JPH07137152A - Manufacture of composite material - Google Patents
Manufacture of composite materialInfo
- Publication number
- JPH07137152A JPH07137152A JP5283532A JP28353293A JPH07137152A JP H07137152 A JPH07137152 A JP H07137152A JP 5283532 A JP5283532 A JP 5283532A JP 28353293 A JP28353293 A JP 28353293A JP H07137152 A JPH07137152 A JP H07137152A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- fiber
- reinforcing fiber
- thermosetting resin
- thermoplastic resin
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、航空機用構造材料や自
動車用途等に適する優れた熱的性質、機械的特性と靭性
を併せ持つ複合材料の製造方法の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a method for producing a composite material having excellent thermal properties, mechanical properties and toughness, which are suitable for aircraft structural materials and automotive applications.
【０００２】[0002]
【従来の技術】炭素繊維などの高強度高弾性繊維を強化
繊維とする複合材料は、その比強度、比弾性に優れると
いう特徴を行かしてスポーツ用途を中心に広く用いられ
てきている。2. Description of the Related Art Composite materials having high-strength and high-elasticity fibers such as carbon fibers as reinforcing fibers have been widely used mainly for sports applications because of their excellent specific strength and specific elasticity.
【０００３】通常マトリックス樹脂として使用されるエ
ポキシ樹脂をはじめとする熱硬化性樹脂は、種々の特長
を有する反面、靭性に乏しいという欠点を有するため複
合材料での衝撃に対し層間剥離を起こし易く、航空機等
の一次構造材料としての適用に至っていなかった。Thermosetting resins such as epoxy resins, which are usually used as matrix resins, have various characteristics, but on the other hand, they have the drawback of being poor in toughness, so that they easily cause delamination upon impact with a composite material. It has not been applied as a primary structural material for aircraft and the like.
【０００４】この欠点を改良する方法としては、マトリ
ックス樹脂である熱硬化性樹脂に、ゴム成分や熱可塑性
樹脂を添加する方法が一般的であるが、十分な靭性改良
効果を得るためには、相当量の添加を要し、熱硬化性樹
脂の優れた扱い性、賦形性、耐熱性等の低下を招く結果
となっていた。As a method for improving this drawback, a method of adding a rubber component or a thermoplastic resin to a thermosetting resin which is a matrix resin is generally used, but in order to obtain a sufficient effect of improving the toughness, A considerable amount of addition is required, resulting in deterioration of excellent handling property, shapeability, heat resistance and the like of the thermosetting resin.
【０００５】また、インターリーフと呼ばれる一種の接
着層、熱可塑性フィルムを層間に挿入する方法も知られ
ているが、強化繊維の含有率が上げられないとか、作業
性が劣るなどの理由で広く実用化される迄には至ってい
ない。A method of inserting a kind of adhesive layer called an interleaf or a thermoplastic film between layers is also known, but it is widely used because the content of reinforcing fibers cannot be increased or the workability is poor. It has not been put to practical use.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、マトリック
ス樹脂の優れた熱的性質及び機械的性質を損なうことな
く、優れた靭性を兼ね備えた繊維強化複合材料を効率良
く製造し得る方法の提供を課題とするものである。DISCLOSURE OF THE INVENTION The present invention provides a method for efficiently producing a fiber-reinforced composite material having excellent toughness without impairing the excellent thermal and mechanical properties of the matrix resin. This is an issue.
【０００７】[0007]
【課題を解決するための手段】本発明は、強化繊維、熱
硬化性樹脂及び繊維状熱可塑性樹脂からフィラメントワ
インディング法により複合材料を製造する方法におい
て、熱硬化性樹脂を付着した強化繊維、あるいは熱硬化
性樹脂を強化繊維に含浸して得られる強化繊維シートを
配置し、次にその外表面に繊維状熱可塑性樹脂を配置す
る工程を少なくとも１工程、積層体の最内部及び／また
は内部を形成する工程に設けることを特徴とする複合材
料の製造方法を上記課題を解決するための手段とするも
のである。The present invention provides a method for producing a composite material from a reinforcing fiber, a thermosetting resin and a fibrous thermoplastic resin by a filament winding method, in which a reinforcing fiber having a thermosetting resin attached, or At least one step of arranging a reinforcing fiber sheet obtained by impregnating a reinforcing fiber with a thermosetting resin and then arranging a fibrous thermoplastic resin on the outer surface of the reinforcing fiber sheet, A method for manufacturing a composite material, which is provided in a forming step, is used as means for solving the above problems.
