JP5703542B2 - Carbon fiber reinforced resin sheet and roll wound body thereof - Google Patents
Carbon fiber reinforced resin sheet and roll wound body thereof Download PDFInfo
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Description
本発明は炭素繊維強化樹脂シート及びそのロール巻回体に係り、詳しくは、シート面内方向の熱伝導率が高いために放熱性に優れ、またシート面内方向の曲げ弾性率が大きいことから、剛直性、自立性に優れる反面、薄肉であるために可撓性にも優れ、ロール巻回体として容易に巻回可能な炭素繊維強化樹脂シートと、そのロール巻回体に関する。 The present invention relates to a carbon fiber reinforced resin sheet and a roll wound body thereof. Specifically, since the thermal conductivity in the in-plane direction of the sheet is high, the heat dissipation is excellent, and the bending elastic modulus in the in-plane direction of the sheet is large. Further, the present invention relates to a carbon fiber reinforced resin sheet that is excellent in rigidity and self-supporting property, but also excellent in flexibility because it is thin, and can be easily wound as a roll wound body, and a roll wound body thereof.
炭素繊維と樹脂を複合化してなる炭素繊維強化樹脂シートは、含有される炭素繊維の良熱伝導性や補強効果を利用して、各種の電気・電子部品等から発生する熱を放熱器等に伝えて放熱するための放熱シート等として、広く用いられている（例えば、特許文献１）。即ち、熱伝導率や曲げ弾性率の点においては、金属シートも優れたものであるが、金属シートに比べて、炭素繊維強化樹脂シートは比重が小さく、部品の軽量化を図ることができ、また発錆の問題もないことから、炭素繊維強化樹脂シートは金属製放熱シートの代替品として、近年、重視されている。 A carbon fiber reinforced resin sheet made of a composite of carbon fiber and resin utilizes the good thermal conductivity and reinforcing effect of the contained carbon fiber to transfer heat generated from various electrical and electronic components to a radiator, etc. It is widely used as a heat dissipation sheet for transmitting and dissipating heat (for example, Patent Document 1). That is, in terms of thermal conductivity and flexural modulus, the metal sheet is also excellent, but compared to the metal sheet, the carbon fiber reinforced resin sheet has a small specific gravity and can reduce the weight of the component. Moreover, since there is no problem of rusting, the carbon fiber reinforced resin sheet has been emphasized in recent years as an alternative to the metal heat dissipating sheet.
このような炭素繊維強化樹脂シートについては、その用途、取り扱い性、加工性等の面から、次のような特性が望まれる。
(1) 放熱シートの用途においては、シート面内方向における熱伝導率が高いことが望まれる。
(2) シートの取り扱い性や、シートを適用する部材の補強効果の面から、シート面内方向における曲げ弾性率が高く、剛性、自立性に優れることが望まれる。
(3) (2)の一方で、製品としての保管、運搬形態、或いは、他のシートとの貼り合わせ等の加工性の面から、可撓性、屈曲性に優れ、容易にロール状に巻回できることが望まれる。即ち、ロール巻回体であれば、コンパクトに保管、運搬することが可能であり、また、ロール巻回体からシートを引き出して、高生産性の、所謂Ｒｏｌｌ ｔｏ Ｒｏｌｌ方式にて、他のシート材等と容易に貼り合わせ加工することができる。
About such a carbon fiber reinforced resin sheet, the following characteristics are desired from the viewpoints of its use, handleability, workability, and the like.
(1) In the use of a heat dissipation sheet, it is desired that the thermal conductivity in the in-plane direction of the sheet is high.
(2) From the viewpoint of sheet handling properties and the reinforcing effect of the member to which the sheet is applied, it is desired that the sheet has a high flexural modulus in the in-plane direction and is excellent in rigidity and independence.
(3) On the other hand, it is excellent in flexibility and flexibility from the viewpoint of workability such as storage as a product, transportation form, or lamination with other sheets, and it can be easily wound into a roll. It is desirable to be able to rotate. In other words, if it is a roll wound body, it can be stored and transported in a compact manner. Also, by pulling out the sheet from the roll wound body and using the so-called Roll to Roll method with high productivity, other sheets can be used. It can be easily bonded to a material or the like.
しかしながら、従来において、上記(1)〜(3)の要求特性をすべて満たす炭素繊維強化樹脂シートは提供されていないのが実状である。即ち、一般に、曲げ弾性率の高いシートは屈曲性、可撓性に劣り、ロール状に巻回することができない。屈曲性、可撓性に優れたシート構成では剛直性、自立性が小さく、また放熱性も劣る傾向がある。 However, the actual situation is that a carbon fiber reinforced resin sheet satisfying all the required properties of the above (1) to (3) has not been provided. That is, in general, a sheet having a high flexural modulus is inferior in flexibility and flexibility and cannot be wound into a roll. A sheet structure excellent in bendability and flexibility tends to be less rigid and self-supporting and have poor heat dissipation.
本発明は、上記従来の実状に鑑みて優れたものであって、面内方向における放熱性及び剛直性が高いシートでありながら、屈曲性、可撓性に優れた炭素繊維強化樹脂シートを提供することを課題とする。 The present invention provides a carbon fiber reinforced resin sheet that is excellent in view of the above-described conventional situation and has excellent flexibility and flexibility while being a sheet having high heat dissipation and rigidity in the in-plane direction. The task is to do.
本発明者は、上記課題を解決すべく鋭意検討した結果、炭素繊維強化樹脂シートを、シート面内方向における熱伝導率及び曲げ弾性率が十分に高いシート構成とした上で、所定範囲の極薄シートとすることにより、屈曲性及び可撓性を付与することができることを見出した。 As a result of intensive studies to solve the above problems, the present inventor made a carbon fiber reinforced resin sheet having a sheet configuration with sufficiently high thermal conductivity and flexural modulus in the in-plane direction of the sheet. It has been found that by using a thin sheet, flexibility and flexibility can be imparted.
本発明は、このような知見に基いて達成されたものであり、以下を要旨とする。 The present invention has been achieved based on such knowledge, and the gist thereof is as follows.
［１］ 炭素繊維と樹脂を複合化してなる炭素繊維強化樹脂製基材シートを含む炭素繊維強化樹脂シートであって、該炭素繊維が、一方向に引き揃えられた長繊維または連続繊維の形態で該シート内に存在し、該炭素繊維強化樹脂製基材シートの両面に、フィルム、織布及び不織布よりなる群から選ばれる１種又は２種以上を積層一体化してなり、該基材シートの面内方向における熱伝導率の最大値が１０Ｗ／ｍＫ以上で、該基材シートの面内方向における曲げ弾性率の最大値が２０ＧＰａ以上であり、かつ、該炭素繊維強化樹脂シートの総厚さが０．０５〜０．５ｍｍの範囲にあり、下記の屈曲性を満たすことを特徴とする炭素繊維強化樹脂シート。
屈曲性：該炭素繊維強化樹脂シートを３０ｃｍ角に切り出し、長手方向及び幅方向のそれぞれについて、曲率半径３０ｍｍでの折り曲げを５回繰り返した際、割れずに屈曲できる。
[1] A carbon fiber reinforced resin sheet including a carbon fiber reinforced resin base material sheet formed by combining carbon fiber and a resin, wherein the carbon fibers are in the form of long fibers or continuous fibers aligned in one direction. in present in the sheet, on both surfaces of the carbon fiber reinforced resin substrate sheet, a film, formed by laminating integrally one or more selected from the group consisting of woven and nonwoven fabrics, the substrate The maximum value of the thermal conductivity in the in-plane direction of the sheet is 10 W / mK or more, the maximum value of the flexural modulus in the in-plane direction of the base sheet is 20 GPa or more, and the total of the carbon fiber reinforced resin sheets A carbon fiber reinforced resin sheet having a thickness in the range of 0.05 to 0.5 mm and satisfying the following flexibility.
Flexibility: When the carbon fiber reinforced resin sheet is cut into a 30 cm square and bent at a radius of curvature of 30 mm for each of the longitudinal direction and the width direction, it can be bent without breaking.
［２］ 該基材シートの面内方向における熱伝導率の最大値が６０Ｗ／ｍＫ以上で、該基材シートの面内方向における曲げ弾性率の最大値が２５０ＧＰａ以上であることを特徴とする［１］に記載の炭素繊維強化樹脂シート。 [2] The maximum value of the thermal conductivity in the in-plane direction of the base sheet is 60 W / mK or more, and the maximum value of the flexural modulus in the in-plane direction of the base sheet is 250 GPa or more. The carbon fiber reinforced resin sheet according to [1].
［３］ 該炭素繊維が、コールタール・ピッチおよび／または石油タール・ピッチ由来の炭素繊維であることを特徴とする［１］又は［２］に記載の炭素繊維強化樹脂シート [3] The carbon fiber-reinforced resin sheet according to [1] or [2], wherein the carbon fiber is carbon fiber derived from coal tar pitch and / or petroleum tar pitch.
［４］ ［１］ないし［３］のいずれかに記載の炭素繊維強化樹脂シートを巻回してなることを特徴とする炭素繊維強化樹脂シートのロール巻回体。 [ 4 ] A roll wound body of a carbon fiber reinforced resin sheet obtained by winding the carbon fiber reinforced resin sheet according to any one of [1] to [ 3 ].
［５］ 該炭素繊維強化樹脂シートの幅が１０ｍｍ以上で、長さが５ｍ以上であることを特徴とする［４］に記載の炭素繊維強化樹脂シートのロール巻回体。 [ 5 ] The roll of carbon fiber reinforced resin sheet according to [ 4 ], wherein the carbon fiber reinforced resin sheet has a width of 10 mm or more and a length of 5 m or more.
本発明の炭素繊維強化樹脂シートは、この炭素繊維強化樹脂シートの主体を構成する基材シートの面内方向の熱伝導率が高く、放熱性に優れる。また、基材シートの面内方向の曲げ弾性率が高く剛直であることから、自立性に優れ、取り扱い性、他部材への補強効果に優れる。 The carbon fiber reinforced resin sheet of the present invention has high heat conductivity in the in-plane direction of the base material sheet constituting the main body of the carbon fiber reinforced resin sheet, and is excellent in heat dissipation. Moreover, since the bending elastic modulus in the in-plane direction of the base material sheet is high and rigid, it is excellent in self-supporting property, excellent in handleability and reinforcing effect on other members.
しかも、本発明の炭素繊維強化樹脂シートは、このように曲げ弾性率が高いにもかかわらず、厚さの薄い極薄シートであるために、屈曲性、可撓性に優れ、長尺シートであっても容易にロール状に巻回することができるため、運搬、保管時の取り扱い性や、他部材への貼り合わせ時の加工性等にも優れる。 In addition, the carbon fiber reinforced resin sheet of the present invention is an extremely thin sheet having a small thickness despite the high bending elastic modulus, and thus has excellent flexibility and flexibility, and is a long sheet. Even if it exists, since it can be wound in a roll shape easily, it is excellent also in the handleability at the time of conveyance and storage, the workability at the time of bonding to another member, etc.
