JP2005126557A - Molding material for and manufacturing method of fiber-reinforced resin composite material - Google Patents
Molding material for and manufacturing method of fiber-reinforced resin composite material Download PDFInfo
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- JP2005126557A JP2005126557A JP2003363045A JP2003363045A JP2005126557A JP 2005126557 A JP2005126557 A JP 2005126557A JP 2003363045 A JP2003363045 A JP 2003363045A JP 2003363045 A JP2003363045 A JP 2003363045A JP 2005126557 A JP2005126557 A JP 2005126557A
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Abstract
Description
本発明は、穴あけや部分的な切断などの加工が容易で、かつ、表面平滑性に優れた繊維
強化樹脂複合材料（以下、ＦＲＰと言う。）用成形材料およびこの成形材料を用いたＦＲ
Ｐの製造方法に関する。
The present invention provides a molding material for a fiber reinforced resin composite material (hereinafter referred to as FRP) which is easy to process such as drilling and partial cutting and has excellent surface smoothness, and an FR using this molding material.
The present invention relates to a method for producing P.
ＦＲＰの製造方法として、プリプレグ等からなるＦＲＰ用成形材料を成形型内で加熱お
よび加圧する方法が知られている。特に、圧縮成形による製造方法は、オートクレーブ成
形や真空バッグ成形等の製造方法と比較して短時間で成形を完了できるため、工業的に有
用な方法である（例えば、特許文献１、２および３参照）。
As a method for producing FRP, a method of heating and pressurizing a molding material for FRP made of prepreg or the like in a molding die is known. In particular, the production method by compression molding is an industrially useful method because the molding can be completed in a short time compared to a production method such as autoclave molding or vacuum bag molding (for example, Patent Documents 1, 2, and 3). reference).
ところで、圧縮成形に限らず、ＦＲＰを製造した後に、他の成形品との接合部を作るな
どの目的で、その表面に穴あけや部分的な切断などの加工を施す場合がある。この場合、
ＦＲＰ表面の強化繊維が一方向に引き揃えられていると、加工時に切断された強化繊維が
剥離し、ささくれ立って、外観表面が悪くなるという問題があった。
一方、ＦＲＰ表面を強化繊維織物で構成すると、一方向に引き揃えられている場合に比
べてささくれなどが生じづらくなる。そこで、穴あけや部分的な切断などの加工を施す必
要があるＦＲＰを製造する場合には、表面ＦＲＰ用成形材料として強化繊維織物プリプレ
グを用いることが多い。
By the way, it is not limited to compression molding, and after manufacturing FRP, the surface may be subjected to processing such as drilling or partial cutting for the purpose of making a joint with another molded product. in this case,
When the reinforcing fibers on the surface of the FRP are aligned in one direction, the reinforcing fibers cut at the time of processing are peeled off and fluttered, resulting in a problem that the appearance surface is deteriorated.
On the other hand, when the FRP surface is composed of a reinforced fiber fabric, it is difficult to produce a backlash or the like as compared with a case where the FRP surface is aligned in one direction. Therefore, when manufacturing FRP that requires processing such as drilling and partial cutting, a reinforced fiber woven prepreg is often used as a molding material for surface FRP.
しかし、表面に強化繊維織物プリプレグを用いて圧縮成形によりＦＲＰを製造すると、
強化繊維織物の織組織の凹凸がそのままＦＲＰの表面に現れるため、ＦＲＰ表面の平滑性
が悪くなる原因となっていた。そのため、外観の表面平滑性が求められる、自動車や鉄道
車輌の外装材等で、穴あけや部分的な切断などの加工が必要な場合は、圧縮成形でＦＲＰ
を製造することは困難であった。
The unevenness of the woven structure of the reinforcing fiber fabric appears as it is on the surface of the FRP, which causes the smoothness of the FRP surface to deteriorate. Therefore, if processing such as drilling or partial cutting is required for exterior materials of automobiles and railway vehicles where surface smoothness of the exterior is required, FRP is used for compression molding.
It was difficult to manufacture.
本発明の課題は、穴あけや部分的切断といった加工後の外観がよく、表面平滑性に優れ
たＦＲＰを圧縮成形により得ることである。
An object of the present invention is to obtain an FRP having a good appearance after processing such as drilling and partial cutting and excellent in surface smoothness by compression molding.
本発明の要旨は、少なくとも成形後に表面平滑性が要求される部分に、目付が１６０ｇ
／ｍ２以下、開口率が４％以下の強化繊維織物と熱硬化性樹脂組成物とからなるプリプレ
グを配置したＦＲＰ用成形材料、および、この成形材料を圧縮成形するＦＲＰの製造方法
である。
The gist of the present invention is that the basis weight is 160 g at least in a portion where surface smoothness is required after molding.
This is a molding material for FRP in which a prepreg composed of a reinforcing fiber woven fabric having a / m 2 or less and an opening ratio of 4% or less and a thermosetting resin composition is disposed, and a method for producing FRP by compression molding the molding material.
本発明のＦＲＰ用成形材料を用いることで、表面平滑性に優れ、かつ、部分的切断や穴
あけなどの穴あけや部分的切断などの加工後の外観がよくＦＲＰを圧縮成形により得るこ
とができる。
By using the molding material for FRP of the present invention, the surface smoothness is excellent, and the appearance after processing such as drilling or partial cutting such as partial cutting or drilling is good, and FRP can be obtained by compression molding.
