合には、イソプロピルアルコールに5wt%になる様にフェノール樹脂を溶解させたフェノール樹脂接着剤（リグナイト株式会社製フェノール樹脂、商品名：ＡＨ-１１４８）を用い、一方で、当該熱硬化性樹脂がエポキシ樹脂(EP)の場合には、エポキシ樹脂接着剤（新日鉄住金化学株式会社製商品名：YSLV-80XY）を用いた。
そして、上で得られた表面処理後３０日経過後の板状基材(M1〜M3)の表面に、卓上コーターを用いて塗布厚１０μmとなるように前記接着剤組成物を塗布し、室温中で１０分乾燥させて接着剤層を形成し、接着剤層付きの板状基材(M1〜M3)を得た。 2. Carbon layer lamination process (adhesive layer forming process)
As an adhesive composition for forming an adhesive layer, including the case of Examples and Comparative Examples described later, thermoplastic resin (polypropylene resin (PP), polyethylene resin (PE), polyamide resin ( PA), polyphenylene sulfide resin (PPS), polymethylpentene resin (PMP), polyether ether ketone resin (PEEK), polyphenylene ether resin (PPE), liquid crystal polymer resin (LCP), polyamideimide resin (PAI), polysulfone resin (PSU), polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT)], a modified polyolefin resin adhesive (Mitsui Chemicals, Unistall) is used, and heat is used as the resin powder. When using a curable resin, if the thermosetting resin is a phenolic resin (PF), it will be 5 wt% in isopropyl alcohol. When a phenol resin adhesive (phenol resin manufactured by Lignite Co., Ltd., trade name: AH-1148) in which a phenol resin is dissolved in the same manner is used, on the other hand, when the thermosetting resin is an epoxy resin (EP), A resin adhesive (trade name: YSLV-80XY, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) was used.
And the said adhesive composition is apply | coated to the surface of the plate-shaped base material (M1-M3) 30 days after surface treatment obtained above using a desktop coater so that it may become application | coating thickness of 10 micrometers, and room temperature Were dried for 10 minutes to form an adhesive layer, and plate-like substrates (M1 to M3) with an adhesive layer were obtained.

〔カーボン層の形成〕
炭素粉末としては、球状黒鉛（伊藤黒鉛株式会社製商品名：SG-BH、平均粒子径：20μm）及び膨張黒鉛（伊藤黒鉛株式会社製商品名：ＥＣ１００、平均粒子径：160μｍ）を使用した。
また、樹脂粉末としては、後述の実施例及び比較例の場合も含めて、熱可塑性樹脂としてポリプロピレン樹脂(PP)（住友精化株式会社製商品名：フローブレンHP-8522）、ポリエチレン樹脂(PE)（住友精化株式会社製商品名：フローセンUF-20S）、ポリアミド樹脂(PA)（東レ株式会社製商品名：TR-2）、ポリフェニレンスルフィド樹脂(PPS)（東レ株式会社製商品名：Ａ900）、及びポリメチルペンテン樹脂(PMP)（三井化学株式会社製商品名：ＭＸ００２）、変性ポリメチルペンテン樹脂(m-PMP)〔開発品、無水マレイン酸変性（変性量：１．０質量％）〕、ポリエーテルエーテルケトン樹脂(PEEK)（クオドラントポリペンコジャパン株式会社製商品名：ケトロン１０００）、ポリフェニレンエーテル樹脂(PPE)（旭化成ケミカルズ株式会社製商品名：ザイロン３００Ｈ）、液晶ポリマー樹脂(LCP)（ＪＸ日鉱日石エネルギー株式会社製商品名：ザイダーＮＸ−１０１）、ポリアミドイミド樹脂(PAI)（東レ株式会社製商品名：ＴＩ−５０１３）、ポリスルホン樹脂(PSU)（ＢＡＳＦ社製商品名：ウルトラゾーンＳ２０１０）、ポリエチレンテレフタレート樹脂(PET)（株式会社帝人製：ＴＲＮ−ＭＴＪ）、及びポリブチレンテレフタレート樹脂(PBT)（三菱エンジニアリングプラスチックス株式会社製商品名：ノバデュラン５０１０Ｒ５）を使用し、また、熱硬化性樹脂としてフェノール樹脂(PF)（リグナイト株式会社製商品名：AH-1148）、及びエポキシ樹脂(EP)（新日鉄住金化学株式会社製商品名：YSLV-80XY）を使用した。 [Formation of carbon layer]
As the carbon powder, spherical graphite (trade name: SG-BH, manufactured by Ito Graphite Co., Ltd., average particle size: 20 μm) and expanded graphite (trade name, manufactured by Ito Graphite Co., Ltd .: EC100, average particle size: 160 μm) were used.
In addition, the resin powder includes polypropylene resin (PP) (trade name: Flowbren HP-8522, manufactured by Sumitomo Seika Co., Ltd.), polyethylene resin (PE ) (Product name: Sumitomo Seika Co., Ltd .: Flocene UF-20S), Polyamide resin (PA) (Product name: TR-2 manufactured by Toray Industries, Inc.), Polyphenylene sulfide resin (PPS) (Product name: A900 manufactured by Toray Industries, Inc.) ), And polymethylpentene resin (PMP) (trade name: MX002, manufactured by Mitsui Chemicals, Inc.), modified polymethylpentene resin (m-PMP) [developed product, maleic anhydride-modified (modified amount: 1.0 mass%) ], Polyetheretherketone resin (PEEK) (Quadrant Polypenco Japan Co., Ltd. trade name: Ketron 1000), polyphenylene ether resin (PPE) (Asahi Kasei Chemicals Co., Ltd. trade name: Zylon 300) ), Liquid crystal polymer resin (LCP) (trade name: Zider NX-101, manufactured by JX Nippon Oil & Energy Corporation), polyamideimide resin (PAI) (trade name: TI-5013, manufactured by Toray Industries, Inc.), polysulfone resin (PSU) (Trade name manufactured by BASF: Ultrazone S2010), polyethylene terephthalate resin (PET) (manufactured by Teijin Limited: TRN-MTJ), and polybutylene terephthalate resin (PBT) (trade name manufactured by Mitsubishi Engineering Plastics Co., Ltd .: Nova Duran 5010R5 ) And phenolic resin (PF) (trade name: AH-1148, manufactured by Lignite Co., Ltd.) and epoxy resin (EP) (trade name: manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .: YSLV-80XY) as thermosetting resins It was used.