なお、本発明の炭素繊維強化樹脂シートは、炭素繊維と樹脂の複合シートを基材シートとするため低比重で、かつ極薄シートであることにより、これを適用した部材の小型、薄肉、軽量化に有効である。 The carbon fiber reinforced resin sheet of the present invention is a low specific gravity and extremely thin sheet because the composite sheet of carbon fiber and resin is used as a base sheet, so that a member to which the carbon fiber reinforced resin sheet is applied is small, thin, and lightweight. It is effective for conversion.
このような本発明の炭素繊維強化樹脂シートは、電気電子機器の回路基板や、薄膜太陽電池の基板、液晶などのフラットディスプレイパネルの基板などに、これを貼着して放熱性を付与する用途等、幅広い用途に適用可能である。 Such a carbon fiber reinforced resin sheet of the present invention is applied to a circuit board of an electric / electronic device, a substrate of a thin film solar cell, a substrate of a flat display panel such as a liquid crystal, and the like to impart heat dissipation. It can be applied to a wide range of uses.
以下、本発明の実施の形態を具体的に説明するが、本発明は、以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々に変更して実施することができる。 Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
［炭素繊維強化樹脂シート］
本発明の炭素繊維強化樹脂シートは、炭素繊維と樹脂を複合化してなる炭素繊維強化樹脂製基材シートを含む炭素繊維強化樹脂シートであって、該基材シートの面内方向における熱伝導率の最大値が１０Ｗ／ｍＫ以上で、該基材シートの面内方向における曲げ弾性率の最大値が２０ＧＰａ以上であり、かつ、該炭素繊維強化樹脂シートの総厚さが０．０５〜０．５ｍｍの範囲にあり、下記の屈曲性を満たすことを特徴とする。
屈曲性：該炭素繊維強化樹脂シートを３０ｃｍ角に切り出し、長手方向及び幅方向のそれぞれについて、曲率半幅３０ｍｍでの折り曲げを５回繰り返した際、割れずに屈曲できる。
[Carbon fiber reinforced resin sheet]
The carbon fiber reinforced resin sheet of the present invention is a carbon fiber reinforced resin sheet including a carbon fiber reinforced resin base material sheet formed by combining carbon fiber and a resin, and the thermal conductivity in the in-plane direction of the base material sheet Is 10 W / mK or more, the maximum value of the flexural modulus in the in-plane direction of the base sheet is 20 GPa or more, and the total thickness of the carbon fiber reinforced resin sheet is 0.05 to 0.00. It is in the range of 5 mm and satisfies the following flexibility.
Flexibility: The carbon fiber reinforced resin sheet is cut into a 30 cm square, and can be bent without breaking when repeated in the longitudinal direction and the width direction at a curvature half width of 30 mm five times.
｛炭素繊維｝
まず、本発明の炭素繊維強化樹脂シートの主体となる炭素繊維強化樹脂製基材シートに含まれる炭素繊維について説明する。
本発明において、炭素繊維としては、ピッチ系炭素繊維を用いることが好ましい。即ち、炭素繊維はポリアクリロニトリル（ＰＡＮ）を原料とするＰＡＮ系炭素繊維と、一連のピッチ類を原料とするピッチ系炭素繊維に分類できるが、市販のＰＡＮ系炭素繊維の引張弾性率は一般的なグレードでは２３０〜４００ＧＰａ程度にとどまる。また、熱伝導率は標準的なグレードで１０Ｗ／ｍＫよりも小さく、高品位なグレードでも１００Ｗ／ｍＫを下回る。これに対して、ピッチ系炭素繊維は一般にＰＡＮ系炭素繊維に比べて高弾性率、高熱伝導率を達成しやすい。ピッチ系炭素繊維は、原料ピッチを溶融紡糸してピッチ繊維を得、次いで不融化、炭化或いは更に黒鉛化することによって得られる。
{Carbon fiber}
First, the carbon fiber contained in the carbon fiber reinforced resin base material sheet which is the main body of the carbon fiber reinforced resin sheet of the present invention will be described.
In the present invention, it is preferable to use pitch-based carbon fibers as the carbon fibers. In other words, carbon fibers can be classified into PAN-based carbon fibers made from polyacrylonitrile (PAN) and pitch-based carbon fibers made from a series of pitches, but the tensile modulus of commercially available PAN-based carbon fibers is general. In a high grade, it remains at about 230 to 400 GPa. Further, the thermal conductivity is smaller than 10 W / mK in a standard grade, and is lower than 100 W / mK even in a high-grade grade. On the other hand, pitch-based carbon fibers generally tend to achieve higher elastic modulus and higher thermal conductivity than PAN-based carbon fibers. The pitch-based carbon fiber is obtained by melt spinning a raw material pitch to obtain a pitch fiber, and then infusibilizing, carbonizing, or further graphitizing.
炭素質原料としては、配向しやすい分子種が形成されており、光学的には異方性の炭素繊維を与えるようなものであれば特に制限はない。例えば、石炭系のコールタール、コールタールピッチ、石炭液化物、石油系の重質油、タール、ピッチ、または、ナフタレンやアントラセンの触媒反応による重合反応生成物等が挙げられる。これらの炭素質原料には、フリーカーボン、未溶解石炭、灰分、窒素分、硫黄分、触媒等の不純物が含まれているが、これらの不純物は、濾過、遠心分離、あるいは溶剤を使用する静置沈降分離等の周知の方法であらかじめ除去しておくことが望ましい。 The carbonaceous material is not particularly limited as long as molecular species that are easily oriented are formed and optically anisotropic carbon fibers are provided. For example, coal-based coal tar, coal tar pitch, coal liquefied product, petroleum-based heavy oil, tar, pitch, or a polymerization reaction product by a catalytic reaction of naphthalene or anthracene can be used. These carbonaceous raw materials contain impurities such as free carbon, undissolved coal, ash, nitrogen, sulfur, and catalysts. These impurities can be filtered, centrifuged, or statically used in a solvent. It is desirable to remove it in advance by a known method such as settling separation.
また、前記炭素質原料を、例えば、加熱処理した後、特定溶剤で可溶分を抽出するといった方法、あるいは、水素供与性溶剤、水素ガスの存在下に水添処理するといった方法で予備処理を行っておいても良い。 In addition, the carbonaceous raw material is subjected to a pretreatment by, for example, a method in which a soluble component is extracted with a specific solvent after heat treatment, or a method in which a hydrogenation treatment is performed in the presence of a hydrogen donating solvent or hydrogen gas. You can go there.
本発明で用いる炭素繊維の繊維径は３〜２０μｍ、特に５〜１２μｍであることが好ましい。炭素繊維の繊維径が細過ぎると、取り扱い性に劣り、また、一般に極細の炭素繊維は高コストであるため、製品コストを押し上げる原因となる。炭素繊維の繊維径が太過ぎると、繊維強度が低下し、折れ易くなるため、好ましくない。 The fiber diameter of the carbon fiber used in the present invention is preferably 3 to 20 μm, particularly preferably 5 to 12 μm. If the fiber diameter of the carbon fiber is too thin, the handleability is inferior, and the ultrafine carbon fiber is generally high in cost, which increases the product cost. If the fiber diameter of the carbon fiber is too thick, the fiber strength is lowered and the fiber is easily broken, which is not preferable.
また、炭素繊維の繊維長さ方向の引張弾性率は４００ＧＰａ以上、特に４４０ＧＰａ以上、例えば５００〜９００ＧＰａ以上で、また、繊維長さ方向の熱伝導率は、９０Ｗ／ｍＫ以上、特に１１０Ｗ／ｍＫ以上、例えば１２０〜６００Ｗ／ｍＫであることが好ましい。
このように、それ自体、引張弾性率及び熱伝導率の高い炭素繊維を用いることにより、得られる炭素繊維強化樹脂製基材シートの曲げ弾性率及び熱伝導率を高くすることができる。炭素繊維は黒鉛化処理することにより、引張弾性率や熱伝導率が向上することが知られており、従って、炭素繊維は黒鉛化炭素繊維であってもよく、また、炭素繊維は適当な段階で（例えば、不織布とした後に）黒鉛化処理して用いてもよい。
Further, the tensile modulus in the fiber length direction of the carbon fiber is 400 GPa or more, particularly 440 GPa or more, for example, 500 to 900 GPa or more, and the thermal conductivity in the fiber length direction is 90 W / mK or more, particularly 110 W / mK or more. For example, it is preferable that it is 120-600 W / mK.
Thus, the bending elastic modulus and thermal conductivity of the obtained carbon fiber reinforced resin base sheet can be increased by using carbon fibers having high tensile elastic modulus and high thermal conductivity. It is known that the carbon fiber is graphitized to improve the tensile modulus and thermal conductivity. Therefore, the carbon fiber may be a graphitized carbon fiber, and the carbon fiber is in an appropriate stage. (For example, after forming into a nonwoven fabric), it may be used after being graphitized.
なお、ここで、炭素繊維の繊維径は、炭素繊維の顕微鏡観察またはレーザー計測器により２０〜３０個の繊維径を測定し、その測定値の平均値で求められる。また、炭素繊維の繊維長さ方向の引張弾性率および熱伝導率は、炭素繊維とエポキシ樹脂の一方向材を作製し、その繊維軸方向の引張弾性率および熱伝導率を測定した値を、複合則に則って、炭素繊維の体積含有率で割り返して、繊維単体の物性としたものである。さらに具体的には、引張弾性率については、ＪＩＳ Ｋ７０７３に準拠し、万能試験機で測定された値からの計算値である。また、熱伝導率は、ＪＩＳ Ｒ１６１１に準拠し、真空理工（株）製レーザーフラッシュ法熱定数測定装置「ＴＣ−３０００」で測定された値からの計算値である。
後掲の実施例においても同様である。
Here, the fiber diameter of the carbon fiber is obtained by measuring 20 to 30 fiber diameters with a microscopic observation of the carbon fiber or a laser measuring instrument, and obtaining the average value of the measured values. In addition, the tensile modulus and thermal conductivity in the fiber length direction of the carbon fiber is a value obtained by preparing a unidirectional material of carbon fiber and epoxy resin, and measuring the tensile modulus and thermal conductivity in the fiber axis direction. In accordance with the composite law, the physical properties of the single fiber are determined by dividing the volume content of the carbon fiber. More specifically, the tensile elastic modulus is a calculated value from a value measured with a universal testing machine in accordance with JIS K7073. The thermal conductivity is a calculated value from a value measured with a laser flash method thermal constant measuring device “TC-3000” manufactured by Vacuum Riko Co., Ltd. in accordance with JIS R1611.
The same applies to the embodiments described later.
また、炭素繊維は、本発明の炭素繊維強化樹脂製基材シート中に様々な形態で存在することができ、例えば、次の(1)〜(4)のいずれか１以上の形態で存在する。 Moreover, carbon fiber can exist in various forms in the carbon fiber reinforced resin base material sheet of the present invention, for example, it exists in any one or more of the following (1) to (4). .
(1) 一方向に引き揃えられた長繊維または連続繊維
(2) 織布
(3) 特定の方向に配向する短繊維
(4) ランダムに分散する短繊維
なお、特定の方向に配向する短繊維及びランダムに分散する短繊維は、通常、不織布として炭素繊維強化樹脂製基材シート中に存在する。
(1) Long or continuous fibers aligned in one direction
(2) Woven fabric
(3) Short fibers oriented in a specific direction
(4) Randomly Dispersed Short Fibers Note that short fibers oriented in a specific direction and randomly dispersed short fibers are usually present in the carbon fiber reinforced resin base sheet as a nonwoven fabric.