以下では、本発明のＦＲＰ用成形材料について説明する。 Below, the molding material for FRP of this invention is demonstrated.
本発明のＦＲＰ用成形材料は、少なくとも成形後に表面平滑性が要求される部分に、目
付が１６０ｇ／ｍ２以下、開口率が４％以下の強化繊維織物と熱硬化性樹脂組成物とから
なるプリプレグを配置したものである。
The molding material for FRP of the present invention comprises a reinforced fiber fabric having a basis weight of 160 g / m 2 or less and an aperture ratio of 4% or less and a thermosetting resin composition at least in a portion where surface smoothness is required after molding. A prepreg is arranged.
（強化繊維織物）
強化繊維織物は、平織、綾織、簾織、朱子織など、いかなる織組織の強化繊維織物であ
ってもよい。
強化繊維織物を構成する強化繊維の種類も特に制限はない。例えば、炭素繊維、アラミ
ド繊維、ボロン繊維、スチール繊維、ＰＢＯ繊維、高強度ポリエチレン繊維、ガラス繊維
などが例示できる。また、強化繊維織物中に、これらの強化繊維を複数種用いてもよい。
(Reinforced fiber fabric)
The reinforcing fiber woven fabric may be a reinforcing fiber woven fabric having any woven structure such as plain weave, twill weave, silk weave and satin weave.
There is also no particular limitation on the type of reinforcing fiber constituting the reinforcing fiber fabric. Examples thereof include carbon fiber, aramid fiber, boron fiber, steel fiber, PBO fiber, high-strength polyethylene fiber, and glass fiber. In addition, a plurality of these reinforcing fibers may be used in the reinforcing fiber fabric.
特に、炭素繊維は比強度および比弾性に優れるので好ましい。アラミド繊維や高強度ポ
リエチレン繊維などの高強度有機繊維は、ＦＲＰに耐衝撃性が付与されるので好ましい。
ガラス繊維を用いると、これら強化繊維の中で比較的安価なわりに強度に優れるので好ま
しい。
In particular, carbon fiber is preferable because it is excellent in specific strength and specific elasticity. High-strength organic fibers such as aramid fibers and high-strength polyethylene fibers are preferable because impact resistance is imparted to the FRP.
It is preferable to use glass fibers because these reinforcing fibers are relatively inexpensive and excellent in strength.
本発明は、目付が１６０ｇ／ｍ２以下の強化繊維織物を用いることを特徴としている。 The present invention is characterized by using a reinforcing fiber fabric having a basis weight of 160 g / m 2 or less.
先に述べたように、ＦＲＰ表面の強化繊維が織物を構成していると強化繊維織物の織組
織の凹凸がＦＲＰ表面に現れることがある。よって、かかる問題を解決するために、織組
織の凹凸ができるだけ小さい強化繊維織物を用いるとよい。
As described above, when the reinforcing fibers on the FRP surface constitute a woven fabric, irregularities of the woven structure of the reinforcing fiber woven fabric may appear on the FRP surface. Therefore, in order to solve such a problem, it is preferable to use a reinforced fiber fabric in which the unevenness of the woven structure is as small as possible.
そこで、本発明では、目付の低い強化繊維織物を用いることで、強化繊維織物の織組織
の凹凸を小さくすることで、より表面平滑性の高いＦＲＰが得られることを見出したので
ある。特に、目付を１６０ｇ／ｍ２以下とすると、成形後に表面平滑性が要求される部分
の表面中心線平均粗さ（Ｒａ）が０．５μｍ以下とすることができる。さらに、目付を１
４０ｇ／ｍ２とするとＲａを０．４μｍ以下とすることができるので好ましい。目付の下
限値は特に限定されないが、目付が１００ｇ／ｍ２未満の強化繊維織物は、織組織が粗に
なりすぎて扱いが難しいので、目付を１００ｇ／ｍ２以上とすることが好ましい。
Therefore, the present invention has found that FRP with higher surface smoothness can be obtained by reducing the unevenness of the woven structure of the reinforcing fiber fabric by using the reinforcing fiber fabric having a low basis weight. In particular, when the basis weight is 160 g / m 2 or less, the surface centerline average roughness (Ra) of the portion where surface smoothness is required after molding can be 0.5 μm or less. Furthermore, the basis weight is 1
When it is 40 g / m 2 , Ra can be 0.4 μm or less, which is preferable. The lower limit value of the basis weight is not particularly limited, but the reinforcing fiber woven fabric having a basis weight of less than 100 g / m 2 is difficult to handle because the woven structure becomes too rough, and thus the basis weight is preferably set to 100 g / m 2 or more.
また、本発明のプリプレグに用いる強化繊維織物の開口率は４％以下ことが必要である
。開口率を小さくすることで、より織組織の凹凸の少ない強化繊維織物となるからである
。特に２％以下であると、強化繊維織物の表面が平滑であるので好ましい。
The opening ratio of the reinforcing fiber fabric used for the prepreg of the present invention is required to be 4% or less. This is because by reducing the aperture ratio, a reinforced fiber fabric with less unevenness in the woven structure is obtained. In particular, 2% or less is preferable because the surface of the reinforcing fiber fabric is smooth.
