JP4288188B2 - Surface-treated metal material with excellent heat absorption and dissipation characteristics - Google Patents
Surface-treated metal material with excellent heat absorption and dissipation characteristics Download PDFInfo
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Description
本発明は、家電用、自動車用、建材用などに利用される表面処理金属材料のうち、特に高い吸熱性および放熱性が必要とされる表面処理金属材料に関するものである。詳しくは、モーター類のハウジングや家電製品等の筐体として、あるいは放熱板として好適に用いることができる吸放熱特性に優れた表面処理金属材料に関するものである。 The present invention relates to a surface-treated metal material that requires particularly high heat absorption and heat dissipation among surface-treated metal materials used for home appliances, automobiles, building materials, and the like. More specifically, the present invention relates to a surface-treated metal material having excellent heat-absorbing and heat-dissipating characteristics that can be suitably used as a housing for motors, home appliances, or the like, or as a heat sink.
家電製品をはじめとした電気機器類では、大容量化する一方でサイズは小型化する場合が多く、機器内部の素子、部品から発生する熱を効率よく外部に放出することが大きな問題となっている。従来は、放熱器を取り付けることによって温度上昇を防いだり、発熱する部品の周囲にある程度の大きさの空間を作って、放射（輻射）と対流によって熱を放出するケースが多かった。 In electric appliances such as home appliances, the capacity is often reduced while the capacity is increased, and it is a big problem to efficiently release the heat generated from the elements and components inside the equipment to the outside. Yes. In the past, there were many cases where heat was released by radiation (radiation) and convection by preventing the temperature rise by attaching a radiator or creating a space of a certain size around the heat-generating component.
しかしながら、小型化の進展とともに、放熱器を取り付けるためのスペースがとれなかったり、熱を逃がすための十分な空間が確保できなくなりつつある。このため、内部の部品については、過酷な環境下で動作している場合も多く、結果として寿命が短くなるといった問題点を抱えていた。この問題に対しては、家電製品の筐体や外装ケースから効率よく放熱することがひとつの解決策になると考えられる。 However, with the progress of miniaturization, it is becoming impossible to secure a space for attaching a radiator or securing a sufficient space for releasing heat. For this reason, internal components often operate in harsh environments, resulting in a problem that the lifespan is shortened. To solve this problem, it is considered that efficient heat dissipation from the housing and outer case of home appliances is one solution.
また、パソコンに関しても、近年の演算速度の向上に伴って中央演算素子（CPU）からの発熱量は大幅に増加しており、この熱をいかに放散するかが大きな課題となっている。通常、熱の放散にはファンが用いられており、発熱が激しい場合にはファンの回転数を上げて風量を増やしているが、回転数の増加とともに騒音が大きくなるといった問題点があった。この場合においても、パソコンの筐体から放射によって熱を放散することができれば、ファンの回転数の増加に伴う騒音の問題を気にすることなく、放熱の問題を解決することができる。 As for the personal computer, the amount of heat generated from the central processing unit (CPU) has been greatly increased along with the recent improvement in the calculation speed, and how to dissipate this heat is a big issue. Usually, a fan is used to dissipate heat. When the heat generation is intense, the fan speed is increased to increase the air volume, but there is a problem that noise increases as the speed increases. Even in this case, if heat can be dissipated from the housing of the personal computer by radiation, the problem of heat dissipation can be solved without worrying about the problem of noise associated with an increase in the rotational speed of the fan.
以上のように、放熱に対する要求は強いものの、内部の空気の流れがほとんどないか、あっても小さい場合においては、筐体やハウジングからの放熱性を向上させることで、内部の部品を長寿命化することができ、ひいては省エネルギーに寄与することができると考えられる。 As described above, although there is a strong demand for heat dissipation, if there is little or no internal air flow, improving the heat dissipation from the housing and housing will make the internal components longer It can be considered that it can contribute to energy saving.
上述の課題に対して、これまで検討された例はほとんどないが、（特許文献１）、（特許文献２）には、家電製品の筐体等に適した熱放射性に優れた鋼板に関する技術が開示されている。この技術は、高い熱放射性の塗膜を有する表面処理材料に関するものであるが、熱の放射に優れる塗膜は熱の吸収にも優れるため、熱の吸収と放射のバランスによっては、予想したほど機器内部の温度が低下しないといったケースも考えられる。また、これら文献には、２層に形成した塗膜のうち、内側の塗膜に熱放射性に優れた塗膜を用いる技術も開示されているが、前述した通り、熱の放射に優れる塗膜は熱の吸収にも優れるため、外層の塗膜の性状によっては、吸収した熱が内側の塗膜に蓄えられて、鋼板の温度が上昇する可能性も考えられる。 Although there are few examples examined so far with respect to the above-mentioned problems, (Patent Document 1) and (Patent Document 2) include a technology related to a steel sheet excellent in thermal radiation suitable for a housing of a home appliance. It is disclosed. This technology is related to surface treatment materials with highly heat-radiative coatings, but coatings that excel in heat radiation also excel in heat absorption, so depending on the balance between heat absorption and radiation, There may be cases where the temperature inside the device does not decrease. In addition, these documents also disclose a technique of using a coating film excellent in thermal radiation for the inner coating film among the coating films formed in two layers, but as described above, the coating film excellent in heat radiation. Is also excellent in heat absorption, and depending on the properties of the outer coating film, the absorbed heat may be stored in the inner coating film and the temperature of the steel sheet may increase.
本発明は、上記の問題点を解決し、効率よく熱の吸収と放散を行うことができる表面処理金属材料を提供することを目的としている。 An object of the present invention is to provide a surface-treated metal material that can solve the above-described problems and can efficiently absorb and dissipate heat.
