JP2003138043A - Prepreg with carrier sheet and carrier sheet for prepreg - Google Patents
Prepreg with carrier sheet and carrier sheet for prepregInfo
- Publication number
- JP2003138043A JP2003138043A JP2001339420A JP2001339420A JP2003138043A JP 2003138043 A JP2003138043 A JP 2003138043A JP 2001339420 A JP2001339420 A JP 2001339420A JP 2001339420 A JP2001339420 A JP 2001339420A JP 2003138043 A JP2003138043 A JP 2003138043A
- Authority
- JP
- Japan
- Prior art keywords
- prepreg
- sheet
- carrier sheet
- fiber
- carrying sheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、担持シートの片面
に、強化繊維に熱硬化性樹脂を含浸させたプリプレグが
形成された担持シート付きプリプレグ、及びプリプレグ
用担持シートに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a prepreg with a carrier sheet, in which a prepreg obtained by impregnating reinforcing fibers with a thermosetting resin is formed on one surface of the carrier sheet, and a carrier sheet for a prepreg.
【０００２】[0002]
【従来の技術】強化繊維と熱硬化型樹脂とからなる繊維
強化複合材は、軽量で優れた機械特性を有することか
ら、釣竿、ゴルフシャフト等のスポーツレジャー用部
材、航空機、自動車、船舶、建築物等の部材として広く
用いられている。かかる繊維強化複合材は、例えば、エ
ポキシ樹脂等の熱硬化性樹脂を、炭素繊維、アラミド繊
維、ガラス繊維等の強化繊維に含浸させ、半硬化状態と
した、シート状等の繊維強化熱硬化性樹脂プリプレグを
複数積層させた後、加熱・加圧し、プリプレグを硬化す
ることにより製造されている。なお、本明細書では、
「繊維強化熱硬化性樹脂プリプレグ」のことを単にプリ
プレグと称す。2. Description of the Related Art Fiber-reinforced composite materials composed of reinforcing fibers and thermosetting resins are lightweight and have excellent mechanical properties, and therefore, they are used for sports and leisure members such as fishing rods and golf shafts, aircraft, automobiles, ships, and construction. It is widely used as a member of things. Such a fiber reinforced composite material is, for example, a thermosetting resin such as an epoxy resin impregnated into a reinforcing fiber such as carbon fiber, aramid fiber or glass fiber to be a semi-cured state. It is manufactured by stacking a plurality of resin prepregs, and then heating and pressing to cure the prepregs. In this specification,
The "fiber reinforced thermosetting resin prepreg" is simply referred to as a prepreg.
【０００３】このように繊維強化複合材を製造する際に
用いて好適なプリプレグは、一般に、強化繊維若しくは
強化繊維の織物等を、あらかじめ片面に熱硬化性樹脂を
塗布しておいた２枚の担持シート間に挟持させ、加熱・
加圧し、繊維に樹脂を含浸させた後、一方の担持シート
を剥離し、プリプレグを１枚の担持シートに保持させた
担持シート付きプリプレグの形態で製造されている。そ
して、この担持シート付きプリプレグの形態で、搬送・
保管され、繊維強化複合材を製造する直前に、残りの担
持シートを剥離して使用されるようになっている。The prepreg suitable for use in the production of the fiber-reinforced composite material is generally composed of two sheets of reinforcing fiber or a woven fabric of the reinforcing fiber, which is coated with a thermosetting resin on one side in advance. It is sandwiched between carrier sheets and heated.
It is manufactured in the form of a prepreg with a carrying sheet, in which one carrying sheet is peeled off after pressure is applied to the fibers to impregnate the resin, and the prepreg is held by one carrying sheet. And, in the form of this prepreg with a carrying sheet,
Immediately before manufacturing the fiber-reinforced composite material, the remaining supporting sheet is peeled off and used.
【０００４】ところで、機械的特性の低下を防ぐために
は、ボイドのない緻密な繊維強化複合材を製造すること
が重要である。しかしながら、複数のプリプレグを積層
させて繊維強化複合材を製造する場合には、積層された
複数のプリプレグの層間に、空気や熱硬化性樹脂から揮
発した揮発物等の気体が取り込まれるため、この気体が
成形後の繊維強化複合材内に残留し、比較的大きな層間
ボイドが形成されやすいという問題があった。なお、ボ
イドとしては、プリプレグの層内に形成される層内ボイ
ドもあるが、層内ボイドは微小であり、繊維強化複合材
の機械的特性に対する影響は無視できる程度に小さい。
そのため、層間ボイドの形成を抑制するために、従来
は、一枚若しくは複数枚のプリプレグを積層する度に、
ピンやカツター刃などを用いて通気孔を形成したり、樹
脂フィルム等により被覆し、内部を真空状態にするなど
して、脱気を行う必要があり、製造プロセスが複雑化す
るという問題があった。By the way, in order to prevent deterioration of mechanical properties, it is important to produce a void-free and dense fiber-reinforced composite material. However, when manufacturing a fiber-reinforced composite material by laminating a plurality of prepregs, gas such as volatile matter volatilized from air or thermosetting resin is taken in between the layers of the laminated prepregs. There is a problem that gas remains in the fiber-reinforced composite material after molding, and relatively large interlayer voids are easily formed. As voids, there are intralayer voids formed in the layer of the prepreg, but the intralayer voids are minute and the influence on the mechanical properties of the fiber-reinforced composite material is negligibly small.
Therefore, in order to suppress the formation of interlayer voids, conventionally, every time one or more prepregs are laminated,
There is a problem that the manufacturing process is complicated because it is necessary to deaerate by forming a ventilation hole using a pin or a cutter blade, or by covering with a resin film etc. and making the inside a vacuum state. It was
【０００５】そこで、本発明者らは、特許２８０７８９
１号において、脱気作業を行うことなく、層間ボイドの
ない緻密な繊維強化複合材を製造することが可能なプリ
プレグとして、少なくとも片面に複数の溝部を有するプ
リプレグを提案している。本発明者らは、かかる構成の
プリプレグを複数積層して繊維強化複合材を製造するこ
とにより、複数設けた溝部が積層されたプリプレグの層
間の通気孔として機能し、自然に脱気が行われるため、
脱気作業を行うことなく、簡易に層間ボイドのない緻密
な繊維強化複合材を製造することができることを見出し
た。なお、複数の溝部を有するプリプレグは、プリプレ
グの表面に、溝部の形状や形成位置に対応した凸部を有
する溝付きロール等を押圧することにより、製造するこ
とができる。Therefore, the inventors of the present invention have proposed the patent 280789.