炭素繊維を基材シート中にこのような形態で存在させる方法については、炭素繊維強化樹脂シートの製造方法の項で後述する。 The method for causing the carbon fiber to exist in such a form in the base sheet will be described later in the section of the method for producing a carbon fiber reinforced resin sheet.
なお、炭素繊維を織布又は不織布として用いる場合、その繊維の目付、すなわち単位面積あたりの繊維の重量（Fiber Areal Weight、以下「ＦＡＷ」と記す）は２０〜５００ｇ／ｍ２、特に１００〜２５０ｇ／ｍ２であることが好ましい。ＦＡＷの小さいものは、所望の放熱性及び剛直性、自立性を達成するために織布又は不織布の積層枚数を多くする必要があり、製造工程が煩雑となる。逆にＦＡＷの大きいものは、樹脂の含浸性が悪く、複合化が困難となる。 When carbon fiber is used as a woven or non-woven fabric, the basis weight of the fiber, that is, the fiber weight per unit area (Fiber Areal Weight, hereinafter referred to as “FAW”) is 20 to 500 g / m 2 , particularly 100 to 250 g. / M 2 is preferable. In the case where the FAW is small, it is necessary to increase the number of woven fabrics or nonwoven fabrics to be laminated in order to achieve desired heat dissipation, rigidity, and self-supporting properties, and the manufacturing process becomes complicated. On the other hand, those with a large FAW have poor resin impregnation properties, making it difficult to form a composite.
なお、炭素繊維の織布の形態としては特に制限はなく、従来公知の二次元織物を用いることができる。織物組織としては、平織、朱子織など、経糸と緯糸が一定の法則に従って直角に交錯した二軸織物が好ましい。 In addition, there is no restriction | limiting in particular as a form of the woven fabric of carbon fiber, A conventionally well-known two-dimensional fabric can be used. As the woven fabric structure, a biaxial woven fabric in which warp and weft cross at right angles according to a certain rule, such as plain weave and satin weave, is preferable.
また、炭素繊維短繊維の場合、その繊維長さとしては、０．１〜１００ｍｍ、特に１〜５０ｍｍ程度であることが好ましい。短繊維の長さが短か過ぎると得られるシートの曲げ弾性率や熱伝導率を十分に高めることができない恐れがあり、短繊維の長さが長過ぎると、不織布シートの作製及び樹脂との複合化が困難になる恐れがある。 In the case of carbon fiber short fibers, the fiber length is preferably about 0.1 to 100 mm, particularly about 1 to 50 mm. If the length of the short fiber is too short, the bending elastic modulus and thermal conductivity of the resulting sheet may not be sufficiently increased. If the length of the short fiber is too long, the production of the nonwoven sheet and the resin There is a risk that compounding will be difficult.
｛樹脂｝
次に、炭素繊維と複合化する樹脂について説明する。
本発明において、炭素繊維と複合化する樹脂については特に制限はなく、各種の熱可塑性樹脂や熱硬化性樹脂が挙げられる。
{resin}
Next, the resin that is combined with the carbon fiber will be described.
In this invention, there is no restriction | limiting in particular about resin combined with carbon fiber, Various thermoplastic resins and thermosetting resins are mentioned.
具体的には、エポキシ樹脂、フェノール樹脂、不飽和ポリエステル樹脂、ビニルエステル樹脂、ポリイミド樹脂、アクリル樹脂などの熱硬化性樹脂、ポリプロリレン（ＰＰ）、ポリメチルペンテン（ＰＭＰ）、ポリアミド（ＰＡ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリカーボネート（ＰＣ）、ポリエチレン（ＰＥ）、ポリエーテルイミド（ＰＥＩ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリエーテルケトン（ＰＥＫ）、ポリエーテルニトリル（ＰＥＮ）、変性ポリフェニレンエーテル（変性ＰＰＥ）、ポリエーテルサルホン（ＰＥＳ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリイミド（ＰＩ）、ポリアセタール（ＰＯＭ）、ポリフェニレンサルファイド（ＰＰＳ）、ポリ塩化ビニル（ＰＶＣ）、ポリスチレン（ＰＳ）、アクリロニトリル／ブタジエン／スチレン共重合体（ＡＢＳ）、ポリメチルメタアクリレート（ＰＭＭＡ）などの熱可塑性樹脂が挙げられる。これらの樹脂は１種を単独で用いてもよく、２種以上を混合して用いてもよい。好ましくは熱硬化性樹脂であり、特に好ましくは、成形性及び各種物性の点でエポキシ樹脂が用いられる。なお、熱硬化剤の代りに紫外線硬化剤を配合した紫外線硬化樹脂であってもよい。 Specifically, epoxy resins, phenol resins, unsaturated polyester resins, vinyl ester resins, polyimide resins, acrylic resins, and other thermosetting resins, polypropylene (PP), polymethylpentene (PMP), polyamide (PA), poly Butylene terephthalate (PBT), polycarbonate (PC), polyethylene (PE), polyetherimide (PEI), polyetheretherketone (PEEK), polyetherketone (PEK), polyethernitrile (PEN), modified polyphenylene ether (modified) PPE), polyethersulfone (PES), polyethylene terephthalate (PET), polyimide (PI), polyacetal (POM), polyphenylene sulfide (PPS), polyvinyl chloride (PVC), polystyrene (PS , Acrylonitrile / butadiene / styrene copolymer (ABS), thermoplastic resins such as polymethyl methacrylate (PMMA). These resins may be used alone or in combination of two or more. A thermosetting resin is preferable, and an epoxy resin is particularly preferable in terms of moldability and various physical properties. In addition, the ultraviolet curable resin which mix | blended the ultraviolet curing agent instead of the thermosetting agent may be sufficient.
これらの樹脂には、難燃剤、カップリング剤、導電性付与剤、無機フィラー、紫外線吸収剤、酸化防止剤、各種染顔料等、通常、樹脂に配合される各種の添加剤を配合してもよい。 These resins may be blended with various additives that are usually blended in resins, such as flame retardants, coupling agents, conductivity-imparting agents, inorganic fillers, ultraviolet absorbers, antioxidants, and various dyes and pigments. Good.
{フィルム／織布／不織布}
本発明の炭素繊維強化樹脂シートは、炭素繊維と樹脂を複合化してなる基材シートを主体とするものであるが、後述の本発明の炭素繊維強化樹脂シートの製造方法の項で説明するように、予め製造された炭素繊維強化樹脂シートを基材シートとして用い、この基材シートの一方の面又は両方の面にフィルム及び／又は織布及び／又は不織布を積層して一体化したものとすることにより、シートの表面性を改善し、耐薬品性や絶縁性といった、炭素繊維強化樹脂では得られない特性を付与したり、また、屈曲性、取り扱い性を向上させるなどの効果が得られ、好ましい。
{Film / Woven / Nonwoven}
The carbon fiber reinforced resin sheet of the present invention is mainly composed of a base material sheet formed by combining carbon fiber and resin, and will be described in the section of the method for producing a carbon fiber reinforced resin sheet of the present invention described later. In addition, a carbon fiber reinforced resin sheet manufactured in advance is used as a base sheet, and a film and / or a woven fabric and / or a non-woven fabric are laminated and integrated on one or both sides of the base sheet. As a result, the surface properties of the sheet can be improved, and properties such as chemical resistance and insulation, which cannot be obtained with carbon fiber reinforced resin, can be obtained, and the flexibility and handleability can be improved. ,preferable.
この場合、基材シートに積層して一体化するフィルムとしては、ポリエステル、ポリカーボネート、ポリメチルメタアクリレート、ポリアミドなどの熱可塑性樹脂からなるフィルムであって、厚さが０．１ｍｍ以下、好ましくは０．０５ｍｍ以下のものが挙げられる。このフィルムの厚さが過度に厚いと薄肉シートを得る本発明の目的を達成し得ない。なお、フィルムの厚さの下限については特に限定しないが、取り扱いの容易さから通常０．００５ｍｍ以上であることが好ましい。 In this case, the film laminated and integrated on the base sheet is a film made of a thermoplastic resin such as polyester, polycarbonate, polymethyl methacrylate, polyamide, etc., and has a thickness of 0.1 mm or less, preferably 0. .05 mm or less. If the film is too thick, the object of the present invention for obtaining a thin sheet cannot be achieved. The lower limit of the thickness of the film is not particularly limited, but is usually preferably 0.005 mm or more for ease of handling.
また、織布／不織布としては、ガラス繊維、炭素繊維などの無機繊維、又はポリエステル繊維、ポリアミド繊維などの有機繊維を製織あるいは解繊して得られた織布／不織布であって、ＦＡＷが１００ｇ／ｍ２以下であるものが用いられる。基材シートに積層する織布／不織布のＦＡＷが大き過ぎると、シート全体の厚さが過大となり、取り扱い性が劣ることになり、また、表面の織布／不織布が厚さ方向で熱抵抗として働き、本発明の炭素繊維強化樹脂シートを適用した被着物と、炭素繊維強化樹脂シート中の基材シートとの間の熱伝導を妨げることになり、好ましくない。織布／不織布のＦＡＷの下限については特に限定しないが、取り扱い性の面から、通常１０ｇ／ｍ２以上である。 The woven / nonwoven fabric is a woven / nonwoven fabric obtained by weaving or defibrating organic fibers such as glass fibers and carbon fibers, or polyester fibers and polyamide fibers, and has a FAW of 100 g. / M 2 or less is used. If the FAW of the woven / nonwoven fabric to be laminated on the base sheet is too large, the thickness of the entire sheet will be excessive, resulting in poor handling, and the surface woven / nonwoven fabric will have a thermal resistance in the thickness direction. This is not preferable because it prevents heat conduction between the adherend to which the carbon fiber reinforced resin sheet of the present invention is applied and the substrate sheet in the carbon fiber reinforced resin sheet. The lower limit of the FAW of the woven / nonwoven fabric is not particularly limited, but is usually 10 g / m 2 or more from the viewpoint of handleability.
炭素繊維強化樹脂製基材シートには、一方の面のみにフィルム及び／又は織布及び／又は不織布を積層してもよく、両面にフィルム及び／又は織布及び／又は不織布を積層してもよい。また、一方の面にフィルムを積層し、他方の面に織布及び／又は不織布を積層してもよく、２枚以上のフィルム及び／又は織布及び／又は不織布を積層したり、フィルムと織布及び／又は不織布とを組み合わせたものを積層してもよい。 The base sheet made of carbon fiber reinforced resin may be laminated with a film and / or woven fabric and / or non-woven fabric only on one side, or may be laminated with a film and / or woven fabric and / or non-woven fabric on both sides. Good. Further, a film may be laminated on one surface, and a woven fabric and / or a nonwoven fabric may be laminated on the other surface, or two or more films and / or a woven fabric and / or a nonwoven fabric may be laminated, or a film and a woven fabric may be laminated. You may laminate what combined cloth and / or a nonwoven fabric.