本発明者らは、上記課題を解決すべく、鋭意検討を行った結果、シロキサン結合に有機基を含む有機‐無機ハイブリッド樹脂またはシリコーン樹脂を主成分としたマトリックスに特定形状の微小炭素繊維を添加し、所定の熱伝導率を有してなる被覆層を形成した表面処理金属材料によって課題が解決できることを見出し、本発明を完成させるに至った。具体的には、以下の通りである。
（１）金属材料表面の少なくとも一部に、シロキサン結合に有機基を含む有機‐無機ハイブリッド樹脂またはシリコーン樹脂から成るマトリックスに平均アスペクト比が３以上の微小炭素繊維を含有してなる被覆層を有する表面処理金属材料であって，マトリックスの熱伝導率が０．５Ｗ／ｍ・Ｋ以上、かつ該被覆層全体の熱伝導率が１．４Ｗ／ｍ・Ｋ以上であることを特徴とする吸放熱特性に優れた表面処理金属材料。
（２）前記微小炭素繊維の含有量が、被覆層全体に対し０．０１〜２５質量％である（１）に記載した吸放熱特性に優れた表面処理金属材料。
（３）前記微小炭素繊維の繊維径が１０μm以下である（１）に記載した吸放熱特性に優れた表面処理金属材料。
（４）前記微小炭素繊維がカーボンナノチューブである（１）に記載した吸放熱特性に優れた表面処理金属材料。
（５）前記金属材料が、めっき鋼材、ステンレス鋼材、チタン材、チタン合金材、アルミニウム材、アルミニウム合金材から選ばれる１種である（１）に記載した表面処理金属材料。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have added microcarbon fibers of a specific shape to a matrix mainly composed of an organic-inorganic hybrid resin or silicone resin containing an organic group in the siloxane bond. And it discovered that a subject could be solved by the surface treatment metal material which formed the coating layer which has predetermined | prescribed thermal conductivity, and came to complete this invention. Specifically, it is as follows.
(1) At least a part of the surface of the metal material has a coating layer containing a fine carbon fiber having an average aspect ratio of 3 or more in a matrix made of an organic-inorganic hybrid resin or silicone resin containing an organic group in a siloxane bond. It is a surface-treated metal material, and the thermal conductivity of the matrix is 0.5 W / m · K or more, and the thermal conductivity of the entire coating layer is 1 . 4 A surface-treated metal material having excellent heat-absorbing and radiating characteristics, characterized by being W / m · K or more.
(2) The surface-treated metal material having excellent heat absorption and radiation characteristics described in (1), wherein the content of the fine carbon fiber is 0.01 to 25% by mass with respect to the entire coating layer.
(3) The surface-treated metal material excellent in the heat absorbing / dissipating properties described in (1), wherein the fine carbon fiber has a fiber diameter of 10 μm or less.
(4) The surface-treated metal material having excellent heat-absorbing / dissipating properties described in (1), wherein the fine carbon fibers are carbon nanotubes.
( 5 ) The surface-treated metal material according to (1), wherein the metal material is one selected from a plated steel material, a stainless steel material, a titanium material, a titanium alloy material, an aluminum material, and an aluminum alloy material.
本発明によれば、例えば、電気機器の内部で発生する熱の吸収および放散に優れた表面処理金属板を容易に得ることができる。本発明の表面処理金属材料の特徴として、被覆層は所定の熱伝導率を有しているため、発熱源から吸収した熱を、固体内の伝導によって効率良く外部に放出することが可能である。 ADVANTAGE OF THE INVENTION According to this invention, the surface treatment metal plate excellent in absorption and dissipation of the heat which generate | occur | produces inside an electric equipment, for example can be obtained easily. As a feature of the surface-treated metal material of the present invention, since the coating layer has a predetermined thermal conductivity, it is possible to efficiently release the heat absorbed from the heat source to the outside by conduction in the solid. .
以下に、本発明の表面処理金属材料について説明する。 The surface-treated metal material of the present invention will be described below.
本発明の表面処理金属材料に形成された被覆層は、その構成主体であるマトリックス、微小炭素繊維からなり、加えて必要に応じて添加する添加物からなっている。 The coating layer formed on the surface-treated metal material of the present invention is composed of a matrix and fine carbon fibers, which are constituent components thereof, and an additive that is added as necessary.
当該被覆層中に含まれる微小炭素繊維は、平均アスペクト比が３以上であることを特徴としている。ここでいう微小炭素繊維とは、直径が10μmを超えない繊維形状を有する炭素化合物の総称であり、繊維状であればいかなるものも好適に用いることができる。繊維状炭素としてしばしば用いられるものには、炭素繊維、ウィスカー、カーボンナノチューブがあげられる。このうち、ウィスカーとは、転位をほとんど含まない単結晶材料のことをいい、炭素化合物のウィスカーとしては、カーボンウィスカー、フラーレンウィスカーなどが知られている。 The fine carbon fibers contained in the coating layer are characterized by having an average aspect ratio of 3 or more. The fine carbon fiber here is a general term for carbon compounds having a fiber shape whose diameter does not exceed 10 μm, and any fiber can be suitably used as long as it is fibrous. Carbon fibers, whiskers, and carbon nanotubes are frequently used as fibrous carbon. Among these, the whisker refers to a single crystal material containing almost no dislocations, and carbon whiskers, fullerene whiskers, and the like are known as whiskers of carbon compounds.
本発明の被覆層に含まれる微小炭素繊維として、とりわけ好ましいのは、カーボンナノチューブである。カーボンナノチューブとは、炭素原子のみから構成される直径0.4〜50nmの筒（チューブ）状物質であり、一般的にはグラファイトの六角網面の１原子層を、筒状に丸めた構造を有するものをいう。また、カーボンナノチューブとは、せまい意味では結晶性の炭素からなるものを指すが、ここでは、周囲に非晶質状態のアモルファスカーボンが存在するものも含めてカーボンナノチューブとよぶことにする。 Carbon nanotubes are particularly preferred as the fine carbon fibers contained in the coating layer of the present invention. A carbon nanotube is a tube (tube) material composed of only carbon atoms and having a diameter of 0.4 to 50 nm, and generally has a structure in which one atomic layer of a hexagonal mesh surface of graphite is rolled into a tube. Say. In addition, the carbon nanotubes refer to those made of crystalline carbon in a narrow sense, but here, carbon nanotubes including those having amorphous carbon in an amorphous state are called carbon nanotubes.