そして、上記の炭素粉末と樹脂粉末とを表１に示す比率で混合して粉末混合物とし、この粉末混合物１．６ｇを、図２に示すように（この場合は、接着剤層付きステンレス鋼製板状基材４は用いない。）プレス装置（東洋精機製作所社製卓上ホットプレスMP-SCL）の50×50×20mmの容積を持つ雌型金型に均等になるように投入し、前プレスとしてのホットプレス〔圧力：２ＭＰａ、温度：180℃(PP)、80℃(PF)〕によりカーボン層３（厚さ：０．４ｍｍ）とした。次いで、図２及び図３のように、この得られたカーボン層３と、前記で準備した接着剤層付きの板状基材４とを重ね、加熱温度１５０℃180℃(PP)又は150℃(PF)（Ｔ）及び圧力５ＭＰａ（Ｐ）で押圧し（本プレス、成型時間１０分）、ステンレス鋼板カーボン複合材１５として得た。   Then, the above carbon powder and resin powder are mixed at a ratio shown in Table 1 to obtain a powder mixture, and 1.6 g of this powder mixture is made of stainless steel with an adhesive layer as shown in FIG. The plate-like base material 4 is not used.) The press machine (Toyo Seiki Seisakusho Co., Ltd., tabletop hot press MP-SCL) is placed evenly into a female die having a volume of 50 x 50 x 20 mm, and the front press The carbon layer 3 (thickness: 0.4 mm) was formed by hot pressing [pressure: 2 MPa, temperature: 180 ° C. (PP), 80 ° C. (PF)]. Next, as shown in FIGS. 2 and 3, the obtained carbon layer 3 and the plate-like base material 4 with the adhesive layer prepared above are stacked, and the heating temperature is 150 ° C. 180 ° C. (PP) or 150 ° C. It was pressed at (PF) (T) and a pressure of 5 MPa (P) (this press, molding time 10 minutes) to obtain a stainless steel plate carbon composite material 15.

上で得られた実施例１〜４に係る表面処理後３０日経過後の板状基材、及びそれを用いて作製されたステンレス鋼板カーボン複合材について、以下の評価を行なった。   The following evaluation was performed about the plate-shaped base material 30 days after the surface treatment which concerns on Examples 1-4 obtained above, and the stainless steel plate carbon composite material produced using it.

〔接触抵抗測定方法〕
図４に接触抵抗の測定方法を示す。先ず、表面処理後３０日経過後の板状基材又はステンレス鋼板カーボン複合材を、それぞれ長さ１７〜２０ｍｍ、幅３〜５ｍｍに加工して試験片Ｓ又はＳ’とし、これと標準とするカーボンペーパ（東レ株式会社製商品名：ＴＧＰ-Ｈ-１２０）３０１とを重ねた。そして、これを２つの金メッキした銅製金具３０２で挟み込み、圧縮応力０．９ＭＰａ(Ｐ’)を付加した状態で２つの金メッキ銅製金具の間に試験片Ｓ／カーボンペーパ接触面積値（単位cm2）と同じ値の直流電流（単位Ａ）を流して、金メッキ銅金具３０２／カーボンペーパ３０１／試験片Ｓ又はＳ’の接続部に生ずる電圧降下を測定することで得られる接触抵抗値（単位：mΩ・cm2）で確認した。測定は10点測定を行い、最大値と最小値を省いた８点の平均値を測定値とした。なお、表面処理直後の板状基材についても、同様の方法で接触抵抗値を測定している。 [Contact resistance measurement method]
FIG. 4 shows a method for measuring contact resistance. First, a plate-like base material or a stainless steel plate carbon composite material after 30 days from the surface treatment is processed into a length of 17 to 20 mm and a width of 3 to 5 mm, respectively, to obtain a test piece S or S ′. Paper (trade name: TGP-H-120, manufactured by Toray Industries, Inc.) 301 was stacked. Then, this is sandwiched between two gold-plated copper fittings 302, and a specimen S / carbon paper contact area value (unit cm 2 ) between the two gold-plated copper fittings with a compressive stress of 0.9 MPa (P ′) applied. The contact resistance value (unit: mΩ) obtained by measuring the voltage drop generated at the connection part of the gold-plated copper metal fitting 302 / carbon paper 301 / test piece S or S ′ by passing the same direct current (unit A)・ Confirmed with cm 2 ). The measurement was performed at 10 points, and the average value of 8 points excluding the maximum and minimum values was taken as the measurement value. In addition, the contact resistance value is measured by the same method also about the plate-shaped substrate immediately after the surface treatment.

〔耐久性試験方法〕
耐久性試験は、前記の試験片Ｓ’（ステンレス鋼板カーボン複合材）を、予め２０ｐｐｍのフッ素（Ｆ）イオンを含んだ８０℃のｐＨ３の硫酸溶液中に４日間浸漬した上で、処理後の試験片Ｓ’を超純水で洗浄し、乾燥した後、上記と同様の方法で接触抵抗値（単位：mΩ・cm2）を測定した。浸漬前後の接触抵抗値の変化を評価することで耐久性（耐食性）を評価した。
得られた結果を下記の表２に示す。 [Durability test method]
In the durability test, the test piece S ′ (stainless steel plate carbon composite) was immersed in a sulfuric acid solution having a pH of 3 at 80 ° C. containing 20 ppm of fluorine (F) ions in advance for 4 days. After the test piece S ′ was washed with ultrapure water and dried, the contact resistance value (unit: mΩ · cm 2 ) was measured by the same method as described above. Durability (corrosion resistance) was evaluated by evaluating changes in contact resistance values before and after immersion.
The obtained results are shown in Table 2 below.