開口率は、強化繊維織物の表面上に面積Ｓ１の領域を設定し、面積Ｓ１内において強化
繊維の開口部の全面積をＳ２としたときの、次式で定義される値Ｘ（％）である。
Ｘ（％）＝（Ｓ１／Ｓ２）×１００
強化繊維織物の開口部の全面積Ｓ２は、強化繊維織物の下部から光を透過し、その光の
透過部分を画像処理センサーを用いて画像処理することにより測定することができる。
The opening ratio is a value X (%) defined by the following equation when a region of area S1 is set on the surface of the reinforcing fiber fabric, and the total area of the openings of the reinforcing fibers in the area S1 is S2. is there.
X (%) = (S1 / S2) × 100
The total area S2 of the opening portion of the reinforcing fiber fabric can be measured by transmitting light from the lower portion of the reinforcing fiber fabric and subjecting the light transmission portion to image processing using an image processing sensor.
開口率が４％以下の強化繊維織物を得るための方法として、強化繊維に開繊処理を施し
て、その開口率を４％以下としても構わない。
強化繊維織物に対する開繊処理の方法は、いかなる方法も用いることができる。例えば
、鋼球で強化繊維織物表面に鋼球を衝突させる方法、強化繊維織物表面を梨地表面で擦過
する方法、強化繊維織物表面に水やエアを吹きつける方法、強化繊維織物表面にローラー
等で振動を与える方法、静電気開繊による方法、超音波開繊による方法などが挙げられる
。特に、鋼球で強化繊維織物表面に鋼球を衝突させる方法は、開繊後の乾燥などの後処理
が不要であるので好ましい。
As a method for obtaining a reinforced fiber woven fabric having an opening ratio of 4% or less, the opening ratio may be set to 4% or less by applying a fiber opening treatment to the reinforcing fibers.
Any method can be used as a method for the fiber opening treatment of the reinforcing fiber fabric. For example, a method in which a steel ball collides with the surface of a reinforcing fiber fabric with a steel ball, a method of rubbing the surface of the reinforcing fiber fabric with a satin surface, a method of spraying water or air on the surface of the reinforcing fiber fabric, a roller or the like on the surface of the reinforcing fiber fabric Examples include a method of applying vibration, a method of electrostatic opening, and a method of ultrasonic opening. In particular, the method of causing the steel ball to collide with the surface of the reinforcing fiber fabric with the steel ball is preferable because post-treatment such as drying after the fiber opening is unnecessary.
（熱硬化性樹脂組成物）
プリプレグに用いる熱硬化性樹脂組成物の種類は特に制限はなく、エポキシ樹脂、フェ
ノール樹脂、不飽和ビニルエステル樹脂、不飽和ポリエステル樹脂、ビスマレイミド樹脂
、ＢＴ樹脂、シアネートエステル樹脂、ベンゾオキサジン樹脂などを主成分とする熱硬化
性樹脂組成物のいずれも好適の用いることができる。
(Thermosetting resin composition)
The type of thermosetting resin composition used for the prepreg is not particularly limited, and includes epoxy resin, phenol resin, unsaturated vinyl ester resin, unsaturated polyester resin, bismaleimide resin, BT resin, cyanate ester resin, benzoxazine resin, etc. Any thermosetting resin composition having a main component can be preferably used.
特に、エポキシ樹脂は、強化繊維との接着性が良いので、強度に優れたＦＲＰを得る場
合に特に好ましく用いることができる。エポキシ樹脂の種類としては、例えば、２官能性
エポキシ樹脂では、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂
、ビスフェノールＳ型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ
樹脂、ジシクロペンタジエン型エポキシ樹脂、フルオレン型エポキシ樹脂およびこれらい
ずれかを変性したエポキシ樹脂等を、３官能以上の多官能性エポキシ樹脂では、フェノー
ルノボラック型エポキシ樹脂、クレゾール型エポキシ樹脂、テトラグリシジルジアミノジ
フェニルメタン、トリグリシジルアミノフェノール、テトラグリシジルアミンのようなグ
リシジルアミン型エポキシ樹脂、テトラキス（グリシジルオキシフェニル）エタンやトリ
ス（グリシジルオキシメタン）のようなグリシジルエーテル型エポキシ樹脂およびこれら
いずれかを変性したエポキシ樹脂をいずれも好適に用いることができる。
In particular, the epoxy resin has good adhesion to the reinforcing fiber, and can be particularly preferably used when obtaining FRP having excellent strength. Examples of the types of epoxy resins include bifunctional epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins. , Fluorene type epoxy resins and epoxy resins modified with any of these are used in polyfunctional epoxy resins having three or more functional groups, such as phenol novolac type epoxy resins, cresol type epoxy resins, tetraglycidyl diaminodiphenylmethane, triglycidyl aminophenol, tetra Glycidylamine type epoxy resin such as glycidylamine, glycidyl ether type epoxy such as tetrakis (glycidyloxyphenyl) ethane and tris (glycidyloxymethane) Both the resin and these either the modified epoxy resin can be suitably used.