No. 1 proposes a prepreg having a plurality of groove portions on at least one surface as a prepreg capable of producing a dense fiber-reinforced composite material without interlayer voids without performing deaeration work. The inventors of the present invention produce a fiber-reinforced composite material by laminating a plurality of prepregs having such a configuration, and thus a plurality of groove portions function as ventilation holes between the layers of the laminated prepregs and are naturally deaerated. For,
It has been found that a dense fiber-reinforced composite material without interlayer voids can be easily manufactured without performing deaeration work. The prepreg having a plurality of grooves can be manufactured by pressing a grooved roll or the like having a protrusion corresponding to the shape and forming position of the groove on the surface of the prepreg.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、複数の
溝部を有するプリプレグでは、以下のような問題点があ
った。すなわち、プリプレグは搬送・保管され、製造か
らある程度期間が経った後、繊維強化複合材の製造に使
用されることが一般的であるが、プリプレグを構成する
熱硬化性樹脂は上述のように半硬化状態であるため、プ
リプレグの製造時に複数の溝部を形成しても、時間の経
過と共に、溝部の深さが浅くなり、繊維強化複合材を製
造する際に、積層されたプリプレグの層間の通気孔とし
ての機能が低下して、気体が残留し、層間ボイドが形成
される恐れがあった。However, the prepreg having a plurality of grooves has the following problems. That is, the prepreg is generally conveyed and stored, and after a certain period of time from the production, it is generally used for the production of the fiber-reinforced composite material. Since it is in the cured state, even if a plurality of grooves are formed during the production of the prepreg, the depth of the grooves becomes shallow with the passage of time, and when the fiber-reinforced composite material is produced, the passage between the layers of the laminated prepregs is reduced. There is a possibility that the function as pores may be deteriorated, gas may remain, and interlayer voids may be formed.
【０００７】また、プリプレグが溝部に沿って裂けるな
ど、機械的強度が低下する恐れや、製造される繊維強化
複合材の表面に、僅かながらも溝部の形状が残ってしま
う恐れもあった。また、溝付きロールが必要になるな
ど、従来に比較して、プリプレグの製造装置が複雑化す
るという問題もあった。Further, the prepreg may be torn along the groove, resulting in a decrease in mechanical strength, or the surface of the fiber-reinforced composite material produced may have a slight groove shape. In addition, there is a problem that the prepreg manufacturing apparatus is complicated as compared with the conventional one, such as the need for grooved rolls.
【０００８】そこで、本発明は上記課題を解決するため
になされたものであって、（１）製造から長期間経過し
た場合においても、層間ボイドのない緻密な繊維強化複
合材を簡易にかつ安定して製造することができると共
に、（２）十分な機械的強度を有し、（３）製造される
繊維強化複合材の表面形状に影響を与える恐れがなく、
（４）簡易に製造することが可能なプリプレグを得るこ
とが可能な手段を提供することを目的とする。Therefore, the present invention has been made to solve the above problems, and (1) easily and stably provides a dense fiber-reinforced composite material free from interlayer voids even after a long time has passed from the manufacture. And (2) has sufficient mechanical strength and (3) does not affect the surface shape of the fiber-reinforced composite material produced,
(4) It is an object to provide means capable of obtaining a prepreg that can be easily manufactured.
【０００９】[0009]
【課題を解決するための手段】本発明者は上記課題を解
決するべく検討を行った結果、以下のプリプレグ用担持
シート、及び担持シート付きプリプレグを発明するに到
った。本発明のプリプレグ用担持シートは、強化繊維に
熱硬化性樹脂を含浸させたプリプレグを担持するための
プリプレグ用担持シートにおいて、少なくともプリプレ
グを担持する側の表面に多数の微細な凹凸が形成されて
おり、その表面粗さが８μｍ以上であることを特徴とす
る。また、本発明のプリプレグ用担持シートにおいて、
少なくともプリプレグを担持する側の表面の表面粗さが
２０μｍ以下であることが好ましい。なお、本明細書に
おいて、「表面粗さ」とは、（株）ミツトヨ製のｓｕｒ
ｆｔｅｓｔ ４０２を用い、ＪＩＳ Ｂ ０６０１に基
づき、基準長さを２．５ｍｍとした時に測定される十点
平均粗さ（Ｒｚ）を意味しているものとする。As a result of studies to solve the above problems, the present inventor has invented the following prepreg carrying sheet and prepreg with a carrying sheet. The prepreg-supporting sheet of the present invention is a prepreg-supporting sheet for supporting a prepreg in which reinforcing fibers are impregnated with a thermosetting resin, and at least many fine irregularities are formed on the surface of the prepreg-supporting side. And its surface roughness is 8 μm or more. In the prepreg-supporting sheet of the present invention,
At least the surface roughness of the surface on which the prepreg is carried is preferably 20 μm or less. In the present specification, "surface roughness" means sur manufactured by Mitutoyo Corporation.
It means 10-point average roughness (Rz) measured by using ftest 402 based on JIS B 0601 and when the reference length is 2.5 mm.
【００１０】上記構成のプリプレグ用担持シートを用い
ることにより、以下の本発明の担持シート付きプリプレ
グを提供することができる。本発明の担持シート付きプ
リプレグは、担持シートの片面に、強化繊維に熱硬化性
樹脂を含浸させたプリプレグが形成された担持シート付
きプリプレグにおいて、前記担持シートの前記プリプレ
グ側表面に多数の微細な凹凸が形成されており、その表
面粗さが８μｍ以上であると共に、該担持シートの表面
形状に沿って前記プリプレグが形成されていることを特
徴とする。また、本発明の担持シート付きプリプレグに
おいて、前記担持シートの前記プリプレグ側表面の表面
粗さが２０μｍ以下であることが好ましい。なお、本明
細書において、「担持シート付きプリプレグ」とは、こ
の形態で搬送・保管され、繊維強化複合材の製造直前
に、担持シートを剥離してプリプレグを得ることが可能
な形態のものを意味しているものとする。By using the prepreg carrying sheet having the above structure, the following prepreg with a carrying sheet of the present invention can be provided. The prepreg with a carrying sheet of the present invention is a prepreg with a carrying sheet in which a prepreg obtained by impregnating a reinforcing fiber with a thermosetting resin is formed on one surface of the carrying sheet, and a large number of fine prepreg-side surfaces of the carrying sheet are provided. The unevenness is formed, the surface roughness is 8 μm or more, and the prepreg is formed along the surface shape of the carrying sheet. Further, in the prepreg with a carrying sheet of the present invention, it is preferable that the surface roughness of the prepreg side surface of the carrying sheet is 20 μm or less. In the present specification, "prepreg with a carrying sheet" refers to a form in which the carrying sheet is transported and stored in this form, and the carrying sheet can be peeled off to obtain a prepreg immediately before the production of the fiber-reinforced composite material. I mean it.