【０００８】以下、本発明を更に詳しく説明する。本発
明に使用される強化繊維としては、通常の繊維強化複合
材料に用いられる、炭素繊維、黒鉛繊維、ボロン繊維、
チラノ繊維、アラミド繊維等が挙げられるが、弾性率
が、２００ＧＰａ以上のものが好ましく、より好ましく
は引張強度３５００ＭＰａ以上の炭素繊維、黒鉛繊維で
あり、更に最も好ましいのは引張強度４５００ＭＰａ以
上、伸度１．７％以上の高強度・高伸度の炭素繊維・黒
鉛繊維である。The present invention will be described in more detail below. The reinforcing fibers used in the present invention are used for ordinary fiber-reinforced composite materials, carbon fibers, graphite fibers, boron fibers,
Tyranno fiber, aramid fiber and the like can be mentioned, but the elastic modulus is preferably 200 GPa or more, more preferably carbon fiber or graphite fiber having a tensile strength of 3500 MPa or more, and most preferably tensile strength of 4500 MPa or more and elongation. It is a carbon fiber / graphite fiber having high strength and high elongation of 1.7% or more.
【０００９】また、熱硬化性樹脂としては、エポキシ樹
脂、ビスマレイミド樹脂等、通常の繊維強化複合材料に
用いられるマトリックス樹脂がそのまま使用される。As the thermosetting resin, an epoxy resin, a bismaleimide resin, or another matrix resin used for ordinary fiber-reinforced composite materials is used as it is.
【００１０】更に、繊維状熱可塑性樹脂としては、繊維
状のポリアミド、ポリエステルのほかにポリエーテルイ
ミド、ポリエーテルエーテルケトン、ポリベンズイミダ
ゾール、ポリイミドなどいわゆるエンジニアリングプラ
スチック、スーパーエンジニアリングプラスチックを繊
維状に賦形したもの等が好適に用いられる。Further, as the fibrous thermoplastic resin, in addition to fibrous polyamide and polyester, so-called engineering plastics such as polyetherimide, polyetheretherketone, polybenzimidazole and polyimide, and super engineering plastics are formed into fibrous shapes. Those that have been used are preferably used.
【００１１】繊維状熱可塑性樹脂の形態としては、モノ
フィラメント又はマルチフィラメントが好ましいが、必
ずしもそれらに限定されるものでない。また、その直径
としては、１００μ以下、特に５０μ以下が好ましい。The form of the fibrous thermoplastic resin is preferably, but not necessarily limited to, monofilament or multifilament. The diameter is preferably 100 μm or less, and particularly preferably 50 μm or less.
【００１２】熱硬化性樹脂が付着した強化繊維は、通常
強化繊維を熱硬化性樹脂中を通過させる公知の方法によ
り得られる。熱硬化性樹脂溶液中を通過させた後に、溶
剤を蒸発させ除去する方法も用いられる。溶剤の除去
は、後の成形硬化過程において行っても良い。The reinforcing fiber to which the thermosetting resin is attached is usually obtained by a known method in which the reinforcing fiber is passed through the thermosetting resin. A method of evaporating and removing the solvent after passing through the thermosetting resin solution is also used. The removal of the solvent may be performed in the subsequent molding and curing process.