｛熱伝導率｝
本発明の炭素繊維強化樹脂シートは、基材シートの面内方向における熱伝導率の最大値が１０Ｗ／ｍＫ以上であることを特徴とする。基材シートの面内方向の熱伝導率の最大値が１０Ｗ／ｍＫ未満では、本発明で目的とする高熱伝導率のシートを実現し得ない。
{Thermal conductivity}
The carbon fiber reinforced resin sheet of the present invention is characterized in that the maximum value of thermal conductivity in the in-plane direction of the base material sheet is 10 W / mK or more. If the maximum value of the thermal conductivity in the in-plane direction of the base sheet is less than 10 W / mK, the sheet having the high thermal conductivity intended in the present invention cannot be realized.
炭素繊維強化樹脂製基材シートの面内方向の好適な熱伝導率は、基材シート構成、特に、基材シート内における炭素繊維の存在形態により異なり、例えば、以下の通りである。 A suitable thermal conductivity in the in-plane direction of the base sheet made of carbon fiber reinforced resin varies depending on the base sheet configuration, in particular, the presence form of the carbon fiber in the base sheet, and is as follows, for example.
＜炭素繊維が織布又は不織布として基材シート内に存在する場合＞
基材シートの面内方向の熱伝導率の最大値は１０Ｗ／ｍＫ以上、好ましくは２０Ｗ／ｍＫ以上である。熱伝導率の最大値の上限については特に規定しないが、熱伝導率向上のためのコスト等を勘案した場合、通常７０Ｗ／ｍＫ程度である。
なお、炭素短繊維が２次元ランダムに分散して基材シート内に存在する場合、面内ＸＹ方向（Ｘ方向は、面内のある一方向、Ｙ方向はＸ方向に直交する方向）における熱伝導率の差は殆どなく、一般的には、面内のどのような方向で測定しても同等の熱伝導率が得られる。一方、炭素短繊維が特定の方向に配向している不織布の場合、あるいは、炭素連続繊維が複数の特定方向のみに配列している織布の場合は、着目する方向での炭素繊維の配向度によって熱伝導率が変わり、最も配向している方向で熱伝導率の最大値が得られる。
<When carbon fiber is present in the base sheet as a woven or non-woven fabric>
The maximum value of the thermal conductivity in the in-plane direction of the base sheet is 10 W / mK or more, preferably 20 W / mK or more. The upper limit of the maximum value of thermal conductivity is not particularly specified, but is usually about 70 W / mK when considering the cost for improving the thermal conductivity.
When carbon short fibers are dispersed two-dimensionally randomly and are present in the base sheet, heat in the in-plane XY direction (X direction is one direction in the plane and Y direction is perpendicular to the X direction) There is almost no difference in conductivity, and generally the same thermal conductivity can be obtained regardless of the direction in the plane. On the other hand, in the case of a nonwoven fabric in which short carbon fibers are oriented in a specific direction, or in the case of a woven fabric in which carbon continuous fibers are arranged only in a plurality of specific directions, the degree of orientation of the carbon fibers in the direction of interest Changes the thermal conductivity, and the maximum value of the thermal conductivity is obtained in the most oriented direction.
＜炭素繊維が一方向に引き揃えられた長繊維または連続繊維として基材シート内に存在する場合＞
基材シートの面内方向の熱伝導率の最大値は６０Ｗ／ｍＫ以上、好ましくは８０Ｗ／ｍＫ以上である。熱伝導率の最大値の上限については特に規定しないが、熱伝導率向上のためのコスト等を勘案した場合、通常２５０Ｗ／ｍＫ程度である。
なお、炭素繊維が一方向に引き揃えられた長繊維または連続繊維として基材シート内に存在する場合、面内ＸＹ方向（Ｘ方向は炭素繊維が引き揃えられた方向、Ｙ方向はＸ方向に直交する方向）における熱伝導率の差は大きく、繊維の引き揃え方向、即ち、繊維の延在方向における熱伝導率は上記値を示すが、これと直交する方向においては通常０．４〜２Ｗ／ｍＫ程度の小さい値を示す。
<When carbon fibers are present in a base sheet as long fibers or continuous fibers aligned in one direction>
The maximum value of the thermal conductivity in the in-plane direction of the base sheet is 60 W / mK or more, preferably 80 W / mK or more. The upper limit of the maximum value of the thermal conductivity is not particularly specified, but is usually about 250 W / mK when considering the cost for improving the thermal conductivity.
When carbon fibers are present in the base sheet as long fibers or continuous fibers aligned in one direction, in-plane XY direction (X direction is the direction in which carbon fibers are aligned, Y direction is in the X direction) The difference in thermal conductivity in the direction orthogonal) is large, and the thermal conductivity in the fiber alignment direction, that is, in the fiber extending direction shows the above value, but in the direction orthogonal to this, it is usually 0.4 to 2 W. A small value of about / mK is shown.
なお、炭素繊維強化樹脂製基材シートの面内方向の熱伝導率は、後述の実施例の項に記載される方法で測定される。 In addition, the thermal conductivity in the in-plane direction of the base sheet made of carbon fiber reinforced resin is measured by the method described in the section of Examples described later.
｛曲げ弾性率｝
本発明の炭素繊維強化樹脂シートは、基材シートの面内方向における曲げ弾性率の最大値が２０ＧＰａ以上であることを特徴とする。基材シートの面内方向の曲げ弾性率の最大値が２０ＧＰａ未満では、本発明で目的とする高曲げ弾性率のシートを実現し得ない。
{Bending elastic modulus}
The carbon fiber reinforced resin sheet of the present invention is characterized in that the maximum value of the flexural modulus in the in-plane direction of the base material sheet is 20 GPa or more. If the maximum value of the bending elastic modulus in the in-plane direction of the base sheet is less than 20 GPa, the sheet having the high bending elastic modulus intended in the present invention cannot be realized.
炭素繊維強化樹脂製基材シートの面内方向の好適な曲げ弾性率は、基材シート構成、特に、基材シート内における炭素繊維の存在形態により異なり、例えば、以下の通りである。 A suitable flexural modulus in the in-plane direction of the base sheet made of carbon fiber reinforced resin varies depending on the base sheet configuration, in particular, the presence form of carbon fibers in the base sheet, and is as follows, for example.
＜炭素繊維が織布又は不織布として基材シート内に存在する場合＞
基材シートの面内方向の曲げ弾性率の最大値は２０ＧＰａ以上、好ましくは４０ＧＰａ以上である。曲げ弾性率の最大値の上限については特に規定しないが、曲げ弾性率向上のためのコスト等を勘案した場合、通常１００ＧＰａ程度である。
なお、炭素短繊維が２次元ランダムに分散して基材シート内に存在する場合、面内ＸＹ方向（Ｘ方向は、面内のある一方向、Ｙ方向はＸ方向に直交する方向）における曲げ弾性率の差は殆どなく、一般的には、面内のどのような方向で測定しても同等の曲げ弾性率が得られる。一方、炭素短繊維が特定の方向に配向している不織布の場合、あるいは、炭素連続繊維が複数の特定方向のみに配列している織布の場合は、着目する方向での炭素繊維の配向度によって曲げ弾性率が変わり、最も配向している方向で曲げ弾性率の最大値が得られる。
<When carbon fiber is present in the base sheet as a woven or non-woven fabric>
The maximum value of the flexural modulus in the in-plane direction of the base sheet is 20 GPa or more, preferably 40 GPa or more. The upper limit of the maximum value of the flexural modulus is not particularly specified, but is usually about 100 GPa when considering the cost for improving the flexural modulus.
In addition, when the short carbon fibers are two-dimensionally dispersed and exist in the base sheet, bending in the in-plane XY direction (X direction is one direction in the plane, Y direction is orthogonal to the X direction) There is almost no difference in elastic modulus, and in general, the same bending elastic modulus can be obtained regardless of the direction in the plane. On the other hand, in the case of a nonwoven fabric in which short carbon fibers are oriented in a specific direction, or in the case of a woven fabric in which carbon continuous fibers are arranged only in a plurality of specific directions, the degree of orientation of the carbon fibers in the direction of interest Changes the bending elastic modulus, and the maximum value of the bending elastic modulus is obtained in the most oriented direction.
＜炭素繊維が一方向に引き揃えられた長繊維または連続繊維として基材シート内に存在する場合＞
基材シートの面内方向の曲げ弾性率の最大値は２５０ＧＰａ以上、好ましくは３００ＧＰａ以上である。曲げ弾性率の最大値の上限については特に規定しないが、曲げ弾性率向上のためのコスト等を勘案した場合、通常４５０ＧＰａ程度である。
なお、炭素繊維が一方向に引き揃えられた長繊維または連続繊維として基材シート内に存在する場合、面内ＸＹ方向（Ｘ方向は炭素繊維が引き揃えられた方向、Ｙ方向はＸ方向に直交する方向）における曲げ弾性率の差は大きく、繊維の引き揃え方向、即ち、繊維の延在方向における曲げ弾性率は上記値を示すが、これと直交する方向においては通常３〜９ＧＰａ程度の小さい値を示す。
<When carbon fibers are present in a base sheet as long fibers or continuous fibers aligned in one direction>
The maximum value of the flexural modulus in the in-plane direction of the base sheet is 250 GPa or more, preferably 300 GPa or more. The upper limit of the maximum value of the flexural modulus is not particularly specified, but is usually about 450 GPa when considering the cost for improving the flexural modulus.
When carbon fibers are present in the base sheet as long fibers or continuous fibers aligned in one direction, in-plane XY direction (X direction is the direction in which carbon fibers are aligned, Y direction is in the X direction) The difference in bending elastic modulus in the direction orthogonal to the direction is large, and the bending elastic modulus in the fiber alignment direction, that is, the fiber extending direction shows the above value, but in the direction orthogonal to this, it is usually about 3 to 9 GPa. Indicates a small value.
なお、炭素繊維強化樹脂製基材シートの面内方向の曲げ弾性率は、後述の実施例の項に記載される方法で測定される。 In addition, the bending elastic modulus in the in-plane direction of the base sheet made of carbon fiber reinforced resin is measured by the method described in the section of Examples described later.
｛炭素繊維／樹脂含有率｝
本発明の炭素繊維強化樹脂シートの主体を構成する炭素繊維強化樹脂製基材シートの炭素繊維及び樹脂の好適な含有率は、基材シート構成、特に基材シート内における炭素繊維の存在形態により異なり、例えば、以下の通りである。
{Carbon fiber / resin content}
The preferred content of carbon fiber and resin of the carbon fiber reinforced resin base sheet constituting the main body of the carbon fiber reinforced resin sheet of the present invention depends on the base sheet configuration, particularly the presence of carbon fibers in the base sheet. For example, it is as follows.