【００１１】また、本発明の担持シート付きプリプレグ
において、前記担持シートとしては、少なくとも前記プ
リプレグ側表面が離型性を有する離型紙が特に好適であ
る。また、本発明者は、このように、担持シートとして
離型紙を用いる場合には、担持シートの膜厚を従来と同
等の７０〜１４０μｍとしても、秤量を従来よりも軽
い、６５〜１３０ｇ／ｍ2とすることができることを見
出した。Further, in the prepreg with a carrying sheet of the present invention, as the carrying sheet, a release paper having a releasing property on at least the prepreg side surface is particularly suitable. Further, when the release sheet is used as the carrier sheet, the present inventor has a weight of 65 to 130 g / m, which is lighter than the conventional one, even when the thickness of the carrier sheet is 70 to 140 μm, which is the same as the conventional one. I have found that it can be 2 .
【００１２】本発明者は、以上の本発明のプリプレグ用
担持シート、担持シート付きプリプレグを用いることに
より、製造から長期間経過した場合においても、層間ボ
イドのない緻密な繊維強化複合材を簡易にかつ安定して
製造することができると共に、十分な機械的強度を有
し、製造される繊維強化複合材の表面形状に影響を与え
る恐れがないプリプレグを提供することができることを
見出した。また、本発明のプリプレグ用担持シート、担
持シート付きプリプレグを用いることにより、かかる特
性を有するプリプレグを簡易に製造することができるこ
とを見出した。The present inventor uses the above prepreg carrying sheet and prepreg with a carrying sheet of the present invention to easily produce a dense fiber-reinforced composite material having no interlayer voids even after a long period of time from production. It has been found that it is possible to provide a prepreg that can be stably manufactured, has sufficient mechanical strength, and does not affect the surface shape of the fiber-reinforced composite material to be manufactured. Further, they have found that by using the prepreg carrying sheet of the present invention and the prepreg with the carrying sheet, a prepreg having such characteristics can be easily produced.
【００１３】[0013]
【発明の実施の形態】以下、本発明について詳細に説明
する。
（プリプレグ用担持シート）本発明のプリプレグ用担持
シートは、少なくともプリプレグを担持する側の表面に
多数の微細な凹凸が形成されており、その表面粗さが８
μｍ以上であることを特徴としている。また、本発明の
プリプレグ用担持シートにおいて、少なくともプリプレ
グを担持する側の表面の表面粗さが２０μｍ以下である
ことが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. (Prepreg Support Sheet) The prepreg support sheet of the present invention has a large number of fine irregularities formed on at least the surface on which the prepreg is supported, and has a surface roughness of 8
It is characterized in that it is at least μm. Further, in the prepreg-supporting sheet of the present invention, it is preferable that at least the surface of the prepreg-supporting surface has a surface roughness of 20 μm or less.
【００１４】従来は、耐熱性を有することなどから、担
持シートとして、シリコーン樹脂等の離型剤を含浸させ
た紙等からなり、少なくともプリプレグを担持する側の
表面が離型性を有する離型紙が広く用いられている。離
型紙は、最後に、スーパーカレンダーロールを用いて、
表面の微細な凹凸を機械的に潰す艶出し工程を経て製造
されるため、その表面は平滑なものとなっているが、本
発明者が、市販のプリプレグ用の離型紙の表面粗さを測
定したところ、６μｍ以下であることが判明した。した
がって、本発明のプリプレグ用担持シートは、少なくと
もプリプレグを担持する側の表面が、従来の担持シート
よりも粗面化されていることが特徴的なものとなってい
る。なお、上述のように、担持シートとしては離型紙が
特に好適であるが、表面に多数の微細な凹凸が形成さ
れ、表面粗さが８μｍ以上の離型紙は、離型紙を製造す
る際の最後の艶出し工程を省くことにより製造すること
ができ、離型紙の製造プロセスをほとんど変えることな
く簡易に製造することができる。Conventionally, since it has heat resistance and the like, the carrier sheet is made of paper impregnated with a mold release agent such as silicone resin, and at least the surface on which the prepreg is supported has a mold release property. Is widely used. Finally, release paper, using a super calendar roll,
Since the surface is smooth because it is manufactured through a polishing process that mechanically crushes fine irregularities on the surface, the present inventor measures the surface roughness of release paper for commercial prepreg. As a result, it was found to be 6 μm or less. Therefore, the supporting sheet for prepreg of the present invention is characterized in that at least the surface on the side for supporting the prepreg is roughened as compared with the conventional supporting sheet. As described above, the release paper is particularly suitable as the carrier sheet, but the release paper having a large number of fine irregularities formed on the surface and having a surface roughness of 8 μm or more is a final release sheet during the production of the release paper. It can be manufactured by omitting the glazing step, and can be easily manufactured with almost no change in the manufacturing process of the release paper.