カーボンナノチューブには、単層、二層、多層ナノチューブなどの種類があるが、本発明で用いるカーボンナノチューブは、これらのうちのいずれであっても特に支障なく用いることができる。また、製造方法としてCVD法、アークジェット法などが知られているが、本発明で用いるナノチューブはいずれも好適に用いることができる。これらの合成の過程で触媒等を用いた場合には、ナノチューブ内に不純物として残留していることがあるが、ナノチューブの電気伝導性には大きな影響を及ぼさないため、これらのナノチューブも好適に用いることができる。 There are various types of carbon nanotubes such as single-walled, double-walled, and multi-walled nanotubes, and any of these can be used without any problem. Further, CVD methods, arc jet methods, and the like are known as manufacturing methods, and any of the nanotubes used in the present invention can be suitably used. When a catalyst or the like is used in the synthesis process, it may remain as an impurity in the nanotube. However, since the electrical conductivity of the nanotube is not greatly affected, these nanotubes are also preferably used. be able to.
本発明で用いる微小炭素繊維の平均アスペクト比を３以上に限定したのは、少量の添加量で優れた吸放熱特性が得られるためであり、好ましくは平均アスペクト比が５以上、より好ましくは１０以上の平均アスペクト比を有する微小炭素繊維を含有していることが好ましい。これらの微小炭素繊維を用いることで、少ない添加量で被覆層に顕著な吸放熱性を付与することが可能となる。これは、炭素材料が持っている優れた吸放熱性に加えて、被覆層の熱伝導率が高くなることによると考えている。すなわち、一般的には、微小炭素繊維の熱伝導率はマトリックス部分と比較して大きいため、長手方向にのびた微小繊維同士が接触することにより、等方的な形状の炭素材料、例えばカーボンブラックなどと比較して、より少ない添加量で熱の通る路が確保され、熱の伝導が向上することによると考えられる。一方で、被覆層に含まれる微小炭素繊維の平均アスペクト比が大きすぎる場合には、繊維同士の凝集が発生しやすくなり、多くのフロックを形成して被覆層中に均一に分散させることが困難になる。これらの点から、好ましい平均アスペクト比は10000以下であり、より好ましくは5000以下、さらに好ましくは3000以下である。 The reason why the average aspect ratio of the fine carbon fiber used in the present invention is limited to 3 or more is that an excellent heat absorption and heat dissipation characteristic can be obtained with a small amount of addition, and the average aspect ratio is preferably 5 or more, more preferably 10 It is preferable to contain fine carbon fibers having the above average aspect ratio. By using these fine carbon fibers, it is possible to impart significant heat absorption and heat dissipation to the coating layer with a small addition amount. This is thought to be due to the fact that the thermal conductivity of the coating layer is increased in addition to the excellent heat-absorbing and radiating properties of the carbon material. That is, generally, since the thermal conductivity of the fine carbon fiber is larger than that of the matrix portion, an isotropic shape carbon material, such as carbon black, is brought about by contacting the fine fibers extending in the longitudinal direction. Compared to the above, it is considered that a path through which heat passes is secured with a smaller addition amount, and heat conduction is improved. On the other hand, if the average aspect ratio of the fine carbon fibers contained in the coating layer is too large, the fibers tend to agglomerate, making it difficult to form many flocs and uniformly disperse them in the coating layer. become. From these points, the preferable average aspect ratio is 10,000 or less, more preferably 5000 or less, and still more preferably 3000 or less.
ここで、アスペクト比とは、繊維の長さを繊維の直径で除した値をいう。すなわち、アスペクト比が３以上の微小炭素繊維とは、微小炭素繊維であって、繊維の長さが直径の３倍以上のものをいう。本発明では、平均アスペクト比で微小炭素繊維の性状を規定しているが、平均アスペクト比とは微小炭素繊維の繊維長さの数平均を繊維直径の数平均で除した数値である。この場合において、種々のアスペクト比の微小炭素繊維を含んでいる場合には、まず、含まれる微小炭素繊維の平均繊維長さを求め、これを炭素繊維の平均繊維直径で除することによって平均アスペクト比を求めることができる。また、微小炭素繊維に枝分かれ、折れ曲がりなどがあったり、複雑な形状をしている場合など、一本の繊維に対しても複数のアスペクト比が定義できる場合がある。この場合には、最も大きなアスペクト比となるような繊維長さと繊維直径を用いて平均アスペクト比を計算することができる。 Here, the aspect ratio refers to a value obtained by dividing the length of the fiber by the diameter of the fiber. That is, the fine carbon fiber having an aspect ratio of 3 or more refers to a fine carbon fiber having a fiber length of 3 times or more of the diameter. In the present invention, the properties of the fine carbon fibers are defined by the average aspect ratio. The average aspect ratio is a numerical value obtained by dividing the number average of the fiber lengths of the fine carbon fibers by the number average of the fiber diameters. In this case, when micro carbon fibers having various aspect ratios are included, first, the average fiber length of the micro carbon fibers contained is obtained, and this is divided by the average fiber diameter of the carbon fibers. The ratio can be determined. Further, there may be a case where a plurality of aspect ratios can be defined for a single fiber, for example, when the minute carbon fiber is branched, bent, or has a complicated shape. In this case, the average aspect ratio can be calculated using the fiber length and fiber diameter that give the largest aspect ratio.