＜炭素繊維が織布又は不織布として基材シート内に存在する場合＞
基材シートの炭素繊維含有率は、１０〜６０ｖｏｌ％、特に２０〜５０ｖｏｌ％、重量割合として１５〜７５ｗｔ％、特に３０〜６５ｗｔ％であることが好ましい。この範囲よりも炭素繊維含有率が少ないと得られるシートの物性が低下し、所望の熱伝導率及び曲げ弾性率を達成し得ない。この範囲よりも炭素繊維含有率が多いと成形時の加圧力を大きくする必要が生じ、実用的ではない。
なお、樹脂含有率は、重量割合として２５〜８５ｗｔ％、特に３５〜７０ｗｔ％であることが好ましい。
<When carbon fiber is present in the base sheet as a woven or non-woven fabric>
The carbon fiber content of the base sheet is preferably 10 to 60 vol%, particularly 20 to 50 vol%, and 15 to 75 wt%, particularly 30 to 65 wt% as a weight ratio. If the carbon fiber content is less than this range, the physical properties of the obtained sheet will be lowered, and the desired thermal conductivity and flexural modulus will not be achieved. If the carbon fiber content is higher than this range, it is necessary to increase the pressing force during molding, which is not practical.
In addition, it is preferable that resin content rate is 25-85 wt% as a weight ratio, especially 35-70 wt%.
＜炭素繊維が一方向に引き揃えられた長繊維または連続繊維として基材シート内に存在する場合＞
基材シートの炭素繊維含有率は、４０〜７０ｖｏｌ％、特に５０〜６５ｖｏｌ％、重量割合として５０〜８０ｗｔ％、特に６０〜７５ｗｔ％であることが好ましい。この範囲よりも炭素繊維含有率が少ないと得られるシートの物性が低下し、所望の熱伝導率及び曲げ弾性率を達成し得ない。この範囲よりも炭素繊維含有率が多いと成形時の加圧力を大きくする必要が生じ、実用的ではない。
なお、樹脂含有率は、重量割合として２０〜５０ｗｔ％、特に２５〜４０ｗｔ％であることが好ましい。
<When carbon fibers are present in a base sheet as long fibers or continuous fibers aligned in one direction>
The carbon fiber content of the base sheet is preferably 40 to 70 vol%, particularly 50 to 65 vol%, and the weight ratio is 50 to 80 wt%, particularly 60 to 75 wt%. If the carbon fiber content is less than this range, the physical properties of the obtained sheet will be lowered, and the desired thermal conductivity and flexural modulus will not be achieved. If the carbon fiber content is higher than this range, it is necessary to increase the pressing force during molding, which is not practical.
In addition, it is preferable that resin content rate is 20-50 wt% as a weight ratio, especially 25-40 wt%.
｛厚さ｝
本発明の炭素繊維強化樹脂シートは総厚さ（この厚さとは、本発明の炭素繊維強化樹脂シートが上述の炭素繊維強化樹脂製基材シートのみで構成される場合は当該炭素繊維強化樹脂製基材シートの厚さであり、炭素繊維強化樹脂製基材シートと前述のフィルム、織布、不織布との積層体よりなる場合は、これらの合計の厚さをさす）が０．０５〜０．５ｍｍであることを特徴とする。
{thickness}
The carbon fiber reinforced resin sheet of the present invention has a total thickness (this thickness means that the carbon fiber reinforced resin sheet of the present invention is made of only the above-mentioned carbon fiber reinforced resin base material sheet. It is the thickness of the base sheet, and in the case of a laminate of the carbon fiber reinforced resin base sheet and the above-mentioned film, woven fabric, and non-woven fabric, it indicates the total thickness of these). 0.5 mm.
炭素繊維強化樹脂シートの厚さが０．０５ｍｍ未満では、機械的強度に劣るものとなり、また、このような薄さで所望の放熱性及び剛直性、自立性を達成することは困難である。炭素繊維強化樹脂シートの厚さが０．５ｍｍを超えると、屈曲性、可撓性が損なわれ、本発明の目的を達成し得ない。
炭素繊維強化樹脂シートの好ましい厚さは０．０５〜０．３ｍｍ、特に０．１〜０．２ｍｍである。
When the thickness of the carbon fiber reinforced resin sheet is less than 0.05 mm, the mechanical strength is inferior, and it is difficult to achieve desired heat dissipation, rigidity, and self-supporting properties with such a thin thickness. When the thickness of the carbon fiber reinforced resin sheet exceeds 0.5 mm, the flexibility and flexibility are impaired, and the object of the present invention cannot be achieved.
The preferred thickness of the carbon fiber reinforced resin sheet is 0.05 to 0.3 mm, particularly 0.1 to 0.2 mm.
｛屈曲性｝
本発明の炭素繊維強化樹脂シートは、これを３０ｃｍ角に切り出し、長手方向及び幅方向のそれぞれについて、曲率半径３０ｍｍでの折り曲げを５回繰り返した際、割れずに屈曲できる優れた屈曲性を示す。
{Flexibility}
Carbon fiber reinforced resin sheets of the present invention, cut it into 30cm square, each of the longitudinal and width directions, when repeated 5 times bending curvature radius 30 mm, an excellent bendability that can bend without cracking Show.
本発明の炭素繊維強化樹脂シートに優れた屈曲性を付与するためには、前述のシート総厚さを採用すると共に、シート内の炭素繊維の存在形態に応じて、本発明で目的とする屈曲性を満たすべく、例えば、次のような工夫を施すことが好ましい。 In order to impart excellent flexibility to the carbon fiber reinforced resin sheet of the present invention, the above-mentioned total sheet thickness is adopted, and depending on the form of carbon fibers in the sheet, the desired bending in the present invention In order to satisfy the characteristics, for example, the following device is preferably applied.
即ち、本発明の炭素繊維強化樹脂シート内の炭素繊維の存在形態としては、前述の如く、
(1) 一方向に引き揃えられた長繊維または連続繊維
(2) 織布
(3) 特定の方向に配向する短繊維
(4) ランダムに分散する短繊維
などが挙げられるが、このうち、一方向に引き揃えられた長繊維または連続繊維の場合、基材シートのみでは屈曲性に難がある場合があることから、一方向に引き揃えられた長繊維または連続繊維を採用する場合には、これを含む基材シートの一方の面又は両面に、前述のフィルム及び／又は織布及び／又は不織布を積層一体化して屈曲性を高めることが好ましい。
これに対して、炭素繊維が、織布、特定の方向に配向する短繊維、或いはランダムに分散する短繊維の場合には、比較的屈曲性に優れた基材シートが得られることから、フィルム等を積層一体化することは、屈曲性の面からは必ずしも必要とされず、その他の要求特性に応じてフィルム等の積層の有無を選択すればよい。
That is, as the presence form of the carbon fiber in the carbon fiber reinforced resin sheet of the present invention, as described above,
(1) Long or continuous fibers aligned in one direction
(2) Woven fabric
(3) Short fibers oriented in a specific direction
(4) Short fibers that are randomly dispersed, etc., but among these, in the case of long fibers or continuous fibers that are aligned in one direction, it may be difficult to bend only with the base sheet, In the case of adopting long fibers or continuous fibers aligned in one direction, the above-mentioned film and / or woven fabric and / or non-woven fabric are laminated and integrated on one side or both sides of the base sheet including the same. It is preferable to increase the flexibility.
On the other hand, when the carbon fiber is a woven fabric, a short fiber oriented in a specific direction, or a short fiber randomly dispersed, a base sheet having a relatively excellent flexibility can be obtained. And the like are not necessarily required from the viewpoint of flexibility, and the presence or absence of lamination of films or the like may be selected according to other required characteristics.
［炭素繊維強化樹脂シートの製造方法］
次に、上述の基材シートの熱伝導率及び曲げ弾性率と総厚さを満たす本発明の炭素繊維強化樹脂シートを製造する方法について説明する。
[Method for producing carbon fiber reinforced resin sheet]
Next, a method for producing the carbon fiber reinforced resin sheet of the present invention satisfying the thermal conductivity and bending elastic modulus and the total thickness of the above-described base sheet will be described.
本発明の炭素繊維強化樹脂シートを製造するには、必要に応じて、予め、シート内の存在形態に加工した炭素繊維を用い、この炭素繊維に樹脂を複合してシートを成形する。このシートを基材シートとして、更に前述のフィルム及び／又は織布及び／又は不織布を積層一体化して本発明の炭素繊維強化樹脂シートを製造してもよく、また、この基材シートをそのまま本発明の炭素繊維強化樹脂シートとしてもよい。
以下においては、基材シート内の炭素繊維の存在形態毎に、本発明の炭素繊維強化樹脂シートの製造方法を説明する。
In order to produce the carbon fiber reinforced resin sheet of the present invention, if necessary, carbon fibers that have been processed into the existing form in the sheet are used in advance, and the carbon fiber is combined with a resin to form a sheet. The carbon fiber reinforced resin sheet of the present invention may be produced by laminating and integrating the above-mentioned film and / or woven fabric and / or non-woven fabric with this sheet as a base material sheet. It is good also as a carbon fiber reinforced resin sheet of invention.
Below, the manufacturing method of the carbon fiber reinforced resin sheet of this invention is demonstrated for every presence form of the carbon fiber in a base material sheet.
｛基材シート内に炭素繊維が一方向に引き揃えられた長繊維または連続繊維として存在するシートの製造方法｝
一方向に引き揃えた炭素繊維束を拡幅し、ここに樹脂を含浸させてシート状のプリプレグを製造する。このプリプレグの製造方法としては、従来公知のいかなる方法をも採用することができ、例えば特開昭５６−４３４３５号公報、特開昭６０−９９６１号公報及び特開平１−２８２３６２号公報、特開２００３−１６５８５１号公報等に記載の方法を採用することができる。また、最終的に炭素繊維強化樹脂シートのロール巻回体を得るためには、このプリプレグの段階でも幅１０ｃｍ以上、長さ５ｍ以上の連続シートとしておくことが好ましい。
{Production method of sheet existing as long fiber or continuous fiber in which carbon fiber is aligned in one direction in substrate sheet}
A carbon fiber bundle aligned in one direction is widened, and a resin is impregnated therein to produce a sheet-like prepreg. As a method for producing this prepreg, any conventionally known method can be employed. For example, JP-A-56-43435, JP-A-60-9961 and JP-A-1-282362, The method described in 2003-165851 gazette etc. is employable. In order to finally obtain a roll of carbon fiber reinforced resin sheet, it is preferable to form a continuous sheet having a width of 10 cm or more and a length of 5 m or more even at the stage of this prepreg.
このプリプレグにおける炭素繊維の目付、すなわちＦＡＷは２０〜５００ｇ／ｍ２、特に１００〜２５０ｇ／ｍ２で、炭素繊維含有率は４０〜７０ｖｏｌ％、特に５０〜６５ｖｏｌ％、樹脂含有率は２０〜５０ｗｔ％、特に２５〜４０ｗｔ％、厚さは０．０５〜０．３ｍｍ、特に０．１〜０．２ｍｍであることが好ましい。ＦＡＷが小さいものは、所望の放熱性及び剛直性、自立性を達成するために、プリプレグの積層枚数を多くする必要があり、製造工程が煩雑となる。ＦＡＷが大き過ぎると、製造工程で繊維に樹脂を含浸するのが難しくなるとともに、得られた製品の厚さが過大となり、屈曲性、可撓性が劣ることになる。 The basis weight of the carbon fiber in this prepreg, that is, FAW is 20 to 500 g / m 2 , particularly 100 to 250 g / m 2 , the carbon fiber content is 40 to 70 vol%, particularly 50 to 65 vol%, and the resin content is 20 to 50 wt. %, Particularly 25 to 40 wt%, and the thickness is preferably 0.05 to 0.3 mm, particularly preferably 0.1 to 0.2 mm. When the FAW is small, it is necessary to increase the number of laminated prepregs in order to achieve desired heat dissipation, rigidity, and self-sustainability, and the manufacturing process becomes complicated. If the FAW is too large, it will be difficult to impregnate the fibers with resin in the production process, and the thickness of the resulting product will be excessive, resulting in poor flexibility and flexibility.