【００１５】以上の構成の本発明のプリプレグ用担持シ
ートを用いることにより、以下の本発明の担持シート付
きプリプレグを提供することができる。
（担持シート付きプリプレグ）本発明の担持シート付き
プリプレグは、担持シートのプリプレグ側表面に多数の
微細な凹凸が形成されており、その表面粗さが８μｍ以
上であると共に、該担持シートの表面形状に沿ってプリ
プレグが形成されていることを特徴としている。また、
本発明の担持シート付きプリプレグにおいて、担持シー
トのプリプレグ側表面の表面粗さが２０μｍ以下である
ことが好ましい。つまり、本発明の担持シート付きプリ
プレグは、前述の本発明のプリプレグ用担持シートのプ
リプレグを担持する側の表面に、その表面形状に沿って
プリプレグが形成されたものである。By using the carrier sheet for prepreg of the present invention having the above constitution, the following prepreg with a carrier sheet of the present invention can be provided. (Prepreg with a carrying sheet) The prepreg with a carrying sheet of the present invention has a large number of fine irregularities formed on the surface of the carrying sheet on the prepreg side and has a surface roughness of 8 μm or more and a surface shape of the carrying sheet. It is characterized in that a prepreg is formed along. Also,
In the prepreg with a carrying sheet of the present invention, the surface roughness of the prepreg side surface of the carrying sheet is preferably 20 μm or less. That is, the prepreg with a carrying sheet of the present invention is one in which the prepreg is formed along the surface shape on the surface of the prepreg carrying sheet of the present invention on which the prepreg is carried.
【００１６】このように、本発明の担持シート付きプリ
プレグは、プリプレグが、粗面化された担持シートの表
面形状に沿って形成されたものであるので、本発明の担
持シート付きプリプレグを構成するプリプレグは、担持
シート側の表面に、多数の微細な凹凸が形成され、粗面
化されたものとなっている。また、プリプレグの表面粗
さは担持シートの表面粗さと略同一になっている。As described above, the prepreg with a carrying sheet of the present invention comprises the prepreg formed along the surface shape of the roughened carrying sheet, and thus constitutes the prepreg with a carrying sheet of the present invention. The prepreg has a large number of fine irregularities formed on the surface on the side of the carrying sheet and is roughened. The surface roughness of the prepreg is substantially the same as the surface roughness of the carrier sheet.
【００１７】本発明者は、かかる構成の担持シート付き
プリプレグを用いて繊維強化複合材を製造することによ
り、プリプレグの片面に形成された多数の微細な凹部
が、積層されたプリプレグの層間の通気孔として機能す
るため、自然に脱気が行われ、脱気作業を行うことな
く、層間ボイドのない緻密な繊維強化複合材を簡易にか
つ安定して製造することができることを見出した。ま
た、本発明の担持シート付きプリプレグを構成するプリ
プレグには、その全面に渡って多数の微細な凹凸が形成
されているので、繊維強化複合材の製造時に、全面に渡
って自然に脱気を行うことができ、複数の溝部を設ける
場合と比較して、脱気効率を向上できることを見出し
た。その結果、層間ボイドのない緻密な繊維強化複合材
を、より簡易にかつ安定して製造することができること
を見出した。The present inventor manufactures a fiber-reinforced composite material by using the prepreg with a carrying sheet having such a structure, whereby a large number of fine recesses formed on one surface of the prepreg are passed through between the layers of the laminated prepreg. It has been found that since it functions as pores, it is naturally degassed, and a dense fiber-reinforced composite material without interlayer voids can be easily and stably manufactured without performing degassing work. Further, the prepreg constituting the prepreg with a carrying sheet of the present invention is formed with a large number of fine irregularities over the entire surface thereof, so that during the production of the fiber-reinforced composite material, the entire surface is naturally degassed. It was found that it can be performed and the degassing efficiency can be improved as compared with the case where a plurality of groove portions are provided. As a result, they have found that a dense fiber-reinforced composite material without interlayer voids can be manufactured more easily and stably.
【００１８】さらに、本発明の担持シート付きプリプレ
グは、この形態で搬送・保管され、繊維強化複合材の製
造直前に担持シートを剥離して使用されるため、プリプ
レグに形成された多数の微細な凹凸は、繊維強化複合材
の製造直前まで担持シートにより完全に保持されること
になる。そのため、製造から長期間経過した場合におい
ても、層間ボイドのない緻密な繊維強化複合材を安定し
て製造することができる。Further, the prepreg with a carrying sheet of the present invention is transported and stored in this form, and is used by peeling off the carrying sheet immediately before the production of the fiber reinforced composite material, so that a large number of fine prepregs formed on the prepreg are used. The irregularities will be completely retained by the carrier sheet until immediately before the production of the fiber-reinforced composite material. Therefore, a dense fiber-reinforced composite material without interlayer voids can be stably manufactured even after a long time has passed since the manufacture.
【００１９】また、本発明者は、本発明の担持シート付
きプリプレグを構成するプリプレグには、その全面に渡
って多数の微細な凹凸が形成されているので、複数の溝
部を設ける場合に比較して、凹部の深さをはるかに浅く
することができ、表面粗さが８μｍ以上で上記効果が得
られることを見出した。なお、担持シートの表面粗さが
８μｍ未満では、プリプレグの片面に形成された微細な
凹部の通気孔としての機能が低下し、上記効果を安定し
て得られない恐れがあり、好ましくない。また、プリプ
レグに形成される凹部の深さを浅くすることができる結
果、プリプレグに形成された多数の微細な凹凸の形状
が、製造される繊維強化複合材の表面に残ってしまう恐
れもない。また、複数の溝部を設ける場合と異なり、プ
リプレグが裂ける恐れもない。Further, the present inventor has a large number of fine irregularities formed on the entire surface of the prepreg which constitutes the prepreg with a carrying sheet of the present invention. It was found that the depth of the recess can be made much shallower and the above effect can be obtained when the surface roughness is 8 μm or more. When the surface roughness of the carrier sheet is less than 8 μm, the function of the minute recesses formed on one surface of the prepreg as the ventilation holes is lowered, and the above effects may not be obtained stably, which is not preferable. In addition, since the depth of the recesses formed in the prepreg can be reduced, there is no fear that many fine irregularities formed in the prepreg remain on the surface of the fiber-reinforced composite material to be manufactured. Further, unlike the case where a plurality of groove portions are provided, there is no risk of the prepreg tearing.