本発明で用いる被覆層中の微小炭素繊維のアスペクト比は、原則として、添加原料として使用する微小炭素繊維の平均アスペクト比で代用することができる。また、原料段階での微小炭素繊維の平均アスペクト比が求められない場合には、当該被覆層を溶剤等によって溶解し、あるいは薬品を用いてマトリックスを分解して得られた微小炭素繊維を顕微鏡によって観察した画像から、あるいはその画像を画像解析装置によって解析することにより求めることができる。さらに簡便な方法としては、被覆層のある断面を顕微鏡によって観察し、観察される微小炭素繊維の切断面の形状から計算によって求めることができる。これらの方法で平均アスペクト比を計算する場合には、できるだけ多くの微小炭素繊維に対して行うことが望ましいが、観察できる微小炭素繊維には限界があり、少なくとも100本の微小炭素繊維の測定結果をもって微小炭素繊維の性質として代表することができる。 In principle, the aspect ratio of the fine carbon fibers in the coating layer used in the present invention can be substituted by the average aspect ratio of the fine carbon fibers used as the additive raw material. In addition, when the average aspect ratio of the fine carbon fibers at the raw material stage is not required, the fine carbon fibers obtained by dissolving the coating layer with a solvent or the like and decomposing the matrix with a chemical agent are examined with a microscope. It can be obtained from the observed image or by analyzing the image with an image analyzer. As a simpler method, a cross-section with a coating layer can be observed with a microscope, and can be obtained by calculation from the observed shape of the cut surface of the fine carbon fiber. When calculating the average aspect ratio using these methods, it is desirable to use as many microcarbon fibers as possible. However, there is a limit to the observable microcarbon fibers, and the measurement results of at least 100 microcarbon fibers. Can be represented as the nature of the fine carbon fiber.
本発明で用いる微小炭素繊維は、マトリックスに添加され、被覆層を形成している。微小炭素繊維の含有量は、被覆層全体の質量に対する割合で０．０１％以上２５％以下であるが、好ましくは０．１％以上２０％以下であり、より好ましくは０．１％以上１０％以下である。微小炭素繊維の含有量がこれらの範囲を超えて少なすぎる場合、目的とする吸放熱特性が得られない場合が多く、逆に含有量がこれらの範囲を超えて多すぎる場合には、マトリックスが本来有している種々の性質が損なわれ、また、基材と良好な密着性が得られない可能性がある。これらの点を考慮すると、添加量はできるだけ少ない方が好ましく、必要な吸放熱特性が得られる範囲で最小限の含有量とするのが望ましい。 Fine carbon fiber for use in the present invention is added to Matrix, to form a coating layer. The content of the fine carbon fiber is 0.01% or more and 25% or less in a ratio to the mass of the entire coating layer, preferably 0.1% or more and 20% or less, more preferably 0.1% or more and 10% or less. % Or less. If the content of the minute carbon fiber is too small beyond these ranges, the intended heat absorption / release characteristics are often not obtained. Conversely, if the content exceeds these ranges, the matrix is not sufficient. Various inherent properties may be impaired, and good adhesion to the substrate may not be obtained. Considering these points, it is preferable that the addition amount be as small as possible, and it is desirable to set the content to the minimum as long as the necessary heat absorption / release characteristics are obtained.
また、被覆層の熱伝導率は１W/m・K以上であることが望ましく、2.5W/m・K以上であるとより好ましい。本発明の表面処理金属板の機能を、(a)発熱体からの熱を効率よく吸収する、(b)吸収した熱を効率よく放散する、に分けて考えた場合、被覆層の熱伝導率を特定の値以上にすることは、特に(b)の機能に対して重要である。熱の吸収と放散とは表裏一体の関係にあり、熱の吸収に優れた塗膜は吸収した熱も容易に放出する傾向にある。したがって、被覆層の熱伝導率が低い場合には、吸収した熱の移動がほとんど起こらず、吸収した熱をそのまま放散することとなる。これに対して、熱伝導率の高い被覆層を有する金属板においては、熱を吸収した面から温度の低い面への熱の移動が起こり、反対面から効率よく熱の放散が起こることになる。この場合でも熱を吸収した面からそのまま熱の放散が生じるが、反対側への熱の移動が大きい分、低い温度で定常状態となることが考えられる。 Further, the thermal conductivity of the coating layer is preferably 1 W / m · K or more, and more preferably 2.5 W / m · K or more. When the function of the surface-treated metal sheet of the present invention is divided into (a) efficiently absorbing heat from the heating element, and (b) efficiently dissipating absorbed heat, the thermal conductivity of the coating layer It is particularly important for the function (b) to set the value to a specific value or more. The absorption and dissipation of heat are in an integrated relationship, and a coating film excellent in absorption of heat tends to easily release the absorbed heat. Therefore, when the thermal conductivity of the coating layer is low, the absorbed heat hardly moves and the absorbed heat is dissipated as it is. On the other hand, in a metal plate having a coating layer with high thermal conductivity, heat transfer occurs from a surface that absorbs heat to a surface having a low temperature, and heat is efficiently dissipated from the opposite surface. . Even in this case, heat is directly dissipated from the heat-absorbing surface, but it is conceivable that a steady state is reached at a low temperature because the heat transfer to the opposite side is large.
１．４Ｗ／ｍ・Ｋ以上の熱伝導率を有する被覆層は、シロキサン結合に有機基を含む有機‐無機ハイブリッド樹脂またはシリコーン樹脂から成るマトリックスに平均アスペクト比が３以上の微小炭素繊維を添加することによって達成される。また、特に熱伝導率を高めることを目的として、熱伝導性の良い無機化合物粒子などを含有していても一向に差し支えない。これらの目的に対しては、一般的には酸化物、複酸化物粒子が用いられるが、炭化物、窒化物、炭窒化物、ホウ化物なども必要に応じて用いることができる。 1 . The coating layer having a thermal conductivity of 4 W / m · K or higher is obtained by adding fine carbon fibers having an average aspect ratio of 3 or more to a matrix made of an organic-inorganic hybrid resin or silicone resin containing an organic group in a siloxane bond. Achieved by: In particular, for the purpose of increasing the thermal conductivity, inorganic compound particles having a good thermal conductivity may be included. For these purposes, oxides and double oxide particles are generally used, but carbides, nitrides, carbonitrides, borides and the like can also be used as necessary.