〔可撓性評価（曲げ強度評価）〕
実施例１〜４で得られた各ステンレス鋼板カーボン複合材から、それぞれ５０mm×５mm×０．６mmの大きさの試験片として切り出し、この各試験片を、JIS K7171に準拠して、万能試験機（島津製作所社製AUTOGRAPH AG-IS型）によりStress-Strain曲線を測定し、歪み１．５%又は０．８%の時における各試験片の破壊（亀裂）の発生の有無を目視で観察し、下記の基準で評価した。
得られた結果を下記の表２に示す。
◎：１．５%歪みで破壊しない場合
○：０．８%歪みで破壊しない場合
×：０．８%歪みで破壊する場合 [Flexibility evaluation (bending strength evaluation)]
Each stainless steel plate carbon composite obtained in Examples 1 to 4 was cut out as a test piece having a size of 50 mm × 5 mm × 0.6 mm, and each test piece was universally tested in accordance with JIS K7171. Measure the stress-strain curve using the AUTOGRAPH AG-IS model (manufactured by Shimadzu Corporation) and visually observe the occurrence of breakage (cracking) of each specimen when the strain is 1.5% or 0.8%. The evaluation was based on the following criteria.
The obtained results are shown in Table 2 below.
◎: When not breaking at 1.5% strain ○: When not breaking at 0.8% strain ×: When breaking at 0.8% strain

＜実施例５〜７＞
前記板状基材(M1)を用いて、先ず、前処理液として塩酸（関東化学社製特級）及び塩化鉄(FeCl3)（関東化学社製特級）をそれぞれ３０質量%の濃度で溶解された塩化鉄含有酸溶液を用い、この前処理液中に５０℃及び１分間の処理条件で浸漬し、次いで超純水を用いて表面を洗浄し、前処理後の板状基材(M1)を調製した。 <Examples 5-7>
First, hydrochloric acid (special grade made by Kanto Chemical Co., Ltd.) and iron chloride (FeCl 3 ) (special grade made by Kanto Chemical Co., Ltd.) were dissolved as pretreatment liquids at a concentration of 30% by mass using the plate-like substrate (M1). A plate-like substrate (M1) after pretreatment by using an iron chloride-containing acid solution and immersing in this pretreatment solution at 50 ° C. for 1 minute and then washing the surface with ultrapure water. Was prepared.

〔板状基材の表面処理工程：酸化被膜の形成〕
上で得られた前処理後の板状基材(M1)について、それぞれ、表面処理液として表１に示す濃度のフッ化水素酸水溶液を用い、この表面処理液中に５０℃及び１０分間の処理条件で浸漬し、次いで超純水を用いて表面を洗浄し、板状基材の表面に酸化皮膜からなる表面層が形成された表面処理後の板状基材(M1)を調製した。 [Surface treatment step of plate-like substrate: formation of oxide film]
About the plate-like base material (M1) after the pretreatment obtained above, a hydrofluoric acid aqueous solution having a concentration shown in Table 1 was used as the surface treatment solution, and the surface treatment solution was subjected to 50 ° C. and 10 minutes. The plate-like substrate (M1) after the surface treatment in which the surface layer was formed by forming a surface layer made of an oxide film on the surface of the plate-like substrate was prepared by immersing under treatment conditions and then washing the surface with ultrapure water.

その後、得られた表面処理後の各板状基材(M1)について、前述の実施例１〜４と同様に、表面処理後３０日経過後の酸化皮膜の厚み、元素比(O/Fe)及び接触抵抗値を測定し、また、同じように、当該板状基材に接着剤層及びカーボン層（樹脂粉末としてPPを使用）を積層させてステンレス鋼板カーボン複合材を得ると共に、接触抵抗値の測定、耐久性試験及び可撓性評価を行なった。なお、表面処理直後の板状基材についても、同様の方法で接触抵抗値を測定している。
得られた結果を下記の表２に示す。 Thereafter, for each obtained plate-like substrate (M1) after the surface treatment, as in Examples 1 to 4, the thickness of the oxide film, the element ratio (O / Fe) after 30 days after the surface treatment, and Similarly, the contact resistance value is measured, and similarly, an adhesive layer and a carbon layer (PP is used as the resin powder) are laminated on the plate-like base material to obtain a stainless steel plate carbon composite material. Measurement, durability test and flexibility evaluation were performed. In addition, the contact resistance value is measured by the same method also about the plate-shaped substrate immediately after the surface treatment.
The obtained results are shown in Table 2 below.

＜実施例８〜１０、比較例１〜４＞
前記実施例５〜７において、表面処理液として使用したフッ化水素酸水溶液に代えて、表面処理液として硝酸（関東化学社製特級）及びフッ化水素酸（関東化学社製特級）を表１に示す割合で含有するフッ化水素酸・硝酸混合水溶液を用いた以外は、実施例５〜７と同様の方法で前処理及び表面処理を行った板状基材(M1)を調製し、同じように、表面処理後３０日経過後の酸化皮膜の厚み、元素比(O/Fe)及び接触抵抗値を測定し、また、同じように、表面処理後３０日経過後の板状基材に接着剤層及びカーボン層を積層させてステンレス鋼板カーボン複合材を得ると共に、接触抵抗値の測定、耐久性試験及び可撓性評価を行なった。なお、表面処理直後の板状基材についても、同様の方法で接触抵抗値を測定している。
得られた結果を下記の表２に示す。 <Examples 8 to 10 and Comparative Examples 1 to 4>
In Examples 5 to 7, instead of the hydrofluoric acid aqueous solution used as the surface treatment liquid, nitric acid (special grade made by Kanto Chemical Co.) and hydrofluoric acid (special grade made by Kanto Chemical Co., Ltd.) were used as the surface treatment liquid. A plate-like base material (M1) that was pretreated and surface-treated in the same manner as in Examples 5 to 7 except that the hydrofluoric acid / nitric acid mixed aqueous solution contained in the ratio shown in FIG. Thus, the thickness, element ratio (O / Fe) and contact resistance value after 30 days from the surface treatment were measured, and similarly, the adhesive was applied to the plate-like substrate after 30 days from the surface treatment. A stainless steel plate carbon composite was obtained by laminating a layer and a carbon layer, and a contact resistance value measurement, a durability test, and a flexibility evaluation were performed. In addition, the contact resistance value is measured by the same method also about the plate-shaped substrate immediately after the surface treatment.
The obtained results are shown in Table 2 below.