エポキシ樹脂組成物として、エポキシ樹脂と分子内に硫黄原子を含む硬化剤とを併用す
ると、エポキシ樹脂の効果速度を速める傾向があるため、短時間で成形が完了するので好
ましい。特に、分子内の硫黄原子含有率が７質量％以上とするとより好ましい。
分子内に硫黄原子を含む硬化剤の例としては、４，４’−ジアミノジフェニルスルフォ
ン、ジアミノジフェニルスルファイド、ビス（４−（４アミノフェノキシ）フェニル）ス
ルフォン、ビス（４−（３アミノフェノキシ）フェニル）スルフォン、４，４’−ジアミ
ノジフェニルスルファイド、o−トリアジンスルフォン、などが挙げられる。
When an epoxy resin and a curing agent containing a sulfur atom in the molecule are used in combination as the epoxy resin composition, the effect speed of the epoxy resin tends to be increased, and thus molding is completed in a short time. In particular, the sulfur atom content in the molecule is more preferably 7% by mass or more.
Examples of curing agents containing a sulfur atom in the molecule include 4,4′-diaminodiphenylsulfone, diaminodiphenylsulfide, bis (4- (4aminophenoxy) phenyl) sulfone, and bis (4- (3aminophenoxy). Phenyl) sulfone, 4,4′-diaminodiphenyl sulfide, o-triazine sulfone, and the like.
また、熱硬化性樹脂組成物には、硬化剤の他にも、３−（３，４−ジクロロフェニル−
１，１−ジメチルウレア（ＤＣＭＵ）や３−フェニル−Ｎ，Ｎ−ジメチルウレア（ＰＤＭ
Ｕ）などの尿素化合物やジシアンジアミドなどのアミン化合物といった硬化助剤、ポリビ
ニルフォルマールやフェノキシ樹脂といった熱可塑性樹脂、金属酸化物や金属水酸化物と
いった難燃剤を加えることもできる。
In addition to the curing agent, the thermosetting resin composition includes 3- (3,4-dichlorophenyl-
1,1-dimethylurea (DCMU) or 3-phenyl-N, N-dimethylurea (PDM)
Curing aids such as urea compounds such as U) and amine compounds such as dicyandiamide, thermoplastic resins such as polyvinyl formal and phenoxy resins, and flame retardants such as metal oxides and metal hydroxides can also be added.
（ＦＲＰ用成形材料）
本発明のＦＲＰ用成形材料の、成形後に表面平滑性が要求される部分の表面に配置した
、強化繊維織物と熱硬化性樹脂組成物とからなるプリプレグ以外の部分（以下、基材とい
う。）は、いかなるものを用いてもよいが、特に、強化繊維と熱硬化性樹脂組成物からな
っているとＦＲＰとしたときの強度の向上が見込めるので好ましい。
基材に用いる強化繊維の種類は特に制限はなく、炭素繊維、アラミド繊維、ボロン繊維
、スチール繊維、ＰＢＯ繊維、高強度ポリエチレン繊維、ガラス繊維などが例示できる。
また、基材に用いる熱硬化性樹脂組成物の種類にも特に制限はなく、エポキシ樹脂、フェ
ノール樹脂、不飽和ビニルエステル樹脂、不飽和ポリエステル樹脂、ビスマレイミド樹脂
、ＢＴ樹脂、シアネートエステル樹脂、ベンゾオキサジン樹脂などを主成分とする熱硬化
性樹脂組成物が例として挙げられる。
基材の形状も、いかなる形態であってよい。例えば、一方向プリプレグ、織物プリプレ
グ、シートモールディングコンパウンド、またはこれらの組み合わせいずれであってもよ
い。
本発明でいう、成形後に表面平滑性が要求される部分の表面とは、ＦＲＰ用成形材料の
表面全体であっても、表面の一部分であってもよく、製造するＦＲＰの用途に応じて決定
できる。
(FRP molding material)
The part other than the prepreg composed of the reinforcing fiber fabric and the thermosetting resin composition (hereinafter referred to as the base material) disposed on the surface of the part requiring surface smoothness after molding of the molding material for FRP of the present invention. Any material may be used, but it is particularly preferable that it is composed of a reinforcing fiber and a thermosetting resin composition since strength improvement can be expected when FRP is used.
The type of reinforcing fiber used for the substrate is not particularly limited, and examples thereof include carbon fiber, aramid fiber, boron fiber, steel fiber, PBO fiber, high-strength polyethylene fiber, and glass fiber.
Further, the type of thermosetting resin composition used for the substrate is not particularly limited, and epoxy resin, phenol resin, unsaturated vinyl ester resin, unsaturated polyester resin, bismaleimide resin, BT resin, cyanate ester resin, benzo An example is a thermosetting resin composition mainly composed of an oxazine resin.
The shape of the substrate may be any form. For example, the unidirectional prepreg, the woven prepreg, the sheet molding compound, or a combination thereof may be used.
In the present invention, the surface of the portion requiring surface smoothness after molding may be the entire surface of the molding material for FRP or a part of the surface, and is determined according to the use of the FRP to be manufactured. it can.