一方、被覆層の熱伝導率は大きすぎても特に支障はないが、実用的な観点からは50W/m・K以下、望ましくは30W/m・K以下とすると良い。これらの上限に近い熱伝導率は、熱伝導率が高い無機系のマトリックスに、微小炭素繊維あるいは前述した熱伝導性が良い無機化合物粒子を必要に応じて添加することによって得られる。 On the other hand, if the thermal conductivity of the coating layer is too large, there is no particular problem, but from a practical viewpoint, it is 50 W / m · K or less, preferably 30 W / m · K or less. The thermal conductivity close to these upper limits can be obtained by adding fine carbon fibers or the above-described inorganic compound particles having good thermal conductivity to an inorganic matrix having high thermal conductivity as required.
また、マトリックスには、目的、用途に応じて一般に公知の顔料、あるいは着色、防錆等を目的とした成分を含んでいてもかまわない。 In addition, the Matrix, purpose, generally known pigments according to the application, or colored, may also contain components for the purpose of rust prevention and the like.
前述のマトリックスは、本願発明で用いる微小炭素繊維や前述の無機化合物粒子を含有しない状態で０．５Ｗ／ｍ・Ｋ以上の熱伝導率を有している。これは、マトリックスの熱伝導率が高いほど金属材料表面の被覆層の熱伝導率を高くすることができるためであり、結果として吸放熱特性に優れた表面処理金属材料を得ることができる。より好ましいマトリックスの熱伝導率は１．２Ｗ／ｍ・Ｋ以上である。マトリックスの熱伝導率の上限は特に限定は受けないが、実用的な観点からは５０Ｗ／ｍ・Ｋ以下であり、望ましくは３０Ｗ／ｍ・Ｋ以下とするのが良い。 Matrix before mentioned is that have a 0.5 W / m · K thermal conductivity of at least in a state containing no fine carbon fiber and the foregoing inorganic compound particles used in the present invention. This is because the higher the thermal conductivity of the matrix, the higher the thermal conductivity of the coating layer on the surface of the metal material. As a result, it is possible to obtain a surface-treated metal material having excellent heat dissipation / heat dissipation characteristics. More preferred thermal conductivity of the matrix is on the 1.2 W / m · K or more. The upper limit of the thermal conductivity of the matrix is not particularly limited, but it is 50 W / m · K or less, preferably 30 W / m · K or less, from a practical viewpoint.
これらの熱伝導率は、マトリックスとしてシロキサン結合に有機基を含む有機‐無機ハイブリッド樹脂あるいはシリコーン樹脂を用いることで好適に達成することができる。また、多くの無機化合物が熱伝導率が高いことを利用して、無機化合物とこれらの複合体、混合体として用いることも可能である。複合体あるいは混合体の望ましい態様としては、上記マトリックス中に無機化合物の粒子を混合する方法、あるいは逆に無機化合物の母材中に上記マトリックス混合をする方法を好適に用いることができる。 These thermal conductivities can be suitably achieved by using an organic-inorganic hybrid resin or a silicone resin containing an organic group in a siloxane bond as a matrix. Moreover, it can also be used as an inorganic compound, these composites, and a mixture using the high thermal conductivity of many inorganic compounds. Desirable embodiments of the complex or mixture may be used a method of the matrix mixing matrix in method or conversely inorganic compound, mixing particles of an inorganic compound in the matrix suitably.
被覆層の厚さは特に限定を受けるものではなく、目的に応じて適宜決定すればよい。高い吸放熱特性を得るためには、被覆層の厚さは厚い方が好ましい。しかしながら厚すぎる場合も経済的でなく、0.1μm以上20μm以下とするのが良く、好ましくは0.1μm以上15μm以下、より好ましくは0.5μm以上15μm以下である。 The thickness of the coating layer is not particularly limited and may be appropriately determined according to the purpose. In order to obtain high heat absorbing / dissipating properties, the coating layer is preferably thick. However, if it is too thick, it is not economical, and it may be 0.1 μm or more and 20 μm or less, preferably 0.1 μm or more and 15 μm or less, more preferably 0.5 μm or more and 15 μm or less.
本発明の被覆層は、通常、基材金属材料表面に直接形成されているが、金属材料と被覆層との間に、例えば密着性を確保するための処理層を設けても差し支えない。あるいは耐食性など特定の機能を持った中間層を設けることも可能である。また、本発明で用いる被覆層表面に別の機能を有する皮膜を形成することもできる。この場合には、本発明の被覆層は、発熱物からの熱には直接接触しないため、間接的な熱の吸収あるいは高い熱伝導率を生かした放熱の役割をになうことになる。 The coating layer of the present invention is usually formed directly on the surface of the base metal material. However, for example, a treatment layer for ensuring adhesion can be provided between the metal material and the coating layer. Alternatively, an intermediate layer having a specific function such as corrosion resistance can be provided. Moreover, the film | membrane which has another function can also be formed in the coating layer surface used by this invention. In this case, since the coating layer of the present invention is not in direct contact with the heat from the exothermic material, it serves as an indirect heat absorption or a heat dissipation utilizing the high thermal conductivity.