【００１３】熱硬化性樹脂を強化繊維に含浸して得られ
る強化繊維シートとは、強化繊維を一方向に引き揃えた
シート、又は強化繊維からなる織物等に熱硬化性樹脂を
含浸して得られる強化繊維シートである。繊維強化複合
材料では一般にプリプレグと称されるものであり、熱硬
化性樹脂を加熱し強化繊維に含浸する方法、熱硬化性樹
脂を適当な溶剤に溶解し粘度を適正化し強化繊維に含浸
する方法などにより一般に製造される。A reinforcing fiber sheet obtained by impregnating a thermosetting resin into a reinforcing fiber is a sheet obtained by aligning the reinforcing fibers in one direction, or a woven fabric made of the reinforcing fibers impregnated with the thermosetting resin. It is a reinforced fiber sheet. Fiber-reinforced composite materials are generally called prepregs. A method of heating a thermosetting resin to impregnate the reinforcing fibers, a method of dissolving the thermosetting resin in an appropriate solvent to optimize the viscosity, and impregnating the reinforcing fibers. Are generally manufactured by
【００１４】熱硬化性樹脂が付着した強化繊維、あるい
は熱硬化性樹脂を強化繊維に含浸し得られる強化繊維シ
ートにおいて強化繊維と熱硬化性樹脂の組成分率として
は、強化繊維／熱硬化性樹脂＝６０／４０〜７５／２５
重量比が取扱性・成形性の点から好ましい。In the reinforcing fiber to which the thermosetting resin is attached or the reinforcing fiber sheet obtained by impregnating the reinforcing fiber with the thermosetting resin, the composition ratio of the reinforcing fiber and the thermosetting resin is as follows: Resin = 60/40 to 75/25
The weight ratio is preferable from the viewpoint of handleability and moldability.
【００１５】本発明では、熱硬化性樹脂を付着した強化
繊維、あるいは熱硬化性樹脂を強化繊維に含浸して得ら
れる強化繊維シート、及び／またはその外表面に繊維状
熱可塑性樹脂を配置するためにフィラメントワインディ
ング法が使用される。In the present invention, the reinforcing fibers to which the thermosetting resin is attached, or the reinforcing fiber sheet obtained by impregnating the reinforcing fibers with the thermosetting resin, and / or the fibrous thermoplastic resin is arranged on the outer surface thereof. The filament winding method is used for this purpose.
【００１６】本発明において、これらの熱硬化性樹脂が
付着した強化繊維、あるいは熱硬化性樹脂を強化繊維に
含浸して得られる強化繊維シートを配置する方法は、た
とえば、熱硬化性樹脂が付着した強化繊維を使用する場
合、この熱硬化性樹脂が付着した強化繊維をマンドレル
あるいは成形型上等に所定の間隔、角度で巻つける方
法、あるいは強化繊維シートを配置する方法としては、
所定の大きさの強化繊維シートをマンドレル等に巻つけ
る方法、あるいはこれらを組み合わせた方法等、公知の
方法を使用できる。In the present invention, the method of arranging the reinforcing fibers to which these thermosetting resins are adhered or the reinforcing fiber sheet obtained by impregnating the reinforcing fibers with the thermosetting resin is, for example, the thermosetting resin adhered. In the case of using the reinforced fiber, the thermosetting resin-attached reinforced fiber is wound on the mandrel or the molding die at a predetermined interval, at an angle, or as a method of arranging the reinforced fiber sheet,
Known methods such as a method of winding a reinforcing fiber sheet of a predetermined size around a mandrel or the like, or a method of combining these can be used.