（ＦＲＰの製造方法）
このようなＦＲＰ用成形材料を圧縮成形して、熱硬化性樹脂組成物を硬化することによ
り、本発明のＦＲＰを製造することができる。本発明の圧縮成形の条件は、ＦＲＰ用成形
材料の熱硬化性樹脂組成物の、種類や含有率等によって適宜決定できる。特に、短時間で
成形を完了したい場合は、成形型の温度をあらかじめ１２０℃以上に調温してからＦＲＰ
用成形材料を成形型内に配置し、成形型の温度を保ったまま型締めして、２ＭＰａ以上の
圧力で成形すると、成形が短時間で終了する。中でも、成形条件を、成形型の温度を１４
０℃以上、成形圧力８ＭＰａとすると５分以内での成形が可能となる。
(FRP manufacturing method)
The FRP of the present invention can be produced by compression-molding such a molding material for FRP and curing the thermosetting resin composition. The compression molding conditions of the present invention can be appropriately determined depending on the type and content of the thermosetting resin composition of the FRP molding material. In particular, if you want to complete the molding in a short time, adjust the temperature of the mold in advance to 120 ° C or higher before FRP
When the molding material is placed in a mold, the mold is clamped while maintaining the temperature of the mold, and molding is performed at a pressure of 2 MPa or more, the molding is completed in a short time. Among them, the molding conditions were set at a mold temperature of 14
If the temperature is 0 ° C. or higher and the molding pressure is 8 MPa, molding within 5 minutes becomes possible.
以下、実施例および比較例により本発明をさらに詳しく説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
＜熱硬化性樹脂組成物＞
本実施例では、熱硬化性樹脂組成物として、以下の成分を、均一になるまで８０℃で混
合して得られるエポキシ樹脂組成物を用いた。
・エピコート８２８（ビスフェノールＡ型エポキシ樹脂（室温で液状）、ジャパンエポキ
シレジン(株)製）５０重量部、
・エピコート１００９（ビスフェノールＡ型エポキシ樹脂（室温で固体）、ジャパンエポ
キシレジン(株)製）５０質量部、
・セイカキュアＳ（４，４’−ジアミノジメチルスルフォン、和歌山精化（株）製）１０
質量部
・オミキュア９４（３−フェニル−１，１−ジメチルウレア、ＰＴＩジャパン（株））５
質量部
・ＤＩＣＹ１５（ジシアンジアミド、ジャパンエポキシレジン(株)製）５質量部
<Thermosetting resin composition>
In this example, an epoxy resin composition obtained by mixing the following components at 80 ° C. until uniform was used as the thermosetting resin composition.
・ Epicoat 828 (bisphenol A type epoxy resin (liquid at room temperature), Japan Epoxy Resin Co., Ltd.) 50 parts by weight,
・ Epicoat 1009 (bisphenol A type epoxy resin (solid at room temperature), manufactured by Japan Epoxy Resins Co., Ltd.) 50 parts by mass,
Seikacure S (4,4′-diaminodimethylsulfone, manufactured by Wakayama Seika Co., Ltd.) 10
Part by mass / Omicure 94 (3-phenyl-1,1-dimethylurea, PTI Japan Ltd.) 5
Mass part · DICY15 (Dicyandiamide, manufactured by Japan Epoxy Resin Co., Ltd.) 5 parts by mass
＜強化繊維織物の製造＞
三菱レイヨン（株）製炭素繊維ＴＲ３０Ｓ（フィラメント数３０００本）をたて糸およ
びよこ糸として、津田駒製のレピア織機を用いて平織の強化繊維織物を製織した。以下の
実施例では、表１に記載したとおりの目付である、異なる４種類の強化繊維織物Ａ、Ｂ、
ＣおよびＤを得た。
<Manufacture of reinforced fiber fabric>
A plain fiber reinforced fiber fabric was woven using a rapier loom made by Tsuda Koma using Mitsubishi Rayon Co., Ltd. carbon fiber TR30S (3,000 filaments) as warp and weft. In the following examples, four different types of reinforcing fiber fabrics A, B, having a basis weight as described in Table 1,
C and D were obtained.
＜開口率の測定＞
強化繊維織物の開口率の測定は以下のようにして行った。まず（株）キーエンス製、一
方から光を当てた強化繊維織物表面の様子を画像処理装置ＣＶ−１００を用いて画像処理
することにより、強化繊維織物の１００ｍｍ２あたりの開口部の全面積Ｓ２（ｍｍ２）を
測定し、このＳ２を式（１）に代入して開口率Ｘを算出した。
Ｘ（％）＝（Ｓ２（ｍｍ２）／１００（ｍｍ２））×１００…（１）
この方法で測定した、強化繊維織物Ａ〜Ｄそれぞれの開口率を表１に示した。
<Measurement of aperture ratio>
The aperture ratio of the reinforcing fiber fabric was measured as follows. First, an entire area S2 of the opening per 100 mm 2 of the reinforcing fiber fabric is obtained by performing image processing on the surface of the reinforcing fiber fabric, which is manufactured by Keyence Co., Ltd., using the image processing apparatus CV-100. mm 2 ) was measured, and the aperture ratio X was calculated by substituting S2 into the equation (1).