本発明の被覆層によって少なくとも一部が被覆された基材は、優れた吸放熱特性を発揮するほか、被覆部分は腐食性ガス、熱、摩擦、酸素、水、水蒸気、各種薬品などから保護されるため外部環境の影響を受けにくい。ここでいう基材とは特に限定されるものではないが、めっき鋼材、ステンレス鋼材、チタン材、チタン合金材、アルミニウム材、アルミニウム合金材が好ましい。めっき鋼材としては亜鉛めっき鋼材、亜鉛−鉄合金めっき鋼材、亜鉛−ニッケル合金めっき鋼材、亜鉛−クロム合金めっき鋼材、亜鉛−アルミ合金めっき鋼材、アルミめっき鋼材、亜鉛−アルミ−マグネシウム合金めっき鋼材、亜鉛−アルミ−マグネシウム−シリコン合金めっき鋼材、アルミ−シリコン合金めっき鋼材、亜鉛めっきステンレス鋼材、アルミめっきステンレス鋼材等が挙げられる。 The substrate that is at least partially coated with the coating layer of the present invention exhibits excellent heat-absorbing and radiating properties, and the coated portion is protected from corrosive gas, heat, friction, oxygen, water, water vapor, various chemicals, etc. Therefore, it is not easily affected by the external environment. Although it does not specifically limit with a base material here, plated steel material, stainless steel material, titanium material, titanium alloy material, aluminum material, and aluminum alloy material are preferable. As galvanized steel materials, galvanized steel materials, zinc-iron alloy plated steel materials, zinc-nickel alloy plated steel materials, zinc-chromium alloy plated steel materials, zinc-aluminum alloy plated steel materials, aluminum-plated steel materials, zinc-aluminum-magnesium alloy plated steel materials, zinc -Aluminum-magnesium-silicon alloy plated steel, aluminum-silicon alloy plated steel, galvanized stainless steel, aluminum plated stainless steel, etc.
ステンレス鋼材としてはフェライト系ステンレス鋼材、マルテンサイト系ステンレス鋼材、オーステナイト系ステンレス鋼材等があげられる。 チタン材、チタン合金材としては、純度の高いαチタンのほかα＋βチタン、βチタンなどがあげられる。α＋βチタンにはTi-6Al-4V、βチタンにはTi-15V-3Cr-3Sn-3Al、Ti-22V-4Alなどの成分系があり、これらのいずれも好適に用いることができる。アルミニウム合金材としてはＪＩＳ１０００番系（純Ａｌ系）、ＪＩＳ２０００番系（Ａｌ−Ｃｕ系）、ＪＩＳ３０００番系（Ａｌ−Ｍｎ系）、ＪＩＳ４０００番系（Ａｌ−Ｓｉ系）、ＪＩＳ５０００番系（Ａｌ−Ｍｇ系）、ＪＩＳ６０００番系（Ａｌ−Ｍｇ−Ｓｉ系）、ＪＩＳ７０００番系（Ａｌ−Ｚｎ系）等があげられる。 Examples of stainless steel materials include ferritic stainless steel materials, martensitic stainless steel materials, and austenitic stainless steel materials. Examples of the titanium material and the titanium alloy material include α titanium having high purity, α + β titanium, β titanium, and the like. α + β titanium has component systems such as Ti-6Al-4V, and β titanium has Ti-15V-3Cr-3Sn-3Al, Ti-22V-4Al, and any of these can be suitably used. As the aluminum alloy material, JIS 1000 series (pure Al series), JIS 2000 series (Al-Cu series), JIS 3000 series (Al-Mn series), JIS 4000 series (Al-Si series), JIS 5000 series (Al--) Mg series), JIS6000 series (Al-Mg-Si series), JIS7000 series (Al-Zn series), and the like.
本発明で用いる金属材料の形状は、平板状のものはもちろんのこと、パイプ状、棒状、あるいはH形、矢板のような特殊な形状であっても差し支えない。これら金属材料の厚さも特に限定されるものではなく、薄いものから厚いものまで幅広い厚さの材料に対して適用することができる。また、金属材料の表面は、ブライトアニール、バフ研磨、あるいはブラストなどの処理を施してあってもよい。 The shape of the metal material used in the present invention may be a plate shape, a pipe shape, a rod shape, or a special shape such as an H shape or a sheet pile. The thickness of these metal materials is not particularly limited, and can be applied to materials having a wide range of thickness from thin to thick. Further, the surface of the metal material may be subjected to a treatment such as bright annealing, buffing, or blasting.
本発明で用いる被覆層は、一般に公知の技術を用いて形成することができる。シロキサン結合に有機基を含む有機‐無機ハイブリッド樹脂またはシリコーン樹脂から成るマトリックスに微小炭素繊維を添加、混合する。混合には、ロールミル、ペイントシェーカー等の公知の技術を、あるいはボールミル、振動ミルなど粒子の微粉砕技術と組み合わせ、粉砕した微小繊維を塗料と混合する方法も好適に用いることができる。 The coating layer used in the present invention can be generally formed using a known technique. The organic containing an organic group to the siloxane bond - adding fine carbon fibers from inorganic hybrid resin or silicone resin for forming Ru matrix mix. For mixing, a known technique such as a roll mill, a paint shaker, or the like, or a technique for finely pulverizing particles such as a ball mill or a vibration mill, and a method of mixing the pulverized microfibers with a paint can be suitably used.
本発明の微小炭素繊維は、被覆層中に均一に分散している状態が最も望ましいが、必ずしも均一な分散が必要とされているものではない。本願発明で用いる微小炭素繊維は、その凝集体が大きくても塗膜の厚さより小さくなっていることが好ましい。微小炭素繊維の大きさが、塗膜の厚さより大きい場合には、塗膜表面に凝集体に起因する凹凸が発生するため適当でない。 The fine carbon fiber of the present invention is most desirably dispersed uniformly in the coating layer, but does not necessarily require uniform dispersion. The fine carbon fiber used in the present invention is preferably smaller than the thickness of the coating film even if the aggregate is large. If the size of the fine carbon fiber is larger than the thickness of the coating film, unevenness due to aggregates is generated on the coating film surface, which is not appropriate.