【００１７】このようにして熱硬化性樹脂が付着した強
化繊維、あるいは熱硬化性樹脂を強化繊維に含浸して得
られる強化繊維シートを配置した後、繊維状熱可塑性樹
脂をその外表面に配置するが、繊維状熱可塑性樹脂の配
置方法としては、繊維状熱可塑性樹脂を一定間隔で巻つ
ける方法、繊維状熱可塑性樹脂からなる織物又は短繊維
シートを巻つける方法、及び短繊維を表面に回転させな
がら振りかけ付着させる方法など何れの方法でも良く、
適宜選択すればよいが、作業効率の面からは、一定間隔
で繊維状熱可塑性樹脂のマルチフィラメントを巻つけ方
法が好ましい。After arranging the reinforcing fiber to which the thermosetting resin is adhered in this way or the reinforcing fiber sheet obtained by impregnating the reinforcing fiber with the thermosetting resin, the fibrous thermoplastic resin is arranged on the outer surface thereof. However, as a method of arranging the fibrous thermoplastic resin, a method of winding the fibrous thermoplastic resin at regular intervals, a method of winding a woven fabric or a short fiber sheet made of the fibrous thermoplastic resin, and short fibers on the surface. Any method such as sprinkling and attaching while rotating,
It may be appropriately selected, but from the viewpoint of work efficiency, a method of winding multifilaments of fibrous thermoplastic resin at regular intervals is preferable.
【００１８】表面の繊維状熱可塑性樹脂による隠蔽率は
９５％以下であることが好ましい。より好ましくは８０
％以下である。ここで言う隠蔽率（％）とは、先に配置
された熱硬化性樹脂が付着した強化繊維、あるいは熱硬
化性樹脂を強化繊維に含浸して得られる強化繊維シート
が覆う面積に対し、それを繊維状熱可塑性樹脂が蔽う面
積の割合を意味する。隠蔽率が、９５％を越えるとあら
かじめ配置された熱硬化性樹脂が付着した強化繊維、あ
るいは熱硬化性樹脂を強化繊維に含浸し得られる強化繊
維シートが表面に露出する部分が少なくなり、次に熱硬
化性樹脂を付着した強化繊維、あるいは熱硬化性樹脂を
強化繊維に含浸し得られる強化繊維シートを配置する上
において、所定の粘着性、タックをその表面に付与でき
ず、作業性が低下してしまう。The hiding ratio of the fibrous thermoplastic resin on the surface is preferably 95% or less. More preferably 80
% Or less. The concealment rate (%) referred to here means the area covered by the reinforced fiber to which the thermosetting resin is previously attached or the reinforced fiber sheet obtained by impregnating the reinforced fiber with the thermosetting resin. Means the ratio of the area covered by the fibrous thermoplastic resin. When the hiding ratio exceeds 95%, the reinforcing fibers to which the thermosetting resin arranged in advance is attached, or the reinforcing fiber sheet obtained by impregnating the reinforcing fibers with the thermosetting resin is less exposed on the surface. When arranging a reinforcing fiber having a thermosetting resin attached thereto or a reinforcing fiber sheet obtained by impregnating a reinforcing fiber with a thermosetting resin, predetermined adhesiveness and tack cannot be imparted to the surface, and workability is improved. Will fall.
【００１９】本発明では、熱硬化性樹脂を付着した強化
繊維、あるいは熱硬化性樹脂を強化繊維に含浸して得ら
れる強化繊維シートを配置し（以下この操作をＬと略記
する場合がある）、次にその外表面に繊維状熱可塑性樹
脂を配置する（以下この操作をＴと略記する場合があ
る）工程（ＬＴ）を積層体の最内部及び／または内部を
形成する工程に少なくとも１工程設ける必要があり、こ
の工程を設けないと、得られる成形硬化物に所望の優れ
た耐衝撃性を付与することができない。In the present invention, a reinforcing fiber having a thermosetting resin attached thereto or a reinforcing fiber sheet obtained by impregnating the reinforcing fiber with a thermosetting resin is arranged (hereinafter, this operation may be abbreviated as L). Then, a step (LT) of disposing a fibrous thermoplastic resin on the outer surface thereof (hereinafter, this operation may be abbreviated as T) is performed in at least one step of forming the innermost portion and / or the inner portion of the laminate. It is necessary to provide it, and if this step is not provided, desired excellent impact resistance cannot be imparted to the obtained molded cured product.