X (%) = (S2 (mm 2 ) / 100 (mm 2 )) × 100 (1)
The opening ratios of the reinforcing fiber fabrics A to D measured by this method are shown in Table 1.
＜表面中心線平均粗さ（Ｒａ）の測定＞
表面中心線平均粗さ（Ｒａ）の測定は、（株）ミツトヨ製サーフテスターを用いて測定
した。カットオフ値０．８ｍｍ、測定長さ２．４ｍｍの測定条件でＦＲＰの表面の中心３
ヶ所について測定し、この３ヶ所の測定地の平均として算出した。
＜実施例１＞
<Measurement of surface centerline average roughness (Ra)>
The surface centerline average roughness (Ra) was measured using a Mitutoyo Surf Tester. The center 3 of the surface of the FRP under the measurement conditions of a cut-off value of 0.8 mm and a measurement length of 2.4 mm
Measurements were taken at the three locations and calculated as the average of these three locations.
<Example 1>
まず、強化繊維織物Ａの開繊処理を鋼球衝突開繊装置（鋼球の速度：１ｍｍ／分）を用
いて行った。開繊処理は、強化繊維織物Ａに１５０℃の熱風を付与しながら、鋼球を強化
繊維織物Ａに衝突させることにより行った。次に、開繊処理を施した強化繊維織物Ａ（開
口率２．９％）に、エポキシ樹脂組成物を樹脂フィルム状にしたものを７５℃に加熱した
２対の加熱ロールを用いて含浸して、プリプレグ中のエポキシ樹脂組成物の含有率が４０
％の織物プリプレグを得た。
一方、エポキシ樹脂組成物の樹脂フィルムを、三菱レイヨン（株）製炭素繊維ＴＲ５０
Ｓを繊維目付２５０ｇ／ｍ２で一方向に引き揃えたシートに、７５℃に加熱した２対の加
熱ロールを用いて含浸して、樹脂含有率３０％の一方向プリプレグを製造した。そして、
この一方向プリプレグを３００ｍｍ×３００ｍｍに切りそろえたものを、第一層の繊維配
向が０°方向、次の層が９０°方向となるように交互に重ねて９プライ積層して積層体と
した。さらに、この積層体の片面に織物プリプレグを貼り合わせて本発明のＦＲＰ用成形
材料を得た。
First, the opening treatment of the reinforcing fiber fabric A was performed using a steel ball collision opening device (steel ball speed: 1 mm / min). The fiber opening treatment was performed by causing a steel ball to collide with the reinforcing fiber fabric A while applying 150 ° C. hot air to the reinforcing fiber fabric A. Next, the reinforcing fiber fabric A (opening ratio: 2.9%) subjected to the fiber opening treatment is impregnated with two pairs of heating rolls heated to 75 ° C. in the form of a resin film of the epoxy resin composition. The content of the epoxy resin composition in the prepreg is 40
% Woven prepreg was obtained.
On the other hand, the resin film of the epoxy resin composition is carbon fiber TR50 manufactured by Mitsubishi Rayon Co., Ltd.
A sheet in which S was aligned in one direction with a fiber basis weight of 250 g / m 2 was impregnated using two pairs of heating rolls heated to 75 ° C. to produce a unidirectional prepreg with a resin content of 30%. And
The unidirectional prepregs cut to 300 mm × 300 mm were alternately stacked so that the fiber orientation of the first layer was in the 0 ° direction and the next layer was in the 90 ° direction, thereby laminating 9 plies to obtain a laminate. Further, a woven fabric prepreg was bonded to one side of the laminate to obtain the FRP molding material of the present invention.
このＦＲＰ用成形材料を、予め成形型の温度を１４０℃に調温した上型と下型とからな
る成形型内に配置した。ＦＲＰ用成形材料を配置した後すぐに、上型を降ろして成形型を
締め、ＦＲＰ用成形材料に８ＭＰａの圧力を５分間かけた後、型開きを行い、成形型の温
度を１４０℃に保ったまま、成形型に備え付けられたイジェクタピンを用いて、縦３００
ｍｍ、横３００ｍｍ、厚さ２．２ｍｍの平板状のＦＲＰを取り出した。このＦＲＰについ
て目視による外観検査を行ったところ、表面外観が鮮明であった。また、このＦＲＰのＲ
ａは０．３１μｍであり、非常に平滑なものが得られた。
＜実施例２＞
This molding material for FRP was placed in a molding die composed of an upper die and a lower die whose temperature was adjusted to 140 ° C. in advance. Immediately after placing the molding material for FRP, the upper die is lowered and the molding die is tightened. After applying a pressure of 8 MPa to the molding material for FRP for 5 minutes, the mold is opened and the temperature of the molding die is maintained at 140 ° C. While using the ejector pin provided in the mold,
A flat plate-shaped FRP having a thickness of 300 mm, a width of 300 mm, and a thickness of 2.2 mm was taken out. When this FRP was visually inspected, the surface appearance was clear. The R of this FRP
a was 0.31 μm, and a very smooth product was obtained.