【００２０】また、担持シートの表面粗さが粗い程、プ
リプレグの表面粗さを粗くすることができ、繊維強化複
合材の製造時に高い脱気効果が得られるが、担持シート
の表面粗さが２０μｍ超になると、本発明の担持シート
付きプリプレグから担持シートを剥離する際に、担持シ
ートの微細な凹部に入り込んだプリプレグの熱硬化性樹
脂が担持シート側に残留する恐れがあるため、好ましく
ない。また、担持シートとして、離型紙を用いる場合に
は、離型紙の表面粗さを２０μｍ超にすることが製造上
困難であるという問題もある。Further, the rougher the surface roughness of the carrier sheet, the greater the surface roughness of the prepreg, and the high deaeration effect can be obtained during the production of the fiber-reinforced composite material. When it exceeds 20 μm, the thermosetting resin of the prepreg which has entered into the minute recesses of the carrying sheet may remain on the carrying sheet side when peeling the carrying sheet from the prepreg with a carrying sheet of the present invention, which is not preferable. . Further, when a release paper is used as the carrier sheet, there is a problem in that it is difficult to manufacture the release paper having a surface roughness of more than 20 μm.
【００２１】また、担持シートとしては離型紙が特に好
適であり、表面に多数の微細な凹凸が形成され、表面粗
さが８μｍ以上の離型紙は、離型紙を製造する際の最後
の艶出し工程を省くことにより、簡易に製造することが
可能であることを述べたが、一般に、離型紙を製造する
際には、艶出し工程において、表面の微細な凹凸を機械
的に潰して平滑化しているので、艶出し工程前に比較し
て艶出し工程後の離型紙の厚みは薄くなり、プリプレグ
用に市販されている離型紙の厚みは、一般に７０〜１４
０μｍ、秤量は７０〜１４０ｇ／ｍ2となっている。こ
れに対して、本発明では、艶出し工程を経ずに製造され
る離型紙を担持シートとして用いれば良いので、従来と
同等の厚みである７０〜１４０μｍとしても、秤量を従
来よりも軽い、６５〜１３０ｇ／ｍ2とすることができ
る。したがって、離型紙の原料量を削減することができ
ると共に、繊維強化複合材の製造時に廃棄される離型紙
量を削減することができ、環境面からも優れている。但
し、従来と同程度の秤量としても良く、この場合には、
従来よりも厚みが厚くなるので、離型紙の機械的強度を
向上させることができる。Release paper is particularly suitable as the carrying sheet, and a lot of fine irregularities are formed on the surface of the release sheet, and the release paper having a surface roughness of 8 μm or more is the final gloss in the production of the release paper. Although it was possible to easily manufacture by omitting the process, in general, when manufacturing release paper, in the polishing step, fine irregularities on the surface are mechanically crushed and smoothed. Therefore, the thickness of the release paper after the polishing step becomes thinner than that before the polishing step, and the thickness of the release paper commercially available for prepreg is generally 70 to 14
0 μm, and the weight is 70 to 140 g / m 2 . On the other hand, in the present invention, since the release paper manufactured without undergoing the polishing step may be used as the carrier sheet, even if the thickness is 70 to 140 μm, which is the same as the conventional thickness, the weighing amount is lighter than the conventional one. It can be 65 to 130 g / m 2 . Therefore, it is possible to reduce the amount of the release paper as a raw material, and it is possible to reduce the amount of the release paper discarded at the time of manufacturing the fiber-reinforced composite material, which is also excellent from the environmental aspect. However, it is possible to weigh as much as the conventional one. In this case,
Since the thickness is thicker than in the conventional case, the mechanical strength of the release paper can be improved.
【００２２】このように担持シートとして離型紙を用い
ることにより、離型紙を製造する際の艶出し工程を省く
だけで、本発明のプリプレグ用担持シートを簡易に得る
ことができると共に、離型紙の原料量や繊維強化複合材
の製造時に廃棄される離型紙量を削減することができる
という効果が得られ、好適であるが、本発明はこれに限
定されるものではない。本発明の担持シート付きプリプ
レグの製造プロセスにおける最高加熱温度に耐え得るだ
けの耐熱性を有し、少なくとも片面に多数の微細の凹凸
が形成され、その表面粗さが８μｍ以上であり、離型性
を有するものであれば、いかなる材質の担持シートを用
いても良い。By using the release paper as the carrier sheet in this way, the carrier sheet for prepreg of the present invention can be easily obtained and the release paper of the release paper can be obtained simply by omitting the polishing step in manufacturing the release paper. This is preferable because the amount of raw materials and the amount of release paper discarded during the production of the fiber-reinforced composite material can be reduced, which is preferable, but the present invention is not limited to this. It has heat resistance sufficient to withstand the maximum heating temperature in the manufacturing process of the prepreg with a carrying sheet of the present invention, has a large number of fine irregularities formed on at least one surface, and has a surface roughness of 8 μm or more and releasability. Any material may be used as long as it has
【００２３】また、本発明者は、表面が粗面化された担
持シートを用いた本発明の担持シート付きプリプレグ
は、平滑な担持シートを用いたものに比較して、担持シ
ートとプリプレグとの密着性が低く、繊維強化複合材の
製造時に担持シートを剥離しやすく、繊維強化複合材の
生産効率を向上できるという効果も得られることを見出
した。Further, the present inventor has found that the prepreg with a carrying sheet of the present invention using a carrying sheet having a roughened surface has a carrying sheet and a prepreg as compared with those using a smooth carrying sheet. It has been found that the adhesiveness is low, the carrier sheet can be easily peeled off during the production of the fiber-reinforced composite material, and the production efficiency of the fiber-reinforced composite material can be improved.
【００２４】また、本発明の担持シート付きプリプレグ
は、担持シートを変えるだけで、従来のプリプレグの製
造プロセスを何ら変えることなく簡易に製造することが
できるので、従来のプリプレグの製造装置をそのまま利
用することができ、好適である。Further, the prepreg with a carrying sheet of the present invention can be simply manufactured by changing the carrying sheet without changing the manufacturing process of the conventional prepreg. Therefore, the conventional prepreg manufacturing apparatus can be used as it is. It is possible and preferable.