【００２０】本発明において、積層体の最内部及び／ま
たは内部を形成する工程とは、最外層を形成する工程以
外の工程を意味する。たとえば積層体の構成として、
（ＬＴ）ｎＬ［ｎは１以上の整数］、又は（ＬＴ）ＬＬ
（ＬＴ）Ｌ等であり、その構成は耐衝撃性要求度合い等
により、適宜決定すればよい。このように構成すること
により、強化繊維と熱硬化性樹脂とから形成される層の
少なくとも１層間に選択的に繊維状熱可塑性樹脂を配置
することができ、その後加熱硬化、一体化し、さらに脱
型することにより、耐衝撃性に優れた複合材料を得るこ
とができる。In the present invention, the step of forming the innermost portion and / or the inner portion of the laminate means a step other than the step of forming the outermost layer. For example, as a laminate structure,
(LT) nL [n is an integer of 1 or more], or (LT) LL
(LT) L and the like, and the configuration thereof may be appropriately determined depending on the degree of demand for impact resistance and the like. With such a configuration, the fibrous thermoplastic resin can be selectively disposed between at least one of the layers formed of the reinforcing fiber and the thermosetting resin, and then the resin is heat-cured, integrated, and further removed. By molding, a composite material having excellent impact resistance can be obtained.
【００２１】本発明における好ましい実施態様は以下の
通りである。すなわち、 １）強化繊維として炭素繊維、熱硬化性樹脂としてエポ
キシ樹脂あるいはビスマレイミド樹脂、繊維状熱可塑性
樹脂としてポリアミド系繊維またはポリエーテルイミド
樹脂またはポリイミド樹脂のマルチフィラメントを用
い、炭素繊維の束に熱硬化性樹脂を含浸したもの（トウ
プリプレグ）をフィラメントワインディング装置により
マンドレル上に所定パタンで巻つけ、次にその表面に繊
維状熱可塑性樹脂を一定間隔で巻つけ、さらにこれらの
操作をくり返し、最後に最外層にトウプリプレグを巻つ
けたものを加熱硬化する複合材料の製造方法。及び、The preferred embodiments of the present invention are as follows. That is, 1) carbon fiber is used as a reinforcing fiber, epoxy resin or bismaleimide resin is used as a thermosetting resin, and multifilament of polyamide fiber or polyetherimide resin or polyimide resin is used as a fibrous thermoplastic resin to form a bundle of carbon fibers. Wrap a thermosetting resin impregnated (tow prepreg) on a mandrel with a predetermined pattern by a filament winding device, then wind a fibrous thermoplastic resin on its surface at regular intervals, and repeat these operations. Finally, a method for producing a composite material, in which a tow prepreg wound on the outermost layer is heat-cured. as well as,
【００２２】２）強化繊維として炭素繊維、熱硬化性樹
脂としてエポキシ樹脂あるいはビスマレイミド樹脂、繊
維状熱可塑性樹脂としてポリアミド系繊維またはポリエ
ーテルイミド樹脂またはポリイミド樹脂のマルチフィラ
メントを用い、炭素繊維の束に熱硬化性樹脂を含浸した
もの（トウプリプレグ）をフィラメントワインディング
装置によりマンドレル上に所定パタンで巻つけ、あるい
は、熱硬化性樹脂と炭素繊維からなるシート（プリプレ
グ）を巻つけ、次にその表面に繊維状熱可塑性樹脂を一
定間隔で巻つけ、さらにこれらを繰り返し、最後に最外
層にトウプリプレグあるいはプリプレグを巻つけたもの
を加熱硬化する複合材料の製造方法である。2) Carbon fiber is used as the reinforcing fiber, epoxy resin or bismaleimide resin is used as the thermosetting resin, and multifilament of polyamide fiber, polyetherimide resin or polyimide resin is used as the fibrous thermoplastic resin, and a bundle of carbon fibers is used. Wound with thermosetting resin (tow prepreg) on the mandrel with a filament winding device in a predetermined pattern, or a sheet (prepreg) consisting of thermosetting resin and carbon fiber, and then the surface This is a method for producing a composite material in which a fibrous thermoplastic resin is wound at a constant interval, the above steps are repeated, and finally, a tow prepreg or a prepreg wound around the outermost layer is heat-cured.