＜実施例１１〜３２＞
前記実施例５〜７において、表面処理液として使用したフッ化水素酸水溶液の濃度４質量%とした以外は、実施例５〜７と同様の方法で前処理及び表面処理を行なった板状基材(M1)を調製し、同じように、表面処理後３０日経過後の酸化皮膜の厚み、元素比(O/Fe)及び接触抵抗値を測定した。なお、表面処理直後の板状基材についても、同様の方法で接触抵抗値を測定している。そして、実施例５〜７において使用した樹脂粉末に代えて、表１に記載の通り、樹脂粉末をそれぞれPE、PA、PPS、PMP、m-PMP、PEEK、PSU、LCP、PET、PAI、PPE、PBT、PF又はEPとすると共に、カーボン層を形成する際の前プレスの温度をそれぞれ130℃(PE)、250℃(PA、PBT、PPE、m-PMP)、300℃(PPS、PET、PAI)、350℃(LCP)、400℃(PEEK、PSU)、250℃(PMP)及び80℃（PF及びEP）とした以外は、実施例５〜７と同様にカーボン層を形成し、また、同じように、表面処理後３０日経過後の板状基材に接着剤層及びカーボン層を積層させてステンレス鋼板カーボン複合材を得ると共に、接触抵抗値の測定、耐久性試験及び可撓性評価を行なった。なお、表面処理後３０日経過後の板状基材に接着剤層付きのカーボン層を積層させてステンレス鋼板カーボン複合材を得る際の本プレスの温度は、それぞれ130℃(PE)、250℃(PA、PBT、PPE、m-PMP)、300℃(PPS、PET、PAI)、350℃(LCP)、400℃(PEEK、PSU)、150℃（PF及びEP）とした。
得られた結果を下記の表２に示す。 <Examples 11-32>
In the said Examples 5-7, the plate-shaped board | substrate which performed the pre-processing and the surface treatment by the method similar to Examples 5-7 except having set it as the density | concentration of 4 mass% of the hydrofluoric acid aqueous solution used as a surface treatment liquid. The material (M1) was prepared, and the thickness, element ratio (O / Fe), and contact resistance value of the oxide film 30 days after the surface treatment were measured in the same manner. In addition, the contact resistance value is measured by the same method also about the plate-shaped substrate immediately after the surface treatment. And instead of the resin powder used in Examples 5-7, as described in Table 1, resin powders were respectively PE, PA, PPS, PMP, m-PMP, PEEK, PSU, LCP, PET, PAI, PPE. , PBT, PF or EP, and the temperature of the pre-press when forming the carbon layer is 130 ° C (PE), 250 ° C (PA, PBT, PPE, m-PMP), 300 ° C (PPS, PET, PAI), 350 ° C. (LCP), 400 ° C. (PEEK, PSU), 250 ° C. (PMP) and 80 ° C. (PF and EP) except that a carbon layer was formed in the same manner as in Examples 5 to 7, and Similarly, a stainless steel plate carbon composite material is obtained by laminating an adhesive layer and a carbon layer on a plate-like substrate 30 days after the surface treatment, and a contact resistance value measurement, a durability test, and a flexibility evaluation Was done. In addition, the temperature of this press at the time of laminating | stacking the carbon layer with an adhesive layer on the plate-shaped base material 30 days after surface treatment and obtaining a stainless steel plate carbon composite is 130 degreeC (PE), 250 degreeC ( PA, PBT, PPE, m-PMP), 300 ° C. (PPS, PET, PAI), 350 ° C. (LCP), 400 ° C. (PEEK, PSU), 150 ° C. (PF and EP).
The obtained results are shown in Table 2 below.

＜実施例３３〜３５、比較例５〜６＞
前記実施例５〜７において、表面処理液として使用したフッ化水素酸水溶液の濃度４質量%とした以外は、実施例５〜７と同様の方法で前処理及び表面処理を行なった板状基材(M1)を調製し、同じように、表面処理後３０日経過後の酸化皮膜の厚み、元素比(O/Fe)及び接触抵抗値を測定した。なお、表面処理直後の板状基材についても、同様の方法で接触抵抗値を測定している。そして、実施例５〜７において使用した炭素粉末及び樹脂粉末の配合比率を表１に示す比率とした以外は、実施例５〜７と同様にカーボン層を形成し、同じように、表面処理後３０日経過後の板状基材に接着剤層及びカーボン層を積層させてステンレス鋼板カーボン複合材を得ると共に、接触抵抗値の測定、耐久性試験及び可撓性評価を行なった。
得られた結果を下記の表２に示す。 <Examples 33 to 35, Comparative Examples 5 to 6>
In the said Examples 5-7, the plate-shaped board | substrate which performed the pre-processing and the surface treatment by the method similar to Examples 5-7 except having set it as the density | concentration of 4 mass% of the hydrofluoric acid aqueous solution used as a surface treatment liquid. The material (M1) was prepared, and the thickness, element ratio (O / Fe), and contact resistance value of the oxide film 30 days after the surface treatment were measured in the same manner. In addition, the contact resistance value is measured by the same method also about the plate-shaped substrate immediately after the surface treatment. And the carbon layer was formed in the same manner as in Examples 5 to 7 except that the mixing ratio of the carbon powder and the resin powder used in Examples 5 to 7 was the ratio shown in Table 1, and after the surface treatment in the same manner. A stainless steel plate carbon composite was obtained by laminating an adhesive layer and a carbon layer on the plate-like substrate after 30 days, and a contact resistance value measurement, a durability test and a flexibility evaluation were performed.
The obtained results are shown in Table 2 below.