【００２５】以下、図１に基づいて、本発明の担持シー
ト付きプリプレグを製造する際に用いて好適な製造装
置、及びこの製造装置を用いた担持シート付きプリプレ
グの製造方法について簡単に説明する。なお、以下に説
明する製造装置や製造方法は一例であって、本発明はこ
れに限定されるものではない。図１に示す製造装置は、
炭素繊維等の強化繊維を供給するクリール１と、クリー
ル１から供給された強化繊維を一方向に揃えるためのコ
ーム２と、片面にエポキシ樹脂等の熱硬化性樹脂が塗布
された担持シートを供給する巻出しロール３、４と、所
定の温度に加熱されたニップロール５、６、７と、巻出
しロール３から供給された担持シートを巻取る巻取りロ
ール８と、製造された担持シート付きプリプレグを巻取
る巻取りロール９とを具備して構成されている。A manufacturing apparatus suitable for manufacturing the prepreg with a carrier sheet of the present invention and a method for manufacturing a prepreg with a carrier sheet using the manufacturing apparatus will be briefly described below with reference to FIG. Note that the manufacturing apparatus and manufacturing method described below are examples, and the present invention is not limited thereto. The manufacturing apparatus shown in FIG.
A creel 1 for supplying reinforcing fibers such as carbon fibers, a comb 2 for aligning the reinforcing fibers supplied from the creel 1 in one direction, and a carrier sheet coated with a thermosetting resin such as epoxy resin on one side. Unwinding rolls 3 and 4, nip rolls 5, 6, and 7 heated to a predetermined temperature, a winding roll 8 that winds up the carrier sheet supplied from the unwinding roll 3, and the manufactured prepreg with a carrier sheet. And a take-up roll 9 for taking up.
【００２６】以上のように概略構成された製造装置を用
い、以下のようにして、担持シート付きプリプレグを製
造することができる。クリーム１から供給され、コーム
２により一方向に揃えられた強化繊維１０に対して、巻
出しロール３、４から、それぞれ片面に熱硬化性樹脂が
塗布された担持シート２０、３０を供給し、片面に熱硬
化性樹脂が塗布された２枚の担持シート２０、３０によ
り、強化繊維１０を挟持させる。このとき、熱硬化性樹
脂が塗布された側の面が強化繊維１０側に位置するよう
に、熱硬化性樹脂が塗布された担持シート２０、３０を
供給する。続いて、ニップロール５、６、７により加熱
・加圧することにより、熱硬化性樹脂を強化繊維１０に
含浸させ、２枚の担持シートに挟持されたプリプレグが
得られる。次いで、巻出しロール３から供給された担持
シートのみを剥離し、巻取りロール８により巻き取るこ
とにより、担持シート付きプリプレグ１１が得られるの
で、これを巻取りロール９により巻き取ることにより、
担持シート付きプリプレグ１１を製造することができ
る。このように、図１に示す製造装置では、巻出しロー
ル３から供給された担持シートは剥離され、巻出しロー
ル４から供給された担持シートのみが残るので、少なく
とも巻出しロール４から供給する担持シートとして、本
発明の担持シートを用いることにより、本発明の担持シ
ート付きプリプレグを簡易に製造することができる。A prepreg with a carrying sheet can be manufactured in the following manner by using the manufacturing apparatus configured as described above. To the reinforcing fibers 10 supplied from the cream 1 and aligned in one direction by the comb 2, the unwinding rolls 3 and 4 supply the carrier sheets 20 and 30 each coated with the thermosetting resin on one side, The reinforcing fiber 10 is sandwiched by the two carrier sheets 20 and 30 each having a thermosetting resin applied on one side. At this time, the carrier sheets 20 and 30 coated with the thermosetting resin are supplied so that the surface on the side coated with the thermosetting resin is located on the reinforcing fiber 10 side. Then, by heating and pressurizing with the nip rolls 5, 6, and 7, the thermosetting resin is impregnated in the reinforcing fiber 10 to obtain a prepreg sandwiched between two carrier sheets. Next, by peeling off only the carrying sheet supplied from the unwinding roll 3 and winding it up by the winding roll 8, a prepreg 11 with a carrying sheet is obtained. By winding it up by the winding roll 9,
The prepreg 11 with a carrying sheet can be manufactured. As described above, in the manufacturing apparatus shown in FIG. 1, since the carrier sheet supplied from the unwinding roll 3 is peeled off and only the carrier sheet supplied from the unwinding roll 4 remains, at least the carrier sheet supplied from the unwinding roll 4 is carried out. By using the carrier sheet of the present invention as a sheet, the prepreg with a carrier sheet of the present invention can be easily manufactured.
【００２７】以上説明したように、本発明のプリプレグ
用担持シート及び担持シート付きプリプレグを用いるこ
とにより、製造から長期間経過した場合においても、層
間ボイドのない緻密な繊維強化複合材を簡易にかつ安定
して製造することができると共に、十分な機械的強度を
有し、製造される繊維強化複合材の表面形状に影響を与
える恐れがないプリプレグを提供することができる。ま
た、本発明のプリプレグ用担持シート及び担持シート付
きプリプレグを用いることにより、かかる特性のプリプ
レグを、従来のプリプレグの製造プロセスを何ら変える
ことなく簡易に製造することができる。As described above, by using the carrier sheet for prepreg and the prepreg with a carrier sheet of the present invention, a dense fiber-reinforced composite material having no interlayer void can be easily and It is possible to provide a prepreg that can be stably manufactured, has sufficient mechanical strength, and does not affect the surface shape of the fiber-reinforced composite material to be manufactured. Further, by using the carrier sheet for prepreg and the prepreg with a carrier sheet of the present invention, a prepreg having such characteristics can be easily manufactured without changing the conventional prepreg manufacturing process.
【００２８】なお、１枚の担持シートを有する担持シー
ト付きプリプレグを取り上げて説明したが、本発明はこ
れに限定されるものではない。本発明は、２枚の担持シ
ートでプリプレグを挟持した構造の担持シート付きプリ
プレグにも適用可能である。この場合には、担持シート
付きプリプレグを製造する際に１枚の担持シートを剥離
せずに、２枚の担持シートでプリプレグを挟持した状態
で巻き取れば良い。Although the prepreg with a carrying sheet having one carrying sheet has been described, the present invention is not limited to this. The present invention is also applicable to a prepreg with a carrying sheet having a structure in which a prepreg is sandwiched between two carrying sheets. In this case, when manufacturing a prepreg with a carrying sheet, it is possible to wind the prepreg while sandwiching the prepreg with two carrying sheets without peeling off one carrying sheet.