また、炭素繊維含有率が少なく、樹脂含有率が多過ぎると、所望の熱伝導率及び曲げ弾性率を達成し得ず、樹脂含有率が少なく、炭素繊維含有率が多過ぎると成形性が損なわれる。
また、厚さが薄過ぎると、所望の放熱性及び剛直性、自立性を達成することは困難であり、厚過ぎると薄肉の本発明の炭素繊維強化樹脂シートを製造し得ない。
Also, if the carbon fiber content is low and the resin content is too high, the desired thermal conductivity and flexural modulus cannot be achieved, the resin content is low, and if the carbon fiber content is too high, the moldability is impaired. It is.
On the other hand, if the thickness is too thin, it is difficult to achieve the desired heat dissipation, rigidity, and self-supporting property. If the thickness is too thick, the thin carbon fiber reinforced resin sheet of the present invention cannot be produced.
このようにして得られたプリプレグをそのまま、或いは、２枚以上積層して、或いは更に、その一方の面又は両面に前述のフィルム及び／又は織布及び／又は不織布を積層して樹脂に適した方法に従って成形することにより、本発明の炭素繊維強化樹脂シートを製造することができる。
この成形方法としては、例えば、樹脂がエポキシ樹脂等の熱硬化性樹脂の場合、プリプレグ等を熱盤で加圧しながら所要温度まで加熱することで硬化させる方法が挙げられる。また、ポリプロピレン等の熱可塑性樹脂の場合、プリプレグ等を樹脂が軟化する温度まで予め加熱した後に加圧しながら軟化点以下の温度まで冷却することで固化する方法が挙げられる。
また、最終的に炭素繊維強化樹脂シートのロール巻回体を得るためには、連続シートのプリプレグと、ロール状のフィルム／織布／不織布を繰り出して貼り合せ、圧延／加熱／冷却ロールを通して連続的に加圧しながら硬化／固化することで、連続したシートをロール状に巻き取ることが好ましい。
The prepreg thus obtained is used as it is, or by laminating two or more sheets, or further, by laminating the above-mentioned film and / or woven fabric and / or non-woven fabric on one or both sides thereof, and suitable for the resin. The carbon fiber reinforced resin sheet of the present invention can be produced by molding according to the method.
As this molding method, for example, in the case where the resin is a thermosetting resin such as an epoxy resin, there is a method of curing by heating to a required temperature while pressing a prepreg or the like with a hot platen. In the case of a thermoplastic resin such as polypropylene, a method of solidifying by preheating the prepreg or the like to a temperature at which the resin softens and then cooling to a temperature below the softening point while applying pressure can be mentioned.
Also, in order to finally obtain a roll of carbon fiber reinforced resin sheet, a continuous sheet prepreg and a roll-like film / woven fabric / nonwoven fabric are unwound and bonded together, and are continuously passed through a rolling / heating / cooling roll. It is preferable to wind up a continuous sheet in a roll shape by curing / solidifying while applying pressure.
なお、樹脂の含浸に先立ち、引き揃えた炭素長繊維を黒鉛化処理して炭素繊維の繊維長さ方向の引張弾性率や熱伝導率を高めるようにしてもよい。 Prior to resin impregnation, the aligned carbon long fibers may be graphitized to increase the tensile elastic modulus and thermal conductivity in the fiber length direction of the carbon fibers.
｛基材シート内に炭素繊維が織布又は不織布として存在するシートの製造方法｝
まず、炭素繊維から常法に従って前述の織布又は不織布を製造する。
炭素繊維の織布は通常の繊維織機により製造することができる。また、炭素繊維の不織布は常法に従って１〜５０ｍｍ程度の長さに切断して得られた炭素短繊維を面状に分散させてシート状とすることにより製造することができる。短繊維状の炭素繊維から不織布を作るには様々な方法があり、その方法は特に限定されるものではない。例えば、乾式解繊によるシートの作製方法としては、機械的に炭素繊維を叩解してシート化する、ランダムウェッバー等の装置を使用する方法、あるいは、繊維を気流中で浮遊・解繊した後にスクリーン上に吸引する方法などがある。また、湿式解繊による作製方法としては、繊維を溶媒中に分散させ、製紙工業で使われるビーター、パルパーなどの装置を使用して解繊させた後に抄紙し、付着した溶媒を乾燥除去してシート化する方法などがある。また、上記のシート化の際に、気流や水流の方向を調整することにより、炭素短繊維を特定の方向に配向させることも、あるいはランダムに分散させることも可能である。また、最終的に炭素繊維強化樹脂シートのロール巻回体を得るためには、この不織布の段階でも幅１０ｃｍ以上、長さ５ｍ以上の連続シートとしておくことが好ましい。
{Method for producing sheet in which carbon fiber is present as woven or non-woven fabric in base sheet}
First, the above-mentioned woven fabric or non-woven fabric is produced from carbon fiber according to a conventional method.
The carbon fiber woven fabric can be produced by an ordinary fiber loom. Moreover, the carbon fiber nonwoven fabric can be manufactured by dispersing carbon short fibers obtained by cutting into lengths of about 1 to 50 mm according to a conventional method into a sheet shape by dispersing the carbon short fibers in a planar shape. There are various methods for producing a nonwoven fabric from short fiber-like carbon fibers, and the method is not particularly limited. For example, as a method for producing a sheet by dry defibration, a method of mechanically beating carbon fibers into a sheet, using a device such as a random webber, or a screen after floating and defibrating fibers in an air stream There is a method of sucking up. Also, as a production method by wet defibration, the fibers are dispersed in a solvent, defibrated using a device such as a beater or a pulper used in the paper industry, paper is made, and the attached solvent is removed by drying. There is a method to make a sheet. In addition, the carbon short fibers can be oriented in a specific direction or can be randomly dispersed by adjusting the direction of the air flow or water flow during the sheet formation. Moreover, in order to finally obtain a roll wound body of a carbon fiber reinforced resin sheet, it is preferable to form a continuous sheet having a width of 10 cm or more and a length of 5 m or more even at the stage of this nonwoven fabric.
次いで、得られた織布又は不織布に樹脂を含浸させ、シート状のプリプレグを得、このプリプレグをそのまま、或いは、２枚以上積層して、或いは更にその一方の面又は両面に前述のフィルム及び／又は織布及び／又は不織布を積層して、樹脂に適した方法に従って成形することにより、本発明の炭素繊維強化樹脂シートを製造することができる。
この成形方法としては、例えば、樹脂がエポキシ樹脂等の熱硬化性樹脂の場合、プリプレグ等を熱盤で加圧しながら所要温度まで加熱することで硬化させる方法が挙げられる。また、ポリプロピレン等の熱可塑性樹脂の場合、樹脂が軟化する温度までプリプレグ等を予め加熱した後に、加圧しながら軟化点以下の温度まで冷却することで固化する方法が挙げられる。
また、最終的に炭素繊維強化樹脂シートのロール巻回体を得るためには、連続シートのプリプレグと、ロール状のフィルム／織布／不織布を繰り出して貼り合せ、圧延／加熱／冷却ロールを通して連続的に加圧しながら硬化／固化することで、連続したシートをロール状に巻き取ることが好ましい。
Next, the obtained woven or non-woven fabric is impregnated with a resin to obtain a sheet-like prepreg. The prepreg as it is, or two or more sheets thereof are laminated, or further on one or both sides of the above film and / or Or the carbon fiber reinforced resin sheet of this invention can be manufactured by laminating | stacking a woven fabric and / or a nonwoven fabric, and shape | molding according to the method suitable for resin.
As this molding method, for example, in the case where the resin is a thermosetting resin such as an epoxy resin, there is a method of curing by heating to a required temperature while pressing a prepreg or the like with a hot platen. In the case of a thermoplastic resin such as polypropylene, a method of solidifying by preheating the prepreg or the like to a temperature at which the resin softens and then cooling to a temperature below the softening point while applying pressure can be mentioned.
Also, in order to finally obtain a roll of carbon fiber reinforced resin sheet, a continuous sheet prepreg and a roll-like film / woven fabric / nonwoven fabric are unwound and bonded together, and are continuously passed through a rolling / heating / cooling roll. It is preferable to wind up a continuous sheet in a roll shape by curing / solidifying while applying pressure.
なお、樹脂の含浸に先立ち、織布又は不織布を黒鉛化処理して、炭素繊維の繊維長さ方向の引張弾性率や熱伝導率を高めるようにしてもよい。 Prior to resin impregnation, the woven fabric or non-woven fabric may be graphitized to increase the tensile elastic modulus or thermal conductivity of the carbon fibers in the fiber length direction.
｛炭素短繊維のシート化と樹脂との複合化を同時に行うシート（基材シート）の製造方法｝
このようなシートは、予め常法に従って、前述の短繊維長さに切断した炭素短繊維とポリプロピレン等の熱可塑性樹脂とを、押し出し機により、加熱して樹脂を溶融させながら剪断力をかけて混練し、Ｔダイから押出して冷却固化することでシートを成形できる。また、この際に、スクリュー構造などの混練条件を調整することにより、炭素短繊維を特定の方向に配向させることも、あるいはランダムに分散させることも可能である。また、最終的に炭素繊維強化樹脂シートのロール巻回体を得るためには、この押出シートの段階でも幅１０ｃｍ以上、長さ５ｍ以上の連続シートとしておくことが好ましい。
{Production method of sheet (base sheet) that simultaneously forms carbon short fiber sheet and resin compound}
Such a sheet is obtained by applying a shearing force while heating the carbon short fibers cut to the above-mentioned short fiber length and a thermoplastic resin such as polypropylene by an extruder and melting the resin in accordance with a conventional method. A sheet can be formed by kneading, extruding from a T-die and solidifying by cooling. At this time, the short carbon fibers can be oriented in a specific direction or can be randomly dispersed by adjusting the kneading conditions such as the screw structure. Moreover, in order to finally obtain a roll of carbon fiber reinforced resin sheet, it is preferable to form a continuous sheet having a width of 10 cm or more and a length of 5 m or more even at the stage of the extruded sheet.
このシートについても更に前述のフィルム及び／又は織布及び／又は不織布を積層一体化させて、本発明の炭素繊維強化樹脂シートとしてもよい。また、最終的に炭素繊維強化樹脂シートのロール巻回体を得るためには、この押出シートがＴダイから押し出された直後の高温の状態のうちに、ロール状のフィルム／織布／不織布を繰り出して貼り合せ、圧延／冷却ロールを通して連続的に加圧しながら冷却固化することで、連続したシートをロール状に巻き取ることが好ましい。 The sheet and / or the woven fabric and / or the nonwoven fabric may be laminated and integrated to form the carbon fiber reinforced resin sheet of the present invention. In addition, in order to finally obtain a roll of carbon fiber reinforced resin sheet, a roll film / woven fabric / nonwoven fabric is used in a high temperature state immediately after the extruded sheet is extruded from the T die. It is preferable that the continuous sheet is wound up into a roll shape by unwinding and bonding, and solidifying by cooling while continuously pressing through a rolling / cooling roll.