＜実施例３６〜３９＞
前記実施例５〜７において、表面処理液として使用したフッ化水素酸水溶液の濃度４質量%とした以外は、実施例５〜７と同様の方法で前処理及び表面処理を行なった板状基材(M1)を調製し、同じように表面処理後３０日経過後の酸化皮膜の厚み、元素比(O/Fe)及び接触抵抗値を測定した。なお、表面処理直後の板状基材についても、同様の方法で接触抵抗値を測定している。そして、実施例５〜７において使用した炭素粉末の配合比率を表１に示す比率とした以外は、実施例５〜７と同様にカーボン層を形成し、同じように、表面処理後３０日経過後の板状基材に接着剤層及びカーボン層を積層させてステンレス鋼板カーボン複合材を得ると共に、接触抵抗値の測定、耐久性試験及び可撓性評価を行なった。
得られた結果を下記の表２に示す。 <Examples 36 to 39>
In the said Examples 5-7, the plate-shaped base which performed the pre-processing and the surface treatment by the method similar to Examples 5-7 except having set it as the density | concentration of 4 mass% of the hydrofluoric acid aqueous solution used as a surface treatment liquid. A material (M1) was prepared, and the thickness, element ratio (O / Fe), and contact resistance value of the oxide film 30 days after the surface treatment were measured in the same manner. In addition, the contact resistance value is measured by the same method also about the plate-shaped substrate immediately after the surface treatment. And the carbon layer was formed in the same manner as in Examples 5 to 7 except that the mixing ratio of the carbon powder used in Examples 5 to 7 was changed to the ratio shown in Table 1, and after 30 days had passed since the surface treatment. A stainless steel plate carbon composite was obtained by laminating an adhesive layer and a carbon layer on the plate-shaped substrate, and a contact resistance value measurement, a durability test, and a flexibility evaluation were performed.
The obtained results are shown in Table 2 below.

＜実施例４０〜４６＞
前記実施例５〜７において、前処理液として、塩酸及び塩化鉄(FeCl3)が表１に記載の通りの濃度で溶解された塩化鉄含有酸溶液を用い、且つ、表面処理液として使用したフッ化水素酸水溶液の濃度４質量%とした以外は、実施例５〜７と同様の方法で前処理及び表面処理を行なった板状基材(M1)を調製し、同じように、表面処理後３０日経過後の酸化皮膜の厚み、元素比(O/Fe)及び接触抵抗値を測定した。なお、表面処理直後の板状基材についても、同様の方法で接触抵抗値を測定している。そして、実施例５〜７と同じように、表面処理後３０日経過後の板状基材に接着剤層及びカーボン層を積層させてステンレス鋼板カーボン複合材を得ると共に、接触抵抗値の測定、耐久性試験及び可撓性評価を行なった。
得られた結果を下記の表２に示す。 <Examples 40 to 46>
In Examples 5 to 7, an acid solution containing iron chloride in which hydrochloric acid and iron chloride (FeCl 3 ) were dissolved in the concentrations shown in Table 1 was used as a pretreatment solution, and used as a surface treatment solution. Except that the concentration of the hydrofluoric acid aqueous solution was changed to 4% by mass, a plate-like substrate (M1) that had been pretreated and surface-treated in the same manner as in Examples 5 to 7 was prepared. After 30 days, the thickness, element ratio (O / Fe), and contact resistance value of the oxide film were measured. In addition, the contact resistance value is measured by the same method also about the plate-shaped substrate immediately after the surface treatment. And like Example 5-7, while laminating | stacking an adhesive bond layer and a carbon layer on the plate-shaped base material 30 days after surface treatment, and obtaining a stainless steel plate carbon composite, measurement of a contact resistance value, durability Property test and flexibility evaluation.
The obtained results are shown in Table 2 below.

＜比較例７＞
前記板状基材(M3)を用いて、これを２質量%硫酸（関東化学社製）中に浸漬させて、温度３０℃において、＋2A/dm2×１秒、-2A/dm2×１秒、＋2A/dm2×１秒、-2A/dm2×１秒、及び＋2A/dm2×１秒（+がアノード電極、-がカソード電極）の順に電解処理（前処理）を行った。次いで、表面処理液として５質量%のフッ化水素酸水溶液と3質量%の硝酸を混合した酸溶液を用い、前記電解処理後の板状基材を５５℃及び９０秒間の処理条件で浸漬し、次いで超純水を用いて表面を洗浄し、板状基材の表面に酸化皮膜からなる表面層が形成された表面処理後の板状基材(M3)を調製した。
その後、得られた表面処理後の板状基材(M3)について、前述の実施例１〜４と同様に、表面処理後３０日経過後の酸化皮膜の厚み、元素比(O/Fe)及び接触抵抗値を測定した。なお、表面処理直後の板状基材についても、同様の方法で接触抵抗値を測定している。接着剤層及びカーボン層の積層は行なわず、当該表面処理後の各板状基材(M3)としたまま、実施例１〜４と同様の方法を用いて、耐久性試験及び可撓性評価を行なった。
得られた結果を下記の表２に示す。 <Comparative Example 7>
Using the plate-like substrate (M3), it is immersed in 2% by mass sulfuric acid (manufactured by Kanto Chemical Co., Inc.) at a temperature of 30 ° C., +2 A / dm 2 × 1 second, −2 A / dm 2 × 1 Second, +2 A / dm 2 × 1 second, −2 A / dm 2 × 1 second, and +2 A / dm 2 × 1 second (+ is an anode electrode, − is a cathode electrode) in this order (electrolytic treatment (pretreatment)). Next, an acid solution in which 5% by mass of hydrofluoric acid aqueous solution and 3% by mass of nitric acid are mixed as the surface treatment solution is used, and the plate-like substrate after the electrolytic treatment is immersed at 55 ° C. for 90 seconds. Then, the surface was washed with ultrapure water to prepare a surface-treated plate-like substrate (M3) in which a surface layer made of an oxide film was formed on the surface of the plate-like substrate.
Thereafter, with respect to the obtained plate-like substrate (M3) after the surface treatment, the thickness of the oxide film, the element ratio (O / Fe), and the contact after 30 days from the surface treatment, as in Examples 1 to 4 above. The resistance value was measured. In addition, the contact resistance value is measured by the same method also about the plate-shaped substrate immediately after the surface treatment. The lamination of the adhesive layer and the carbon layer is not performed, and the durability test and the flexibility evaluation are performed using the same method as in Examples 1 to 4 while keeping the plate-like base material (M3) after the surface treatment. Was done.
The obtained results are shown in Table 2 below.