【００２９】[0029]
【実施例】次に、本発明に係る実施例及び比較例につい
て説明する。
（実施例）本発明の担持シートとして、艶出し工程を省
くことにより、表面粗さが１２μｍの２枚の離型紙を作
製し、それぞれの片面に、２５０°Ｆ硬化型エポキシ樹
脂を塗布した。この２枚の離型紙と、引張強度が４４１
０ＭＰａ、弾性率が２３５ＧＰａ、１２０００フィラメ
ントの炭素繊維とを用い、図１に示したのと同様の製造
装置を用いて、本発明の担持シート付きプリプレグを製
造した。なお、繊維目付１５０ｇ／ｍ2、樹脂含有率３
５質量％のプリプレグを製造するように、製造条件を設
定した。得られた担持シート付きプリプレグから離型紙
を剥離し、３枚のプリプレグを±４５°に積層した後、
外径１０ｍｍφの鉄製マンドレルに巻き付け、最外層の
プリプレグの外側にさらに、厚さ３０μｍ、幅１５ｍｍ
のポリプロピレンフィルムテープを張力４ｋｇ／１５ｍ
ｍで巻き付けた。次いで、１３０℃で１時間加熱するこ
とにより、長さ５００ｍｍのパイプ状の繊維強化複合材
を成形した。EXAMPLES Next, examples and comparative examples according to the present invention will be described. (Example) As the carrier sheet of the present invention, two release papers having a surface roughness of 12 μm were prepared by omitting the polishing step, and a 250 ° F. curable epoxy resin was applied to one surface of each release paper. With these two release papers, the tensile strength is 441
A prepreg with a carrying sheet of the present invention was manufactured using 0 MPa, a modulus of elasticity of 235 GPa, and carbon fibers of 12000 filaments and the same manufacturing apparatus as shown in FIG. The fiber areal weight is 150 g / m 2 , the resin content is 3
The manufacturing conditions were set so as to manufacture 5% by mass of prepreg. After releasing the release paper from the obtained prepreg with a carrying sheet and stacking three prepregs at ± 45 °,
Wrapped around an iron mandrel with an outer diameter of 10 mmφ, and further outside the outermost prepreg, thickness 30 μm, width 15 mm
Tension of polypropylene film tape of 4kg / 15m
wrapped around m. Then, the pipe-shaped fiber-reinforced composite material having a length of 500 mm was molded by heating at 130 ° C. for 1 hour.
【００３０】（比較例）担持シートとして、艶出し工程
を経た、表面粗さが６μｍの市販の離型紙を用いた以外
は実施例と同様にして、担持シート付きプリプレグ、及
び繊維強化複合材を作製した。Comparative Example A prepreg with a carrying sheet and a fiber reinforced composite material were prepared in the same manner as in the example except that a commercially available release paper having a surface roughness of 6 μm which had been subjected to a glazing process was used as the carrying sheet. It was made.
【００３１】（評価及び結果）実施例、比較例において
用いた離型紙の表面粗さ、得られたプリプレグの繊維目
付、樹脂含有率を表１に示す。また、得られた繊維強化
複合材を長手方向に１００ｍｍ毎に４箇所切断し、各断
面を研磨した後、光学顕微鏡により観察し、３０μｍ以
上の径の層間ボイド数を数え、その平均を計算した結果
を表１に合わせて示す。表１に示すように、担持シート
として、表面粗さが１２μｍの離型紙を用いた実施例で
は、いずれの断面においても層間ボイドが全く観察され
なかったのに対し、担持シートとして、表面粗さが６μ
ｍの離型紙を用いた比較例では、層間ボイドが平均で１
５個観察され、本発明によれば、層間ボイドのない繊維
強化複合材を安定して製造することができることが判明
した。なお、本発明者は表面粗さが８μｍ以上の離型紙
を用いることにより、同様の結果が得られることを確認
している。(Evaluation and Results) Table 1 shows the surface roughness of the release paper used in Examples and Comparative Examples, the fiber areal weight of the obtained prepreg, and the resin content. Further, the obtained fiber-reinforced composite material was cut at four 100 mm intervals in the longitudinal direction, each cross section was polished, and then observed with an optical microscope to count the number of interlayer voids having a diameter of 30 μm or more and calculate the average thereof. The results are also shown in Table 1. As shown in Table 1, in the examples in which the release sheet having a surface roughness of 12 μm was used as the carrying sheet, no interlayer void was observed in any cross section, whereas the surface roughness of the carrying sheet was Is 6μ
In the comparative example using m release paper, the interlayer voids are 1 on average.
Five pieces were observed, and it was found that according to the present invention, a fiber-reinforced composite material without interlayer voids can be stably manufactured. The inventor has confirmed that similar results can be obtained by using a release paper having a surface roughness of 8 μm or more.
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【発明の効果】以上詳述したように、本発明のプリプレ
グ用担持シート及び担持シート付きプリプレグを用いる
ことにより、製造から長期間経過した場合においても、
層間ボイドのない緻密な繊維強化複合材を簡易にかつ安
定して製造することができると共に、十分な機械的強度
を有し、製造される繊維強化複合材の表面形状に影響を
与える恐れがないプリプレグを提供することができる。
また、本発明のプリプレグ用担持シート及び担持シート
付きプリプレグを用いることにより、かかる特性のプリ
プレグを、従来のプリプレグの製造プロセスを何ら変え
ることなく簡易に製造することができる。As described in detail above, by using the carrier sheet for prepreg and the prepreg with a carrier sheet of the present invention, even when a long time has passed from the production,
A dense fiber-reinforced composite material without interlayer voids can be easily and stably produced, has sufficient mechanical strength, and does not affect the surface shape of the fiber-reinforced composite material produced. A prepreg can be provided.
Further, by using the carrier sheet for prepreg and the prepreg with a carrier sheet of the present invention, a prepreg having such characteristics can be easily manufactured without changing the conventional prepreg manufacturing process.
【図面の簡単な説明】[Brief description of drawings]
【図１】 図１は、本発明の担持シート付きプリプレグ
を製造する際に用いて好適な製造装置の構造を示す図で
ある。FIG. 1 is a diagram showing a structure of a manufacturing apparatus suitable for use in manufacturing a prepreg with a carrying sheet of the present invention.