なお、シート内の炭素繊維の存在形態は１種に限らず、２種以上であってもよい。即ち、織布と不織布を用いてもよく、ランダム配向する炭素繊維と一方向に引き揃えられた長繊維または連続繊維とが存在してもよく、この場合は、それぞれのシートの製造方法を組み合わせて、目的のシートを製造することができる。 In addition, the presence form of the carbon fiber in the sheet is not limited to one type, and may be two or more types. That is, a woven fabric and a non-woven fabric may be used, and there may be randomly oriented carbon fibers and long fibers or continuous fibers aligned in one direction. In this case, the manufacturing methods of the respective sheets are combined. Thus, a target sheet can be manufactured.
［ロール巻回体］
本発明のロール巻回体は、上述の本発明の炭素繊維強化樹脂シートをロール状に巻回してなるものである。
このロール巻回体において、炭素繊維強化樹脂シートの幅は１０ｃｍ以上、特に１５ｃｍ以上、例えば２０〜２００ｃｍ程度であることが好ましい。シートは幅の長い状態で生産した後にスリットして所望の幅のシートに小分けしてもよい。幅が１０ｃｍ未満のシートでは太陽電池やフラットディスプレイパネルなどの面積の大きな用途に供する場合に、一つのロールで一度に貼り付けができなくなり、生産性が劣ることになる。
[Roll roll]
The roll wound body of the present invention is obtained by winding the above-described carbon fiber reinforced resin sheet of the present invention in a roll shape.
In this roll wound body, the width of the carbon fiber reinforced resin sheet is preferably 10 cm or more, particularly 15 cm or more, for example, about 20 to 200 cm. The sheet may be produced in a state having a long width and then slitted to be divided into sheets having a desired width. When a sheet having a width of less than 10 cm is used for a large area such as a solar cell or a flat display panel, it cannot be attached at one time with a single roll, resulting in poor productivity.
また、炭素繊維強化樹脂シートの長さは５ｍ以上、特に１０ｍ以上、例えば２０〜１００ｍ程度であることが好ましい。本発明はこのような長さの長い長尺シートに、その優れた屈曲性及び可撓性により、ロール状に巻回可能であることで特有の効果が得られる。 The length of the carbon fiber reinforced resin sheet is preferably 5 m or more, particularly 10 m or more, for example, about 20 to 100 m. In the present invention, the long sheet having such a long length can be wound into a roll shape due to its excellent bendability and flexibility.
なお、本発明のロール巻回体の巻回軸の直径、すなわち、シートを巻き付ける芯部材の直径については特に制限はないが、本発明の炭素繊維強化樹脂シートは、その優れた屈曲性及び可撓性により、直径３０ｃｍ程度の小さな芯部材にも巻回することができ、このようなロール巻回体は、運搬、保管時の取り扱いに優れ、また、各種加工工程への適用性にも優れている。 The diameter of the winding axis of the roll wound body of the present invention, that is, the diameter of the core member around which the sheet is wound is not particularly limited, but the carbon fiber reinforced resin sheet of the present invention has excellent flexibility and good flexibility. Because of its flexibility, it can also be wound on small core members with a diameter of about 30 cm. Such a roll wound body is excellent in handling during transportation and storage, and also excellent in applicability to various processing steps. ing.
以下に実施例を挙げて本発明をより具体的に説明するが、本発明はその要旨を超えない限り、何ら以下の実施例に限定されるものではない。
なお、以下の実施例及び比較例では、実験室レベルでの寸法の小さなシートについて評価を行っているが、本発明の炭素繊維強化樹脂シートは、工業的には、通常、前述の幅及び、長さの長尺状シートとして製造される。
The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
In addition, in the following examples and comparative examples, although evaluation is performed on a sheet having a small dimension at the laboratory level, the carbon fiber reinforced resin sheet of the present invention is industrially usually the above-described width and Manufactured as a long sheet.
以下において、得られた基材シートや炭素繊維強化樹脂シートの厚さ、及び物性の評価は、以下の方法により行った。 In the following, the thickness and physical properties of the obtained base sheet and carbon fiber reinforced resin sheet were evaluated by the following methods.
＜厚さ測定＞
マイクロメーターにより測定した。
<Thickness measurement>
Measured with a micrometer.
＜屈曲性の評価＞
得られたシートを３０ｃｍ角に切り出し、長手方向及び幅方向のそれぞれについて、曲率半径３０ｍｍでの折り曲げを５回繰り返し、割れずに屈曲できるものを屈曲性良好「○」とし、割れてしまうものを屈曲性不良「×」とした。
<Evaluation of flexibility>
The obtained sheet was cut into 30 cm squares, and each of the longitudinal direction and the width direction was repeatedly bent at a radius of curvature of 30 mm five times. Flexibility defect “x”.
＜基材シートの面内方向の熱伝導率の測定＞
得られた基材シートそのものでは、厚さが小さ過ぎるために、熱伝導率を評価できない。そこで、当該シートの製造に使用したのと同じシート状のプリプレグを複数枚積層し、加圧・加熱して、厚さ１０ｍｍ以上の積層板を成形した。そして、その積層板から、熱伝導率を測定する方向を厚さ方向とした、直径１０ｍｍ、厚さ１〜６ｍｍの円盤状試験片を切り出し、ＪＩＳ Ｒ１６１１に準拠して、真空理工（株）製レーザーフラッシュ法熱定数測定装置「ＴＣ−３０００」により、シート面内方向の２方向（炭素繊維が面内で配向している場合は配向度の最も高い方向、配向していない場合はシートの長手方向をＸ方向とし、このＸ方向と直交するＹ方向とする）について熱伝導率の測定を行った。なお、実施例１，２及び比較例１，２において、Ｘ方向は、繊維の引き揃え方向である。
<Measurement of thermal conductivity in in-plane direction of substrate sheet>
In the obtained base material sheet itself, since the thickness is too small, the thermal conductivity cannot be evaluated. Therefore, a plurality of the same sheet-like prepregs used for the production of the sheet were laminated, pressed and heated to form a laminated plate having a thickness of 10 mm or more. A disk-shaped test piece having a diameter of 10 mm and a thickness of 1 to 6 mm was cut out from the laminated plate with the direction of measuring the thermal conductivity as the thickness direction, and manufactured by Vacuum Riko Co., Ltd. in accordance with JIS R1611. Laser flash method thermal constant measuring device “TC-3000” allows two directions in the in-plane direction of the sheet (the direction in which the orientation is highest when the carbon fibers are aligned in the plane, and the longitudinal direction of the sheet when the fibers are not aligned. The thermal conductivity was measured for the X direction and the Y direction perpendicular to the X direction). In Examples 1 and 2 and Comparative Examples 1 and 2, the X direction is the fiber alignment direction.
＜基材シートの面内方向の曲げ弾性率の測定＞
得られた基材シートそのものでは、厚さが小さ過ぎるために、曲げ弾性率を評価できない。そこで、当該シートの製造に使用したのと同じシート状のプリプレグを複数枚積層し、加圧・加熱して、厚さ２ｍｍの積層板を成形した。そして、その積層板から、曲げ弾性率を測定する方向を長さ方向とした、長さ１００ｍｍ、幅１５ｍｍ、厚さ２ｍｍの短冊状試験片を切り出し、ＪＩＳ Ｋ７０７４に準拠して、万能試験機により、支点間距離を８０ｍｍとした３点曲げ試験により、シート面内方向の２方向（炭素繊維が面内で配向している場合は配向度の最も高い方向、配向していない場合はシートの長手方向をＸ方向とし、このＸ方向と直交するＹ方向とする）について曲げ弾性率の測定を行った。なお、実施例１，２及び比較例１，２において、Ｘ方向は、繊維の引き揃え方向である。
<Measurement of flexural modulus in in-plane direction of base sheet>
In the obtained base material sheet itself, since a thickness is too small, a bending elastic modulus cannot be evaluated. Therefore, a plurality of the same sheet-like prepregs used for the production of the sheet were laminated, and pressed and heated to form a 2 mm thick laminate. Then, a strip-shaped test piece having a length of 100 mm, a width of 15 mm, and a thickness of 2 mm was cut out from the laminated plate with the direction in which the flexural modulus was measured as the length direction, and in accordance with JIS K7074, a universal testing machine was used. In a three-point bending test with a distance between supporting points of 80 mm, two directions in the in-plane direction of the sheet (the direction with the highest degree of orientation when the carbon fibers are aligned in the plane, the longitudinal direction of the sheet when not aligned) The bending elastic modulus was measured for the X direction and the Y direction perpendicular to the X direction. In Examples 1 and 2 and Comparative Examples 1 and 2, the X direction is the fiber alignment direction.
また、以下において、製造された基材シートの炭素繊維含有率は、原料である炭素繊維プリプレグのＦＡＷの数値を、得られた基材シートの厚さの数値と、炭素繊維の比重の数値で割ることにより求めた。 In the following, the carbon fiber content of the manufactured base sheet is the FAW value of the raw material carbon fiber prepreg, the thickness value of the obtained base sheet, and the specific value of the carbon fiber. Obtained by dividing.
［実施例１］
繊維長さ方向の引張弾性率６４０ＧＰａ、熱伝導率１４０Ｗ／ｍＫ、繊維径１１μｍのピッチ系炭素連続繊維（三菱樹脂（株）製ダイアリード「Ｋ６３７１２」）を一方向に引き揃え、未硬化のエポキシ樹脂（三菱樹脂（株）製「Ｃ３３３Ｅ」）を含浸させて作製された、ＦＡＷ１７５ｇ／ｍ２、樹脂含有率３２ｗｔ％、厚さ０．１５ｍｍの炭素繊維一方向プリプレグ（三菱樹脂（株）製「ＨｙＥＪ１７Ｍ６５ＰＤ」）を用い、このプリプレグを基材シートとして、その両面に、厚さ０．０２５ｍｍのポリエステルフィルム（三菱樹脂（株）製「Ｔ１００−２５」）を貼りあわせ、１２５℃に加熱した熱盤プレスで挟み込み、５ｋｇ／ｃｍ２の圧力をかけて２０分間保持してエポキシ樹脂を硬化させて、幅２０ｃｍ、長さ３０ｃｍの炭素繊維強化樹脂シートを得た。この炭素繊維強化樹脂シートの評価結果を表１に示す。
[Example 1]
Pitch-based carbon continuous fiber with a tensile modulus of 640 GPa in the fiber length direction, thermal conductivity of 140 W / mK, and fiber diameter of 11 μm (Dialead “K63312” manufactured by Mitsubishi Plastics, Inc.) is aligned in one direction and uncured epoxy Carbon fiber unidirectional prepreg (manufactured by Mitsubishi Plastics Co., Ltd.) manufactured by impregnating a resin ("C333E" manufactured by Mitsubishi Plastics Co., Ltd.) having a FAW of 175 g / m 2 , a resin content of 32 wt%, and a thickness of 0.15 mm HyEJ17M65PD "), using this prepreg as a base sheet, a 0.025 mm thick polyester film (" T100-25 "manufactured by Mitsubishi Resin Co., Ltd.) on both sides, and heated to 125 ° C sandwiched in a press, to cure the epoxy resin and held under a pressure of 5 kg / cm 2 20 min, width 20 cm, length 30cm carbon fiber To obtain a reinforced resin sheet. The evaluation results of this carbon fiber reinforced resin sheet are shown in Table 1.