＜比較例８＞
前記板状基材(M3)を用いて、これを、前処理として濃度５質量％、液温６０℃のオルソケイ酸ナトリウム溶液に浸漬し、電流密度５Ａ／ｄｍ２でアノード電解脱脂を１０秒間実施した後、中和処理のため、濃度５質量％、常温の塩酸酸洗を１０秒間実施した。そして、温度５０℃の１５質量%FeCl3（関東化学社製）中に浸漬させ、アノード電流密度は３．０ｋＡ／ｍ２、カソード電流密度は０．５ｋＡ／ｍ２、交番サイクル２．５Ｈｚの電解処理を６０秒実施し、次いで超純水を用いて表面を洗浄した。
その後、得られた電解処理後の板状基材(M3)について、前述の実施例１〜４と同様に、表面処理後３０日経過後の酸化皮膜の厚み、元素比(O/Fe)及び接触抵抗値を測定した。なお、電解処理直後の板状基材についても、同様の方法で接触抵抗値を測定している。一方で、フェノール樹脂（リグナイト株式会社製商品名：AH-1148）と天然黒鉛粉（伊藤黒鉛株式会社製商品名：SG-BH8）とカーボンブラック（ライオン株式会社製商品名：ECP-600JD）とをそれぞれ３ｇ、６ｇ又は１ｇ（質量比で3:6:1）で混合し、これに、イソシアネート架橋剤（旭化成ケミカルズ株式会社製商品名：MF-B60X）を前記フェノール樹脂質量に対して３倍量添加し、これを混練した。これに酢酸エチレングリコールモノブチルエーテルを添加しスラリー状にした後、前記電解処理後の板状基材(M3)にバーコーターで塗布し275℃で60秒焼き付け処理を経てステンレス鋼板カーボン複合材とした。乾燥後の被覆層厚さは６μｍとした。その後、得られたステンレス鋼板カーボン複合材について、実施例１〜４と同様の方法で、接触抵抗値の測定、耐久性試験及び可撓性評価を行なった。
得られた結果を下記の表２に示す（なお、この比較例８については、表２における「表面処理直後」は『電解処理直後』と読み替え、また、「表面処理３０日後」は『電解処理３０日後』と読み替えるものとする）。 <Comparative Example 8>
Using the plate-like substrate (M3), this was immersed in a sodium orthosilicate solution having a concentration of 5 mass% and a liquid temperature of 60 ° C. as a pretreatment, and anodic electrolytic degreasing was carried out for 10 seconds at a current density of 5 A / dm 2. After that, for neutralization treatment, hydrochloric acid pickling at a concentration of 5 mass% and room temperature was performed for 10 seconds. And it is immersed in 15 mass% FeCl 3 (manufactured by Kanto Chemical Co., Inc.) at a temperature of 50 ° C., the anode current density is 3.0 kA / m 2 , the cathode current density is 0.5 kA / m 2 , and the alternating cycle is 2.5 Hz. Electrolytic treatment was performed for 60 seconds, and then the surface was cleaned with ultrapure water.
Thereafter, with respect to the obtained plate-like substrate (M3) after the electrolytic treatment, the thickness, element ratio (O / Fe), and contact of the oxide film after 30 days from the surface treatment were obtained in the same manner as in Examples 1 to 4 described above. The resistance value was measured. In addition, the contact resistance value was measured by the same method also about the plate-shaped base material immediately after electrolytic treatment. On the other hand, phenol resin (trade name: AH-1148 manufactured by Lignite Co., Ltd.), natural graphite powder (trade name: SG-BH8 manufactured by Ito Graphite Co., Ltd.) and carbon black (trade name: ECP-600JD manufactured by Lion Co., Ltd.) 3 g, 6 g or 1 g (3: 6: 1 by mass ratio), respectively, and an isocyanate cross-linking agent (trade name: MF-B60X, manufactured by Asahi Kasei Chemicals Co., Ltd.) 3 times the phenol resin mass An amount was added and kneaded. After adding ethylene glycol monobutyl ether acetate to this to make a slurry, it was applied to the plate-like substrate (M3) after the electrolytic treatment with a bar coater and baked at 275 ° C. for 60 seconds to obtain a stainless steel plate carbon composite material. . The coating layer thickness after drying was 6 μm. Then, about the obtained stainless steel plate carbon composite, the measurement of a contact resistance value, a durability test, and flexibility evaluation were performed by the method similar to Examples 1-4.
The obtained results are shown in the following Table 2. (For Comparative Example 8, “immediately after the surface treatment” in Table 2 is read as “immediately after the electrolytic treatment”, and “after 30 days after the surface treatment” is “electrolytic treatment”. 30 days later ”).

＜比較例９＞
前記板状基材(M1)を用いて、表面処理を行わなかった以外は、前述の実施例１と同様にして、３０日経過後の酸化皮膜の厚み、元素比(O/Fe)及び接触抵抗値を測定し、また、同じように、当該板状基材に接着剤層及びカーボン層（樹脂粉末としてPPを使用）を積層させてステンレス鋼板カーボン複合材を得ると共に、接触抵抗値の測定、耐久性試験及び可撓性評価を行なった。なお、３０日経過前の板状基材についても、同様の方法で接触抵抗値を測定している（なお、この比較例９については、表面処理を行っていないが、表２における「表面処理直後」は『３０日経過前』と読み替え、また、「表面処理３０日後」は『３０日経過後』と読み替えるものとする）。 <Comparative Example 9>
The thickness, element ratio (O / Fe), and contact resistance of the oxide film after 30 days were the same as in Example 1 except that the surface treatment was not performed using the plate-like substrate (M1). In the same manner, the adhesive layer and the carbon layer (using PP as the resin powder) are laminated on the plate-like base material to obtain a stainless steel plate carbon composite, and the contact resistance value is measured. A durability test and a flexibility evaluation were performed. In addition, also about the plate-shaped base material before 30-day progress, the contact resistance value is measured by the same method (In addition, although the surface treatment is not performed about this comparative example 9, "surface treatment in Table 2 is carried out." “Immediately” is read as “before 30 days”, and “after 30 days of surface treatment” is read as “after 30 days”).