【００２３】[0023]
【実施例】以下実施例により本発明を更に具体的に説明
する。The present invention will be described in more detail with reference to the following examples.
【００２４】（実施例１，２）強化繊維として三菱レイ
ヨン社製中弾性高強度炭素繊維：ＭＲ−５０Ｋ １２Ｍ
（エポキシ樹脂用にはサイズ剤の付着していないもの
を、ビスマレイミド樹脂用にはサイズ剤の付着していな
いものにγ−アミノプロピルトリエトキシシランの０．
１％水溶液で処理したもの）を使用し、熱硬化性樹脂と
して、表１の組成のエポキシ樹脂及びビスマレイミド樹
脂を用い、エポキシ樹脂はメチルエチルケトンを溶剤と
し、ビスマレイミド樹脂は塩化メチレンを溶剤として、
それぞれの熱硬化性樹脂を含む溶液を調整し、強化繊維
を所定の速度でこの溶液中を通過させ、その後乾燥ゾー
ンを通過させて溶剤を除去し、加熱ロールでトウ幅を
３．５ｍｍとして巻き取ることにより、樹脂の含有量が
３５％の熱硬化性樹脂が付着した強化繊維を得た。ま
た、それぞれの樹脂を加熱し離型紙上に引き伸ばすこと
により樹脂目付７５ｇ／ｍ2 の樹脂フィルムを得、さら
にその上に一方向に炭素繊維を引き揃え加熱含浸するこ
とにより炭素繊維目付１４５ｇ／ｍ2 、樹脂含有率３４
％の強化繊維シートをそれぞれ得た。(Examples 1 and 2) Medium elastic high strength carbon fiber manufactured by Mitsubishi Rayon Co., Ltd .: MR-50K 12M as a reinforcing fiber.
(For the epoxy resin, those without sizing agent, for the bismaleimide resin, those without sizing agent, γ-aminopropyltriethoxysilane 0.
1% aqueous solution), as the thermosetting resin, the epoxy resin and bismaleimide resin of the composition of Table 1 are used, the epoxy resin uses methyl ethyl ketone as a solvent, the bismaleimide resin uses methylene chloride as a solvent,
Prepare a solution containing each thermosetting resin, pass the reinforcing fiber through this solution at a predetermined speed, then pass through the drying zone to remove the solvent, and wind with a heating roll to a tow width of 3.5 mm. By taking, a reinforcing fiber having a thermosetting resin with a resin content of 35% was obtained. Further, each resin is heated and stretched on a release paper to obtain a resin film having a resin weight of 75 g / m 2 , and further carbon fibers are unidirectionally aligned and heat-impregnated on the resin film to make a carbon fiber weight of 145 g / m 2. 2 , resin content 34
% Reinforcing fiber sheets were obtained respectively.