<Example 2>
強化繊維織物を強化繊維織物Ｂに変更した以外は、実施例１と同様にしてＦＲＰを得た
。なお、開繊処理を施した強化繊維織物Ｂの開口率は２％であった。
このＦＲＰについて目視による外観検査を行ったところ、表面外観が鮮明なＦＲＰであ
った。また、このＦＲＰのＲａは０．３６μｍであり平滑なものが得られた。
＜実施例３＞
FRP was obtained in the same manner as in Example 1 except that the reinforcing fiber fabric was changed to the reinforcing fiber fabric B. The opening ratio of the reinforcing fiber fabric B subjected to the fiber opening treatment was 2%.
When this FRP was visually inspected, the surface appearance was clear. Further, Ra of this FRP was 0.36 μm, and a smooth one was obtained.
<Example 3>
強化繊維織物を、強化繊維織物Ｃに変更した以外は、実施例１と同様にしてＦＲＰを得
た。なお、開繊処理を施した強化繊維織物Ｃの開口率は、０．０２％であった。
このＦＲＰについて目視による外観検査を行ったところ、表面外観が鮮明なＦＲＰであ
った。また、このＦＲＰのＲａは０．４０μｍであり、平滑なものが得られた。
＜比較例１＞
FRP was obtained in the same manner as in Example 1 except that the reinforcing fiber fabric was changed to the reinforcing fiber fabric C. The opening ratio of the reinforcing fiber fabric C subjected to the fiber opening treatment was 0.02%.
When this FRP was visually inspected, the surface appearance was clear. Moreover, Ra of this FRP was 0.40 μm, and a smooth one was obtained.
<Comparative Example 1>
強化繊維織物を、強化繊維織物Ｄに変更した以外は、実施例１と同様にしてＦＲＰを得
た。なお、開繊処理を施した強化繊維織物Ｄの開口率は０．０１％であった。
このＦＲＰのＲａは０．５５μｍと各実施例で得られた成形品より粗く、目視による外
観検査でもスジ状の欠点も見られた。
＜比較例２＞
FRP was obtained in the same manner as in Example 1 except that the reinforcing fiber fabric was changed to the reinforcing fiber fabric D. The opening ratio of the reinforcing fiber fabric D subjected to the fiber opening treatment was 0.01%.
The Ra of FRP was 0.55 μm, which was coarser than the molded product obtained in each example, and streaky defects were also observed in visual inspection.
<Comparative example 2>
強化繊維織物Ｃに開繊処理を施さずに用いた以外は、実施例３と同様にしてＦＲＰを得
た。なお、開繊処理を施した強化繊維織物Ｃの開口率は、５％であった。このＦＲＰにつ
いて目視による外観検査を行ったところ、わずかに表面外観に欠点が発生した。また、こ
のＦＲＰの平均表面粗さＲａは、０．４７μｍであった。
FRP was obtained in the same manner as in Example 3 except that the reinforcing fiber fabric C was used without being subjected to fiber opening treatment. The opening ratio of the reinforcing fiber fabric C subjected to the fiber opening treatment was 5%. When visual inspection was performed on this FRP, a slight defect occurred in the surface appearance. The average surface roughness Ra of the FRP was 0.47 μm.
本発明の製造方法で得られるＦＲＰは、表面平滑性に優れるので、平滑性が求められか
つ表面に加工が必要な部材に用いることができる。具体的には、オートバイフレーム、カ
ウル、フェンダー等の二輪車用途、ドア、ボンネット、テールゲート、サイドフェンダー
、側面パネル、フェンダー、エネルギー吸収部材、トランクリッド、ハードップ、サイド
ミラーカバー、スポイラー、ディフューザー、スキーキャリアー、エンジンシリンダーカ
バー、エンジンフード、シャシー、エアースポイラー、プロペラシャフト等の自動車部品
用途や、先頭車両ノーズ、ルーフ、サイドパネル、ドア、台車カバー、側スカートなどの
車輌用外板用途、荷物棚、座席等の鉄道車輌用途、インテリア、ウイングトラックにおけ
るウイングのインナーパネル、アウターパネル、ルーフ、フロアー等、自動車や単車に装
着するやサイドスカート、などのエアロパーツ用途や、窓枠、荷物棚、座席、フロアパネ
ル、翼、プロペラ、胴体等の航空機用途、ノートパソコン、携帯電話等の筐体用途、フラ
ットスピーカーパネル、スピーカーコーン等の音響製品用途、ゴルフヘッド、フェースプ
レート、スノーボード、サーフィンボード、プロテクター等のスポーツ用品用途が挙げら
れる。
Since FRP obtained by the production method of the present invention is excellent in surface smoothness, it can be used for a member that requires smoothness and requires processing on the surface. Specifically, motorcycle frames, cowls, fenders and other motorcycles, doors, bonnets, tailgates, side fenders, side panels, fenders, energy absorbing members, trunk lids, hardtops, side mirror covers, spoilers, diffusers, ski carriers , Engine cylinder covers, engine hoods, chassis, air spoilers, propeller shafts and other automotive parts applications, leading vehicle noses, roofs, side panels, doors, bogie covers, side skirts and other vehicle skins, luggage racks, seats Such as railway vehicles, interiors, wing inner panels, outer panels, roofs, floors, aero parts such as side skirts for automobiles and motorcycles, window frames, luggage racks, seats, Air panels, wings, propellers, fuselage aircraft applications, notebook PCs, mobile phone case applications, flat speaker panels, speaker cones and other acoustic product applications, golf heads, faceplates, snowboards, surf boards, protector sports Goods use is mentioned.