Figure 2017071218
Figure 2017071218

Figure 2017071218
Figure 2017071218

１…酸化皮膜層、２…ステンレス鋼製板状基材層、３…カーボン層、４…接着剤層付きステンレス鋼製板状基材、５…燃料電池用セパレータ、６…固体高分子電解質膜、７…アノード（燃料電極）、８…カソード（酸化剤電極）、９…ガスケット、１０…単位セル、１１…ガス供給排出用溝、１２…開口部、１３…固定穴、１４…接着剤層、１５…ステンレス鋼板カーボン複合材、１６…固体高分子形燃料電池、１００…プレス装置、１０１…雄型、１０２…雌型、１０３…金型、１０４…機枠、１０５…油圧シリンダ、３０１…カーボンペーパ、３０２…銅製金具、３０３…測定装置
DESCRIPTION OF SYMBOLS 1 ... Oxide film layer, 2 ... Stainless steel plate-like base material layer, 3 ... Carbon layer, 4 ... Stainless steel plate-like base material with an adhesive layer, 5 ... Fuel cell separator, 6 ... Solid polymer electrolyte membrane , 7 ... Anode (fuel electrode), 8 ... Cathode (oxidant electrode), 9 ... Gasket, 10 ... Unit cell, 11 ... Gas supply / discharge groove, 12 ... Opening, 13 ... Fixing hole, 14 ... Adhesive layer 15 ... stainless steel plate carbon composite, 16 ... solid polymer fuel cell, 100 ... pressing device, 101 ... male, 102 ... female, 103 ... mold, 104 ... machine frame, 105 ... hydraulic cylinder, 301 ... Carbon paper, 302 ... Copper metal fittings, 303 ... Measurement device

Claims (12)