塗装方法としては、例えば浸漬、はけ塗り、スプレー塗装、ロールコーター塗装、カーテンフローコーター塗装、ローラーカーテンコーター塗装、バーコーター塗装、電着塗装、静電塗装などがあげられる。また、被覆した塗膜層を硬化させることを目的として加熱することも可能である。加熱方法は、一般に公知の方法、例えば熱風加熱炉、遠赤外線炉、誘導加熱炉、直火炉などを用いることができる。また、必要に応じて、常温で乾燥する方法や紫外線、電子線による硬化方法を使用することもできる。加熱による硬化方法では、マトリックスの成分、炭素繊維の添加量等に応じて、温度を設定することができる。 Examples of the coating method include dipping, brush coating, spray coating, roll coater coating, curtain flow coater coating, roller curtain coater coating, bar coater coating, electrodeposition coating, electrostatic coating, and the like. It is also possible to heat the coated film layer for the purpose of curing. As a heating method, generally known methods such as a hot air heating furnace, a far-infrared furnace, an induction heating furnace, and a direct-fired furnace can be used. Moreover, the method of drying at normal temperature and the hardening method by an ultraviolet-ray and an electron beam can also be used as needed. In the curing method by heating, the temperature can be set according to the components of the matrix, the amount of carbon fiber added, and the like.
上述の塗膜の形成は、加工前の鋼材の状態で行ってもよく、あるいは所定の形状に加工した後に行うこともできる。使用目的、使用方法、使用部位などに応じて適宜決定することができる。 Formation of the above-mentioned coating film may be performed in the state of a steel material before processing, or may be performed after processing into a predetermined shape. It can be appropriately determined according to the purpose of use, the method of use, the site of use and the like.
本発明を以下の実施例によって具体的に説明する。 The present invention you illustrated by the following examples in detail.
（実施例２）
マトリックス成分としてシロキサン結合が３次元状にネットワークを形成し、側鎖およびネットワーク中にメチル基を有する有機−無機ハイブリッド材料に、微小炭素繊維として、(1)東海カーボン製カーボンウィスカー（直径0.3〜0.6μm、長さ5〜15μm；平均アスペクト比16）、(2) 気相法で合成したナノファイバーＡ（直径200nm、長さ0.5〜5μm；平均アスペクト比3.5、6）および合成条件を変えて合成したナノファイバーＢ（直径150nm、長さ10〜20μm；平均アスペクト比75）、(3) ILJIN社製多層カーボンナノチューブ（直径10〜25nm、長さ1〜50μm；平均アスペクト比180）、(4) シンセン・ナノテクポート社製単層カーボンナノチューブ（直径2nm、長さ1〜10μm；平均アスペクト比1200）を添加して塗料を作製した。また、添加物を含まない塗料および上記の炭素繊維のかわりにカーボンブラック（40nm径、平均アスペクト比1.0）を添加した塗料を比較材として作製した。塗料の作製は、実施例１に準ずる方法で行った。微小炭素繊維の添加量は、いずれもマトリックスの固形分全体に対する質量割合で１％とした。作製した塗料を、下地処理を行っていない0.6mm厚さのステンレス鋼板（SUS430、No.4仕上げ材）に塗布、焼付けを行い、表面処理ステンレス鋼板を得た。塗膜の焼付けは250℃、1分間とし、形成した被覆層の厚さは約3μmである。本実施例においても微小炭素繊維の凝集の凝集が認められたが、凝集の大きさは最大で約2μmであった。
(Example 2)
As a matrix component, a siloxane bond forms a three-dimensional network, and an organic-inorganic hybrid material having a methyl group in the side chain and network. As a fine carbon fiber, (1) Tokai carbon carbon whiskers (diameter 0.3 to 0.6 μm, length 5-15μm; average aspect ratio 16), (2) Nanofiber A synthesized by gas phase method (diameter 200nm, length 0.5-5μm; average aspect ratio 3.5, 6) and synthesis conditions were changed Nanofiber B (diameter 150 nm, length 10-20 μm; average aspect ratio 75), (3) ILJIN multi-wall carbon nanotubes (diameter 10-25 nm, length 1-50 μm; average aspect ratio 180), (4) Single-walled carbon nanotubes (diameter 2 nm, length 1 to 10 μm; average aspect ratio 1200) manufactured by Shenzhen Nanotechport Co. were added to prepare a paint. Further, a paint containing no additive and a paint added with carbon black (40 nm diameter, average aspect ratio 1.0) instead of the above carbon fiber were prepared as comparative materials. The coating material was produced by the method according to Example 1. The addition amount of the fine carbon fibers was 1% in terms of mass ratio with respect to the entire solid content of the matrix. The prepared paint was applied and baked on a 0.6 mm thick stainless steel plate (SUS430, No.4 finishing material) that had not been subjected to the base treatment, to obtain a surface-treated stainless steel plate. The coating film was baked at 250 ° C. for 1 minute, and the thickness of the formed coating layer was about 3 μm. Also in this example, agglomeration of fine carbon fibers was observed, but the maximum agglomeration size was about 2 μm.