Claims (6)
、開口率が４％以下の強化繊維織物と熱硬化性樹脂組成物とからなるプリプレグを配置し
た繊維強化樹脂複合材料用成形材料。 A fiber reinforced resin in which a prepreg composed of a reinforced fiber fabric having a basis weight of 160 g / m 2 or less and an aperture ratio of 4% or less and a thermosetting resin composition is disposed at least on the surface of a portion requiring surface smoothness after molding. Molding material for composite materials.
なる群から選ばれる少なくとも一種類以上の強化繊維である請求項１記載の繊維強化樹脂
複合材料用成形材料。 The molding material for fiber-reinforced resin composite material according to claim 1, wherein the reinforcing fiber is at least one kind of reinforcing fiber selected from the group consisting of carbon fiber, glass fiber, aramid fiber and high-strength polyethylene fiber.
脂複合材料用成形材料。 The molding material for fiber-reinforced resin composite materials according to claim 1 or 2, wherein the thermosetting resin composition is an epoxy resin composition.
ポキシ樹脂組成物である、請求項３記載の繊維強化樹脂複合材料用成形材料。 The molding material for fiber reinforced resin composite materials according to claim 3, wherein the epoxy resin composition is an epoxy resin composition containing an epoxy resin and a curing agent having a sulfur atom in the molecule.
硬化性樹脂組成物を硬化する繊維強化樹脂複合材料の製造方法。 The manufacturing method of the fiber reinforced resin composite material which compression-molds the molding material for fiber reinforced resin composite materials as described in any one of Claims 1-4, and hardens | cures a thermosetting resin composition.
を配置し、型締めして繊維強化樹脂複合材料用成形材料に２ＭＰａ以上の圧力をかける圧
縮成形である請求項５記載の繊維強化樹脂複合材料の製造方法。 Compression molding is a compression molding in which a molding material for fiber reinforced resin composite material is placed in a mold that has been conditioned to 120 ° C or higher in advance, and the mold is clamped to apply a pressure of 2 MPa or more to the molding material for fiber reinforced resin composite material. A method for producing a fiber-reinforced resin composite material according to claim 5.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003363045A JP2005126557A (en) | 2003-10-23 | 2003-10-23 | Molding material for and manufacturing method of fiber-reinforced resin composite material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003363045A JP2005126557A (en) | 2003-10-23 | 2003-10-23 | Molding material for and manufacturing method of fiber-reinforced resin composite material |
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|---|---|
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Family
ID=34642480
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007061044A1 (en) | 2005-11-25 | 2007-05-31 | Hamamatsu Foundation For Science And Technology Promotion | Ultrasonic vibration machining method and fiber reinforced resin produced by said method |
| JP2007224269A (en) * | 2006-01-27 | 2007-09-06 | Shin Kobe Electric Mach Co Ltd | Prepreg for heat- and press-molding, and laminated board |
| JP2009510207A (en) * | 2005-09-30 | 2009-03-12 | エアバス エスパーニャ、ソシエダ リミタダ | Surface treatment of composite structures by atmospheric pressure plasma beam |
| US8152421B2 (en) | 2007-05-18 | 2012-04-10 | Hukuzo Yagishita | Apparatus and method for drilling a work |
| JP2013213710A (en) * | 2012-04-02 | 2013-10-17 | Kawasaki Heavy Ind Ltd | Minute crack sensor of concrete |
| KR20180056454A (en) * | 2016-11-18 | 2018-05-29 | 재단법인 한국탄소융합기술원 | Method for manufacturing carbon fiber reinforced plastic roof rail |
-
2003
- 2003-10-23 JP JP2003363045A patent/JP2005126557A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009510207A (en) * | 2005-09-30 | 2009-03-12 | エアバス エスパーニャ、ソシエダ リミタダ | Surface treatment of composite structures by atmospheric pressure plasma beam |
| WO2007061044A1 (en) | 2005-11-25 | 2007-05-31 | Hamamatsu Foundation For Science And Technology Promotion | Ultrasonic vibration machining method and fiber reinforced resin produced by said method |
| JP2007224269A (en) * | 2006-01-27 | 2007-09-06 | Shin Kobe Electric Mach Co Ltd | Prepreg for heat- and press-molding, and laminated board |
| US8152421B2 (en) | 2007-05-18 | 2012-04-10 | Hukuzo Yagishita | Apparatus and method for drilling a work |
| USRE45948E1 (en) | 2007-05-18 | 2016-03-29 | Hukuzo Yagishita | Apparatus and method for drilling a work |
| JP2013213710A (en) * | 2012-04-02 | 2013-10-17 | Kawasaki Heavy Ind Ltd | Minute crack sensor of concrete |
| KR20180056454A (en) * | 2016-11-18 | 2018-05-29 | 재단법인 한국탄소융합기술원 | Method for manufacturing carbon fiber reinforced plastic roof rail |
| KR101884170B1 (en) * | 2016-11-18 | 2018-09-21 | 재단법인 한국탄소융합기술원 | Method for manufacturing carbon fiber reinforced plastic roof rail |
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