【００２５】繊維状熱可塑性樹脂としては、溶融紡糸に
より得られたナイロン１２繊維（１５０デニール／５６
フィラメント）及び市販のポリイミド（チバガイギー社
製マトリミド５２１８）を塩化メチレンに溶解し所定の
粘度に調整しこれを繊維状に押し出し溶剤を加熱蒸発す
ることにより得たポリイミド繊維（２００デニール／５
６フィラメント）をそれぞれ用意した。このようにして
得られたエポキシ樹脂及びビスマレイミド樹脂が付着し
た強化繊維及び含浸して得られた強化繊維シート並びに
繊維状熱可塑性樹脂を用い、フィラメントワインディン
グ装置と、直径１５ｃｍ長さ３０ｃｍのマンドレルを用
いて、熱硬化性樹脂が付着した強化繊維を３ｍｍ間隔で
隙間なく±４５°に巻つけ、次に表１に示す繊維状熱可
塑性樹脂をそれぞれ２ｍｍ間隔で巻つけて加熱し配置す
る操作（積層操作１）と、０°（マンドレル軸方向）方
向に上記強化繊維シートの強化繊維方向を合わせて１層
巻つけ、次ぎに繊維状熱可塑性樹脂を２ｍｍ間隔でその
上に巻つけ加熱し配置する操作（積層操作２）とを、
（積層操作１）→（積層操作２）の順に４回繰り返した
後、更に（積層操作２）→（積層操作１）の順に４回繰
り返し、最後に最外層に熱硬化性樹脂が付着した強化繊
維を９０°方向に３ｍｍ間隔で巻つけた。次いでポリエ
ステルの収縮テープでラッピングし、オートクレーブ中
でエポキシ樹脂は１７７℃、２時間、ビスマレイミド樹
脂は、１８０℃、６時間それぞれ５気圧で成型後、ポリ
エステルテープを除き、マンドレルを抜き取り、ビスマ
レイミド樹脂を用いた系はさらに熱風炉中で２３２℃で
６時間ポストキュアーすることにより円管状成型品を得
た。As the fibrous thermoplastic resin, nylon 12 fibers (150 denier / 56) obtained by melt spinning are used.
Polyimide fiber (200 denier / 5) obtained by dissolving a filament) and a commercially available polyimide (Matrimid 5218 manufactured by Ciba-Geigy Co., Ltd.) in methylene chloride, adjusting the viscosity to a predetermined value, extruding this into a fibrous state and evaporating the solvent by heating
6 filaments) were prepared. A filament winding device and a mandrel having a diameter of 15 cm and a length of 30 cm are used by using the reinforcing fibers to which the epoxy resin and the bismaleimide resin thus obtained are attached, the reinforcing fiber sheet obtained by impregnation, and the fibrous thermoplastic resin. Using the operation, the reinforcing fibers to which the thermosetting resin is adhered are wound at ± 45 ° at intervals of 3 mm without any gap, and then the fibrous thermoplastic resin shown in Table 1 is wound at intervals of 2 mm and arranged by heating ( The lamination operation 1) and the reinforcing fiber direction of the reinforcing fiber sheet are aligned in the direction of 0 ° (mandrel axis direction) to wind one layer, and then the fibrous thermoplastic resin is wound around it at 2 mm intervals and heated to be arranged. And the operation (stacking operation 2)
After repeating 4 times in the order of (laminating operation 1) → (laminating operation 2), further repeating 4 times in the order of (laminating operation 2) → (laminating operation 1), and finally strengthening with thermosetting resin attached to the outermost layer. The fibers were wound in the 90 ° direction at 3 mm intervals. Then, wrap with polyester shrink tape, mold the epoxy resin in an autoclave at 177 ° C for 2 hours, and the bismaleimide resin at 180 ° C for 6 hours at 5 atm respectively, remove the polyester tape, remove the mandrel, and remove the bismaleimide resin. The system using was further post-cured in a hot air oven at 232 ° C. for 6 hours to obtain a cylindrical molded product.
【００２６】得られた成型品を長さ２０ｃｍに切断し試
験サンプルを得た。サンプルをセットし、円管の側面方
向に、落錘荷重４．９ｋｇ、落錘先端外径９．５ｍｍ、
ノーズ７．９Ｒで、厚み当り４．５Ｊ／ｍｍの衝撃を加
え、衝撃損傷面積を超音波探傷装置により測定した。そ
の結果を表１に示す。The molded product obtained was cut into a length of 20 cm to obtain a test sample. Set the sample, and load the falling weight 4.9 kg, the falling weight tip outer diameter 9.5 mm in the side direction of the circular pipe.
An impact of 4.5 J / mm was applied with a nose of 7.9 R, and the impact damage area was measured by an ultrasonic flaw detector. The results are shown in Table 1.