得られた表面処理ステンレス鋼板について、吸放熱特性を以下の方法により測定した。150mm×300mm×100mm程度の大きさの箱を作製し、そのうちの150×300mmのひとつの面に、被覆層を形成した面が箱の内側となるように表面処理亜鉛めっき鋼板をセットする。箱の内部に模擬発熱体を置き、発熱体から約20mm離れた場所の温度を熱電対で測定する。被覆層を形成した表面処理亜鉛めっき鋼板を通して効率良く熱が吸収、放散されていれば、箱の内部の温度は鋼板の吸放熱特性に応じて低下する。吸放熱特性の評価は、塗装なしの鋼板と比較して測定温度が10℃以上低い場合には◎、7℃以上10℃未満の場合には○、3℃以上7℃未満の場合には△、それより小さい場合には×とした。
さらに、表面被覆層の熱伝導率を測定した。結果を第２表に示した。
The obtained surface-treated stainless steel sheet, the absorption heat radiation characteristics were measured by the following method. A box having a size of about 150 mm × 300 mm × 100 mm is produced, and a surface-treated galvanized steel sheet is set on one side of 150 × 300 mm so that the surface on which the coating layer is formed is inside the box. A simulated heating element is placed inside the box, and the temperature at a location approximately 20 mm away from the heating element is measured with a thermocouple. If heat is efficiently absorbed and dissipated through the surface-treated galvanized steel sheet on which the coating layer is formed, the temperature inside the box decreases according to the heat absorbing / dissipating characteristics of the steel sheet. Evaluation of heat absorption and dissipation characteristics is ◎ when the measured temperature is 10 ℃ or more lower than that of the uncoated steel sheet, ○ when it is 7 ℃ or more and less than 10 ℃, △ when it is 3 ℃ or more and less than 7 ℃ When it was smaller than that, it was set as x.
Furthermore, the thermal conductivity of the surface coating layer was measured. The results are shown in Table 2.
微小炭素繊維を添加していない被覆層、およびカーボンブラック（平均アスペクト比１）を添加した被覆層は熱伝導率が低く、本願発明の熱伝導率に達していない。この結果、これらの被覆層を形成した表面処理鋼板では十分な吸放熱特性が得られていない。一方、平均アスペクト比の平均値が３以上の微小炭素繊維を含有する被覆層では1 W/m・K以上の熱伝導率が得られており、吸放熱特性を測定した結果でも7℃以上温度が低くなっている。また、特に、微小炭素繊維の平均アスペクト比が大きく、2.5W/m・K以上の熱伝導率の被覆層を有する表面処理鋼板は、吸放熱特性の測定結果でも10℃以上低い温度が得られており、優れた吸放熱特性を有していることがわかる。 The coating layer to which fine carbon fibers are not added and the coating layer to which carbon black (average aspect ratio 1) is added have low thermal conductivity, and do not reach the thermal conductivity of the present invention. As a result, the surface-treated steel sheet on which these coating layers are formed does not provide sufficient heat absorbing / dissipating characteristics. On the other hand, the thermal conductivity of 1 W / m · K or more is obtained in the coating layer containing fine carbon fibers with an average value of average aspect ratio of 3 or more. Is low. In particular, a surface-treated steel sheet with a coating layer with a large average aspect ratio of fine carbon fibers and a thermal conductivity of 2.5 W / m It can be seen that it has excellent heat absorption and heat dissipation characteristics.
以上をまとめると、本発明の平均アスペクト比を有する微小炭素繊維を添加物として含有し、所定の熱伝導率の被覆層を形成した鋼板は良好な吸放熱特性を有していることがわかった。
（実施例３）
マトリックス成分としてメチル基を有するシリコーン樹脂、微小炭素繊維として実施例１と同じILJIN社製のCNTを選定し、実施例１と同様の方法により、第３表に示した割合で混合して塗料を作製した。CNTの添加量は、マトリックスの固形分全体に対する質量％である。作製した塗料をクロメート処理を行った0.8mm厚さの溶融亜鉛めっき鋼板に塗布、焼付けを行い、被覆層を有する亜鉛めっき鋼板を得た。塗膜の焼付けは200℃、1分間とし、形成した被覆層の厚さは約10μmである。本実施例の塗膜中におけるCNTの凝集体の大きさは4〜5μm程度であった。
Summarizing the above, it was found that the steel sheet containing the fine carbon fiber having the average aspect ratio of the present invention as an additive and having a coating layer having a predetermined thermal conductivity has good heat absorption and dissipation characteristics. .
(Example 3)
A silicone resin having a methyl group as a matrix component and CNTs manufactured by ILJIN as in Example 1 are selected as fine carbon fibers, and mixed in the same manner as in Example 1 at the ratio shown in Table 3 to form a paint. Produced. The amount of CNT added is mass% with respect to the total solid content of the matrix. The prepared paint was applied to a 0.8 mm thick hot dip galvanized steel sheet that had been chromated and baked to obtain a galvanized steel sheet having a coating layer. The coating was baked at 200 ° C. for 1 minute, and the thickness of the formed coating layer was about 10 μm. The size of the CNT aggregate in the coating film of this example was about 4 to 5 μm.
得られた表面処理鋼板について、実施例２と同様に吸放熱特性、および表面被覆層の熱伝導率を測定した。結果を第３表に示した。 About the obtained surface-treated steel sheet, the heat absorption / release characteristics and the thermal conductivity of the surface coating layer were measured in the same manner as in Example 2 . The results are shown in Table 3.
本実施例では、マトリックスとして高い熱伝導率（1.2 W/m・K）の樹脂を使用したため、特にCNTを含有していない被覆層であっても1W/m・K以上の熱伝導率が得られている。しかしながら、CNTを含有しない被覆層を形成した鋼板では、十分な吸放熱特性が得られていないことがわかる。この結果から、所定の熱伝導率の被覆層を有する鋼板であっても、微小炭素繊維を含有していない場合には良好な吸放熱特性が得られず、被覆層中に微小炭素繊維が存在していることが優れた吸放熱特性を得るために重要であることがわかった。 In this example, a resin with a high thermal conductivity (1.2 W / m · K) was used as the matrix, so that a thermal conductivity of 1 W / m · K or more was obtained even with a coating layer that did not contain CNTs. It has been. However, it can be seen that a steel sheet with a coating layer that does not contain CNTs does not have sufficient heat absorption / release characteristics. From this result, even if the steel sheet has a coating layer with a predetermined thermal conductivity, if it does not contain fine carbon fibers, good heat absorption and dissipation characteristics cannot be obtained, and there are fine carbon fibers in the coating layer. It has been found that it is important to obtain excellent heat absorbing / dissipating characteristics.
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