［実施例２］
ポリエステルフィルムの代りに、厚さ０．０２５ｍｍ、プリプレグ目付５４ｇ／ｍ２のガラス繊維クロス・プリプレグ（日東紡株式会社製「ＷＰＡ
０３ １０４ＥＧ Ｃ」）を用いたこと以外は、実施例１と同様にして炭素繊維強化樹脂シートを得た。
この炭素繊維強化樹脂シートの評価結果を表１に示す。
[Example 2]
Instead of polyester film, glass fiber cloth prepreg with a thickness of 0.025 mm and prepreg weight of 54 g / m 2 (“WPA” manufactured by Nittobo Co., Ltd.)
03 104EG C ") was used in the same manner as in Example 1 to obtain a carbon fiber reinforced resin sheet.
The evaluation results of this carbon fiber reinforced resin sheet are shown in Table 1.
［実施例３］
繊維長さ方向の引張弾性率７９０ＧＰａ、熱伝導率２２０Ｗ／ｍＫ、繊維径７μｍのピッチ系炭素連続繊維（三菱樹脂（株）製ダイアリード「Ｋ１３Ａ１Ｌ」）を平織りに加工して作製された、ＦＡＷ１００ｇ／ｍ２の炭素繊維織物（三菱樹脂（株）製「ＦＰ３Ａ１０７」）に、未硬化のエポキシ樹脂（三菱樹脂（株）製「Ｃ３３３Ｅ」）をメチルエチルケトン溶媒に溶かして含浸させたものを２枚重ね合わせ、１２５℃に加熱した熱盤プレスで挟み込み、５ｋｇ／ｃｍ２の圧力をかけて２０分間保持してエポキシ樹脂を硬化させて幅２０ｃｍ、長さ３０ｃｍの炭素繊維強化樹脂シート（基材シート）を得た。
この炭素繊維強化樹脂シートの評価結果を表１に示す。
[Example 3]
FAW 100g produced by processing a pitch-based carbon continuous fiber (Dialead “K13A1L” manufactured by Mitsubishi Plastics, Inc.) with a tensile elastic modulus of 790 GPa in the fiber length direction, a thermal conductivity of 220 W / mK, and a fiber diameter of 7 μm into a plain weave. / M 2 carbon fiber fabric (“FP3A107” manufactured by Mitsubishi Plastics, Inc.) and two sheets of uncured epoxy resin (“C333E” manufactured by Mitsubishi Plastics) dissolved in methyl ethyl ketone solvent and impregnated. And sandwiching with a hot platen press heated to 125 ° C., holding a pressure of 5 kg / cm 2 for 20 minutes to cure the epoxy resin, and a carbon fiber reinforced resin sheet having a width of 20 cm and a length of 30 cm (base sheet) Got.
The evaluation results of this carbon fiber reinforced resin sheet are shown in Table 1.
［実施例４］
繊維長さ方向の引張弾性率６４０ＧＰａ、熱伝導率１４０Ｗ／ｍＫ、繊維径１１μｍのピッチ系炭素繊維を長さ３０ｍｍに切断加工して得られた短繊維（三菱樹脂（株）製ダイアリード「Ｋ６３７１Ｔ」）を、製紙用の湿式解繊装置に供して作製された、ＦＡＷ２５０ｇ／ｍ２の炭素繊維不織布に未硬化のエポキシ樹脂（三菱樹脂（株）製「Ｃ３３３Ｅ」）をメチルエチルケトン溶媒に溶かして含浸させたものを、１２５℃に加熱した熱盤プレスで挟み込み、２０ｋｇ／ｃｍ２の圧力をかけて２０分間保持してエポキシ樹脂を硬化させて幅２０ｃｍ、長さ３０ｃｍの炭素繊維強化樹脂シート（基材シート）を得た。
この炭素繊維強化樹脂シートの評価結果を表１に示す。
[Example 4]
Short fibers obtained by cutting a pitch-based carbon fiber having a tensile modulus of 640 GPa in the fiber length direction, a thermal conductivity of 140 W / mK, and a fiber diameter of 11 μm into a length of 30 mm (Dialead “K6331T manufactured by Mitsubishi Plastics, Inc.) )) Prepared in a wet defibrating device for papermaking, impregnated with FAW 250 g / m 2 carbon fiber nonwoven fabric by dissolving an uncured epoxy resin (“C333E” manufactured by Mitsubishi Plastics, Inc.) in a methyl ethyl ketone solvent. The carbon fiber reinforced resin sheet having a width of 20 cm and a length of 30 cm is obtained by sandwiching the resulting product with a hot platen press heated to 125 ° C., holding the pressure of 20 kg / cm 2 for 20 minutes to cure the epoxy resin. Material sheet).
The evaluation results of this carbon fiber reinforced resin sheet are shown in Table 1.
［比較例１］
ポリエステルフィルムを使用しないこと以外は、実施例１と同様にして炭素繊維強化樹脂シートを得た。
この炭素繊維強化樹脂シートの評価結果を表１に示す。
[Comparative Example 1]
A carbon fiber reinforced resin sheet was obtained in the same manner as in Example 1 except that no polyester film was used.
The evaluation results of this carbon fiber reinforced resin sheet are shown in Table 1.
［比較例２］
ピッチ系炭素繊維の代りに、繊維長さ方向の引張弾性率２３０ＧＰａ、熱伝導率６Ｗ／ｍＫ、繊維径７μｍのＰＡＮ系炭素連続繊維（三菱レイヨン（株）製パイロフィル「ＴＲ５０Ｓ」）を用いたこと以外は、実施例１と同様にして炭素繊維強化樹脂シートを得た。
この炭素繊維強化樹脂シートの評価結果を表１に示す。
[Comparative Example 2]
Instead of pitch-based carbon fiber, a PAN-based carbon continuous fiber having a tensile modulus of 230 GPa in the fiber length direction, a thermal conductivity of 6 W / mK, and a fiber diameter of 7 μm (Pyrofil “TR50S” manufactured by Mitsubishi Rayon Co., Ltd.) was used. Except for the above, a carbon fiber reinforced resin sheet was obtained in the same manner as in Example 1.
The evaluation results of this carbon fiber reinforced resin sheet are shown in Table 1.
［比較例３］
ピッチ系炭素繊維の代りに、繊維長さ方向の引張弾性率２３０ＧＰａ、熱伝導率６Ｗ／ｍＫ、繊維径７μｍのＰＡＮ系炭素繊維（三菱レイヨン（株）製パイロフィル「ＴＲ５０Ｓ」）を長さ３０ｍｍに切断加工して得られた短繊維を用いたこと以外は、実施例４と同様にして炭素繊維強化樹脂シートを得た。
この炭素繊維強化樹脂シートの評価結果を表１に示す。
[Comparative Example 3]
Instead of pitch-based carbon fiber, PAN-based carbon fiber (Pyrofil "TR50S" manufactured by Mitsubishi Rayon Co., Ltd.) having a tensile modulus of 230 GPa in the fiber length direction, a thermal conductivity of 6 W / mK, and a fiber diameter of 7 μm is 30 mm in length. A carbon fiber reinforced resin sheet was obtained in the same manner as in Example 4 except that short fibers obtained by cutting were used.
The evaluation results of this carbon fiber reinforced resin sheet are shown in Table 1.
表１より、本発明の炭素繊維強化樹脂シートは、基材シートの面内方向の熱伝導率及び曲げ弾性率が高く、また屈曲性に優れることから、各種用途に有用であることが分かる。 From Table 1, it can be seen that the carbon fiber reinforced resin sheet of the present invention has high thermal conductivity and bending elastic modulus in the in-plane direction of the base sheet, and is excellent in flexibility, so that it is useful for various applications.
Claims (5)
該炭素繊維が、一方向に引き揃えられた長繊維または連続繊維の形態で該シート内に存在し、
該炭素繊維強化樹脂製基材シートの両面に、フィルム、織布及び不織布よりなる群から選ばれる１種又は２種以上を積層一体化してなり、
該基材シートの面内方向における熱伝導率の最大値が１０Ｗ／ｍＫ以上で、該基材シートの面内方向における曲げ弾性率の最大値が２０ＧＰａ以上であり、かつ、該炭素繊維強化樹脂シートの総厚さが０．０５〜０．５ｍｍの範囲にあり、下記の屈曲性を満たすことを特徴とする炭素繊維強化樹脂シート。
屈曲性：該炭素繊維強化樹脂シートを３０ｃｍ角に切り出し、長手方向及び幅方向のそれぞれについて、曲率半径３０ｍｍでの折り曲げを５回繰り返した際、割れずに屈曲できる。 A carbon fiber reinforced resin sheet comprising a carbon fiber reinforced resin base sheet made by combining carbon fiber and resin,
The carbon fibers are present in the sheet in the form of long or continuous fibers aligned in one direction;
To both sides of the carbon fiber reinforced resin substrate sheet, a film, formed by laminating integrally one or more selected from the group consisting of woven and nonwoven fabrics,
The maximum value of thermal conductivity in the in-plane direction of the base sheet is 10 W / mK or more, the maximum value of bending elastic modulus in the in-plane direction of the base sheet is 20 GPa or more, and the carbon fiber reinforced resin A carbon fiber reinforced resin sheet having a total thickness of 0.05 to 0.5 mm and satisfying the following flexibility.
Flexibility: When the carbon fiber reinforced resin sheet is cut into a 30 cm square and bent at a radius of curvature of 30 mm for each of the longitudinal direction and the width direction, it can be bent without breaking.
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Families Citing this family (13)
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| JP4086942B2 (en) * | 1997-10-20 | 2008-05-14 | 東邦テナックス株式会社 | Prepreg manufacturing equipment |
| JP2001118974A (en) * | 1999-10-15 | 2001-04-27 | Mitsubishi Chemicals Corp | Heat radiating plate |
| JP3889608B2 (en) * | 2001-11-06 | 2007-03-07 | 北川工業株式会社 | Thermally conductive material and method for producing the same |
| JP4608175B2 (en) * | 2002-04-18 | 2011-01-05 | 三菱レイヨン株式会社 | Method for producing prepreg reinforcing sheet, method for producing prepreg |
| JP4904732B2 (en) * | 2004-07-08 | 2012-03-28 | 東レ株式会社 | Thermally conductive molded body and method for producing the same |
| JP2007276249A (en) * | 2006-04-06 | 2007-10-25 | Toray Ind Inc | Glass scrim cloth prepreg material and its manufacturing method |
| JP2007291204A (en) * | 2006-04-24 | 2007-11-08 | Teijin Ltd | Carbon fiber composite sheet |
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| WO2018142298A1 (en) * | 2017-02-02 | 2018-08-09 | Niteko S.R.L. | Planar heat sink made of high thermal conductivity and high mechanical strength composite material |
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