【００２７】（比較例１，２）繊維状熱可塑性樹脂を使
用せずに、その他は実施例１，２と同様にして円管状成
型品を得、さらに衝撃損傷面積を評価した。その結果を
表１に示す。表１から、本発明により得られた成型品
は、損傷面積が小さく、耐衝撃性能に優れていることが
わかる。(Comparative Examples 1 and 2) Cylindrical molded articles were obtained in the same manner as in Examples 1 and 2 except that the fibrous thermoplastic resin was not used, and the impact damage area was evaluated. The results are shown in Table 1. From Table 1, it can be seen that the molded product obtained by the present invention has a small damaged area and is excellent in impact resistance.
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【発明の効果】上述の如く構成された本発明によれば、
マトリックス樹脂の優れた熱的性質及び機械的性質を損
なうことなく、優れた靭性を兼ね備えた繊維強化複合材
料を、効率良く製造することができるという効果を奏す
る。According to the present invention constructed as described above,
The fiber-reinforced composite material having excellent toughness can be efficiently produced without impairing the excellent thermal properties and mechanical properties of the matrix resin.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 杉森 正裕 愛知県名古屋市東区砂田橋四丁目１番60号 三菱レイヨン株式会社商品開発研究所内 (72)発明者 浅井 肇 愛知県名古屋市東区砂田橋四丁目１番60号 三菱レイヨン株式会社商品開発研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masahiro Sugimori Inventor, Masahiro Sugimori 4-chome, 1-chome, Sunadabashi, Higashi-ku, Nagoya, Aichi Mitsubishi Rayon Co., Ltd. Product Development Laboratory (72) Hajime Asai 4-chome, Sunadabashi, Higashi-ku, Aichi No. 60 Mitsubishi Rayon Co., Ltd. Product Development Laboratory
Claims (2)
塑性樹脂からフィラメントワインディング法で複合材料
を製造する方法において、熱硬化性樹脂を付着した強化
繊維、あるいは熱硬化性樹脂を強化繊維に含浸して得ら
れる強化繊維シートを配置し、次にその外表面に繊維状
熱可塑性樹脂を配置する工程を、積層体の最内部及び／
または内部を形成する工程に少なくとも１工程設けるこ
とを特徴とする複合材料の製造方法。1. A method for producing a composite material from a reinforcing fiber, a thermosetting resin, and a fibrous thermoplastic resin by a filament winding method, wherein a reinforcing fiber having a thermosetting resin attached thereto or a thermosetting resin is used as a reinforcing fiber. The step of disposing the reinforcing fiber sheet obtained by impregnation and then disposing the fibrous thermoplastic resin on the outer surface of
Alternatively, a method for producing a composite material is characterized in that at least one step is provided in the step of forming the inside.
可塑性樹脂による隠蔽率が８０％以下となるように一定
間隔で配置する請求項１記載の複合材料の製造方法。2. The method for producing a composite material according to claim 1, wherein the fibrous thermoplastic resin is arranged at regular intervals so that the hiding ratio of the fibrous thermoplastic resin is 80% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28353293A JP3561282B2 (en) | 1993-11-12 | 1993-11-12 | Manufacturing method of composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28353293A JP3561282B2 (en) | 1993-11-12 | 1993-11-12 | Manufacturing method of composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07137152A true JPH07137152A (en) | 1995-05-30 |
| JP3561282B2 JP3561282B2 (en) | 2004-09-02 |
Family
ID=17666755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28353293A Expired - Fee Related JP3561282B2 (en) | 1993-11-12 | 1993-11-12 | Manufacturing method of composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3561282B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11300870A (en) * | 1998-04-20 | 1999-11-02 | Mitsubishi Rayon Co Ltd | Sandwich board made of fiber reinforced plastic |
-
1993
- 1993-11-12 JP JP28353293A patent/JP3561282B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11300870A (en) * | 1998-04-20 | 1999-11-02 | Mitsubishi Rayon Co Ltd | Sandwich board made of fiber reinforced plastic |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3561282B2 (en) | 2004-09-02 |
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