１０ 強化繊維 ２０、３０ 熱硬化性樹脂を塗布した担持シート １１ 担持シート付きプリプレグ １ クリール ２ コーム ３、４ 巻出しロール ５、６、７ ニップロール ８、９ 巻取りロール 10 Reinforcing fiber 20, 30 Carrier sheet coated with thermosetting resin 11 Prepreg with carrier sheet 1 creel 2 combs 3, 4 unrolling roll 5, 6, 7 nip roll 8, 9 Winding roll
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4F072 AA04 AA07 AB10 AD23 AG03 AG18 AG20 AK05 AL02 AL04 AL17 4F100 AD11 AK01B AK07 AK53 AT00A BA02 DD07A DG01B DG10A DH01B EH46 EH462 EJ42 EJ422 GB07 GB31 GB87 JB13B JK01 JK01B JL14A YY00A ─────────────────────────────────────────────────── ─── Continued front page F-term (reference) 4F072 AA04 AA07 AB10 AD23 AG03 AG18 AG20 AK05 AL02 AL04 AL17 4F100 AD11 AK01B AK07 AK53 AT00A BA02 DD07A DG01B DG10A DH01B EH46 EH462 EJ42 EJ422 GB07 GB31 GB87 JB13B JK01 JK01B JL14A YY00A
Claims (6)
性樹脂を含浸させたプリプレグが形成された担持シート
付きプリプレグにおいて、 前記担持シートの前記プリプレグ側表面に多数の微細な
凹凸が形成されており、その表面粗さが８μｍ以上であ
ると共に、該担持シートの表面形状に沿って前記プリプ
レグが形成されていることを特徴とする担持シート付き
プリプレグ。1. A prepreg with a carrier sheet, in which a prepreg obtained by impregnating a reinforcing fiber with a thermosetting resin is formed on one surface of a carrier sheet, wherein a large number of fine irregularities are formed on the surface of the carrier sheet on the side of the prepreg. A prepreg with a carrying sheet, wherein the prepreg has a surface roughness of 8 μm or more, and the prepreg is formed along the surface shape of the carrying sheet.
の表面粗さが２０μｍ以下であることを特徴とする請求
項１に記載の担持シート付きプリプレグ。2. The prepreg with a carrying sheet according to claim 1, wherein the surface roughness of the prepreg side surface of the carrying sheet is 20 μm or less.
プレグ側表面が離型性を有する離型紙であることを特徴
とする請求項１又は請求項２に記載の担持シート付きプ
リプレグ。3. The prepreg with a carrying sheet according to claim 1, wherein the carrying sheet is a release paper having a releasability at least on the prepreg side surface.
ｍ、秤量が６５〜１３０ｇ／ｍ2であることを特徴とす
る請求項３に記載の担持シート付きプリプレグ。4. The thickness of the carrier sheet is 70 to 140 μm.
The prepreg with a carrying sheet according to claim 3, wherein m and the basis weight are 65 to 130 g / m 2 .
リプレグを担持するためのプリプレグ用担持シートにお
いて、 少なくともプリプレグを担持する側の表面に多数の微細
な凹凸が形成されており、その表面粗さが８μｍ以上で
あることを特徴とするプリプレグ用担持シート。5. A prepreg-supporting sheet for supporting a prepreg in which reinforcing fibers are impregnated with a thermosetting resin, wherein a large number of fine irregularities are formed on at least the surface on which the prepreg is supported, and the surface thereof is formed. A carrier sheet for prepreg, which has a roughness of 8 μm or more.
面の表面粗さが２０μｍ以下であることを特徴とする請
求項５に記載のプリプレグ用担持シート。6. The carrier sheet for prepreg according to claim 5, wherein the surface roughness of at least the surface supporting the prepreg is 20 μm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001339420A JP4000253B2 (en) | 2001-11-05 | 2001-11-05 | Prepreg with carrier sheet and carrier sheet for prepreg |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001339420A JP4000253B2 (en) | 2001-11-05 | 2001-11-05 | Prepreg with carrier sheet and carrier sheet for prepreg |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003138043A true JP2003138043A (en) | 2003-05-14 |
| JP4000253B2 JP4000253B2 (en) | 2007-10-31 |
Family
ID=19153769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001339420A Expired - Fee Related JP4000253B2 (en) | 2001-11-05 | 2001-11-05 | Prepreg with carrier sheet and carrier sheet for prepreg |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4000253B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012025144A (en) * | 2010-02-04 | 2012-02-09 | Dainippon Printing Co Ltd | Embossed mold release paper, prepreg laminate, and method for producing fiber-reinforced composite material |
| JP2014015567A (en) * | 2012-07-10 | 2014-01-30 | Mitsubishi Rayon Co Ltd | Prepreg |
| US20200385540A1 (en) * | 2017-12-22 | 2020-12-10 | Toray Industries, Inc. | A tape-shaped prepreg and a method for production thereof |
| JP2021000802A (en) * | 2019-06-24 | 2021-01-07 | 昭和電工マテリアルズ株式会社 | Method for manufacturing frp precursor, frp precursor, laminated sheet, laminate, printed wiring board and semiconductor package |
-
2001
- 2001-11-05 JP JP2001339420A patent/JP4000253B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012025144A (en) * | 2010-02-04 | 2012-02-09 | Dainippon Printing Co Ltd | Embossed mold release paper, prepreg laminate, and method for producing fiber-reinforced composite material |
| JP2014015567A (en) * | 2012-07-10 | 2014-01-30 | Mitsubishi Rayon Co Ltd | Prepreg |
| US20200385540A1 (en) * | 2017-12-22 | 2020-12-10 | Toray Industries, Inc. | A tape-shaped prepreg and a method for production thereof |
| US11938655B2 (en) * | 2017-12-22 | 2024-03-26 | Toray Industries, Inc. | Tape-shaped prepreg and a method for production thereof |
| JP2021000802A (en) * | 2019-06-24 | 2021-01-07 | 昭和電工マテリアルズ株式会社 | Method for manufacturing frp precursor, frp precursor, laminated sheet, laminate, printed wiring board and semiconductor package |
| JP7346932B2 (en) | 2019-06-24 | 2023-09-20 | 株式会社レゾナック | Method for manufacturing FRP precursor, FRP precursor, laminate sheet, laminate board, printed wiring board, and semiconductor package |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4000253B2 (en) | 2007-10-31 |
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