ステンレス鋼製の板状基材の少なくとも片面に、炭素粉末と熱可塑性樹脂又は熱硬化性樹脂からなる樹脂粉末とを含むカーボン層が積層されたステンレス鋼板カーボン複合材であり、
前記カーボン層は、前記炭素粉末(C)と樹脂粉末(R)とを体積比(C/R)で６／４〜９／１の割合で含み、且つ前記板状基材の表面に形成された酸化皮膜を介して積層されており、また、前記酸化皮膜はＥＤＳ元素分析で測定された酸素(O)と鉄(Fe)との元素比(O/Fe)が０．０７〜０．２６の範囲内であることを特徴とするステンレス鋼板カーボン複合材。 A stainless steel plate carbon composite in which a carbon layer containing carbon powder and a resin powder made of a thermoplastic resin or a thermosetting resin is laminated on at least one side of a plate-like substrate made of stainless steel,
The carbon layer includes the carbon powder (C) and the resin powder (R) at a volume ratio (C / R) of 6/4 to 9/1, and is formed on the surface of the plate-like substrate. The oxide film has an element ratio (O / Fe) of oxygen (O) and iron (Fe) measured by EDS elemental analysis of 0.07 to 0.26. Stainless steel sheet carbon composite material characterized by being within the range of 前記板状基材が、オーステナイト系ステンレス鋼又はフェライト系ステンレス鋼であることを特徴とする請求項１に記載のステンレス鋼板カーボン複合材。   The stainless steel plate carbon composite according to claim 1, wherein the plate-like base material is austenitic stainless steel or ferritic stainless steel. 前記熱可塑性樹脂からなる樹脂粉末が、ポリプロピレン樹脂、ポリエチレン樹脂、ポリアミド樹脂、ポリフェニレンスルフィド樹脂、ポリメチルペンテン樹脂、ポリエーテルエーテルケトン樹脂、ポリフェニレンエーテル樹脂、液晶ポリマー樹脂、ポリアミドイミド樹脂、ポリスルホン樹脂、ポリエチレンテレフタレート樹脂及びポリブチレンテレフタレート樹脂からなる群から選ばれたいずれか１種か又は２種以上の混合物からなる樹脂粉末であることを特徴とする請求項１又は２に記載のステンレス鋼板カーボン複合材。   The resin powder comprising the thermoplastic resin is polypropylene resin, polyethylene resin, polyamide resin, polyphenylene sulfide resin, polymethylpentene resin, polyether ether ketone resin, polyphenylene ether resin, liquid crystal polymer resin, polyamide imide resin, polysulfone resin, polyethylene. 3. The stainless steel plate carbon composite according to claim 1, wherein the stainless steel plate carbon composite material is a resin powder made of one or a mixture of two or more selected from the group consisting of a terephthalate resin and a polybutylene terephthalate resin. 前記熱硬化性樹脂からなる樹脂粉末が、フェノール樹脂及びエポキシ樹脂からなる群から選ばれたいずれか１種か又は２種以上の混合物からなる樹脂粉末であることを特徴とする請求項１又は２に記載のステンレス鋼板カーボン複合材。   The resin powder comprising the thermosetting resin is a resin powder comprising any one or a mixture of two or more selected from the group consisting of a phenol resin and an epoxy resin. The stainless steel plate carbon composite material described in 1. 前記板状基材の表面とこの表面に積層されるカーボン層との間が、接着剤層を介して接合されていることを特徴とする請求項１〜４のいずれかに記載のステンレス鋼板カーボン複合材。   The stainless steel plate carbon according to any one of claims 1 to 4, wherein a surface of the plate-like substrate and a carbon layer laminated on the surface are bonded via an adhesive layer. Composite material. ステンレス鋼製の板状基材の少なくとも片面に、炭素粉末と熱可塑性樹脂又は熱硬化性樹脂からなる樹脂粉末とを含むカーボン層を積層してステンレス鋼板カーボン複合材を製造する方法であり、
前記板状基材の少なくとも片面に、表面処理液として、１〜８質量%のフッ化水素酸水溶液、又は、フッ化水素酸(HF)と硝酸(HNO3)との濃度比(HF/HNO3)が２以上であってＨＦ濃度が２質量%以上のフッ化水素酸・硝酸混合水溶液を接触させる表面処理工程と、
この表面処理後の板状基材の表面に、前記炭素粉末(C)と樹脂粉末(R)との体積比(C/R)が６／４〜９／１の割合であるカーボン層を積層する積層工程とを有することを特徴とするステンレス鋼板カーボン複合材の製造方法。 It is a method for producing a stainless steel plate carbon composite by laminating a carbon layer containing carbon powder and a resin powder made of a thermoplastic resin or a thermosetting resin on at least one side of a plate-like substrate made of stainless steel,
On at least one surface of the plate-like substrate, as a surface treatment liquid, a 1 to 8 mass% hydrofluoric acid aqueous solution, or a concentration ratio of hydrofluoric acid (HF) and nitric acid (HNO 3 ) (HF / HNO 3 ) a surface treatment step in which a hydrofluoric acid / nitric acid mixed aqueous solution having 2 or more and an HF concentration of 2% by mass or more is brought into contact;
A carbon layer having a volume ratio (C / R) of 6/4 to 9/1 between the carbon powder (C) and the resin powder (R) is laminated on the surface of the plate-like substrate after the surface treatment. A method for producing a carbon composite material of a stainless steel plate, comprising: a laminating step. 前記表面処理工程に先駆けて、前記板状基材の少なくとも片面に、前処理液として、酸濃度２５質量%以上及び塩化鉄濃度２０質量%以上の塩化鉄含有酸水溶液を接触させる前処理工程を有することを特徴とする請求項６に記載のステンレス鋼板カーボン複合材の製造方法。   Prior to the surface treatment step, a pretreatment step in which at least one surface of the plate-like substrate is brought into contact with an iron chloride-containing acid aqueous solution having an acid concentration of 25% by mass or more and an iron chloride concentration of 20% by mass or more as a pretreatment liquid. The method for producing a carbon composite material for a stainless steel plate according to claim 6. 前記積層工程では、前記炭素粉末と樹脂粉末とを含む粉末混合物をホットプレスしてカーボン層を形成し、得られたカーボン層を表面処理後の板状基材の表面にホットプレスして積層することを特徴とする請求項６又は７に記載のステンレス鋼板カーボン複合材の製造方法。   In the laminating step, a powder mixture containing the carbon powder and the resin powder is hot-pressed to form a carbon layer, and the obtained carbon layer is hot-pressed and laminated on the surface of the plate-like substrate after the surface treatment. The manufacturing method of the stainless steel plate carbon composite material of Claim 6 or 7 characterized by the above-mentioned. 前記積層工程に先駆けて、表面処理後の板状基材の表面に接着剤組成物を塗布して接着剤層を形成する接着剤層形成工程を有し、積層工程ではこの接着剤層を介して表面処理後の板状基材の表面にカーボン層が積層されることを特徴とする請求項６〜８のいずれかに記載のステンレス鋼板カーボン複合材の製造方法。   Prior to the laminating step, it has an adhesive layer forming step of forming an adhesive layer by applying an adhesive composition to the surface of the plate-like substrate after the surface treatment, and in the laminating step, this adhesive layer is interposed. The method for producing a stainless steel plate carbon composite according to any one of claims 6 to 8, wherein a carbon layer is laminated on the surface of the plate-like substrate after the surface treatment. 前記熱可塑性樹脂からなる樹脂粉末が、ポリプロピレン樹脂、ポリエチレン樹脂、ポリアミド樹脂、ポリフェニレンスルフィド樹脂、ポリメチルペンテン樹脂、ポリエーテルエーテルケトン樹脂、ポリフェニレンエーテル樹脂、液晶ポリマー樹脂、ポリアミドイミド樹脂、ポリスルホン樹脂、ポリエチレンテレフタレート樹脂及びポリブチレンテレフタレート樹脂からなる群から選ばれたいずれか１種か又は２種以上の混合物からなる樹脂粉末であることを特徴とする請求項６〜９のいずれかに記載のステンレス鋼板カーボン複合材の製造方法。   The resin powder comprising the thermoplastic resin is polypropylene resin, polyethylene resin, polyamide resin, polyphenylene sulfide resin, polymethylpentene resin, polyether ether ketone resin, polyphenylene ether resin, liquid crystal polymer resin, polyamide imide resin, polysulfone resin, polyethylene. The stainless steel plate carbon according to any one of claims 6 to 9, wherein the stainless steel plate carbon is a resin powder made of any one kind or a mixture of two or more kinds selected from the group consisting of a terephthalate resin and a polybutylene terephthalate resin. A method of manufacturing a composite material. 前記熱硬化性樹脂からなる樹脂粉末が、フェノール樹脂及びエポキシ樹脂からなる群から選ばれたいずれか１種か又は２種以上の混合物からなる樹脂粉末であることを特徴とする請求項６〜９のいずれかに記載のステンレス鋼板カーボン複合材の製造方法。   The resin powder made of the thermosetting resin is a resin powder made of any one kind or a mixture of two or more kinds selected from the group consisting of a phenol resin and an epoxy resin. The manufacturing method of the stainless steel plate carbon composite material in any one of. 前記板状基材が、オーステナイト系ステンレス鋼又はフェライト系ステンレス鋼であることを特徴とする請求項６〜１１のいずれかに記載のステンレス鋼板カーボン複合材の製造方法。
The method for producing a carbon composite material for a stainless steel plate according to any one of claims 6 to 11, wherein the plate-like substrate is austenitic stainless steel or ferritic stainless steel.
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