JP2006327103A - Method of manufacturing molded article of fiber-reinforced resin composite material - Google Patents

Method of manufacturing molded article of fiber-reinforced resin composite material Download PDF

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JP2006327103A
JP2006327103A JP2005156187A JP2005156187A JP2006327103A JP 2006327103 A JP2006327103 A JP 2006327103A JP 2005156187 A JP2005156187 A JP 2005156187A JP 2005156187 A JP2005156187 A JP 2005156187A JP 2006327103 A JP2006327103 A JP 2006327103A
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mold
resin
prepreg
molded product
fiber
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Tsuneo Takano
恒男 高野
Makoto Matsumoto
誠 松本
Yoshiharu Numata
喜春 沼田
Yuji Kazahaya
祐二 風早
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Mitsubishi Rayon Co Ltd
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Mitsubishi Rayon Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a FRP molded article in good productivity which can be easily removed from a mold in case of compression-molding a prepreg in a mold and having a good appearance. <P>SOLUTION: The method of manufacturing the molded article of a fiber-reinforced resin composite material by compression-molding the prepreg made by impregnating a reinforcing fiber with a thermoplastic resin in mold is characterized in that a resin solution made by dissolving a silicone resin in a solvent containing a synthetic isoparaffin as a major component is applied on the molding surface of the mold in advance to form a film of the silicone resin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、圧縮成形法により繊維強化樹脂複合材料(以下、FRPという。)成形品を製造する方法に関する。   The present invention relates to a method for producing a fiber reinforced resin composite material (hereinafter referred to as FRP) molded product by a compression molding method.

FRPは、軽量かつ高強度で高剛性の特徴を生かし、スポーツ・レジャー用途から自動車や航空機等の産業用途まで、幅広く用いられている。このようなFRPからなる成形品は、強化繊維と熱硬化性樹脂組成物からなるプリプレグや、シートモールディングコンパウンド(以下、SMCという)などの成形材料を用いて成形されることが多いが、特にプリプレグとして、一方向に引き揃えられた強化繊維を含有するUDプリプレグや織物プリプレグなどを用いると、SMCを用いた場合より強度の高いFRP成形品が得られるなどの利点がある。   FRP is widely used from sports / leisure applications to industrial applications such as automobiles and airplanes, taking advantage of its light weight, high strength and high rigidity. Molded products made of such FRP are often molded using molding materials such as prepregs made of reinforcing fibers and thermosetting resin compositions and sheet molding compounds (hereinafter referred to as SMC). As described above, when a UD prepreg or a woven prepreg containing reinforcing fibers aligned in one direction is used, there is an advantage that an FRP molded product having higher strength than that obtained when SMC is used can be obtained.

また、プリプレグからFRP成形品を得る方法としては、オートクレーブを用いた方法(特許文献1参照。)、真空バッグによる方法(特許文献2参照。)、圧縮成形法(特許文献3参照。)などが知られている。圧縮成形法は、プリプレグを金型内に配置し、型締めし、型内を加熱および加圧した後、脱型する方法であって、成形時間が比較的短時間であることから、FRP成形品の大量生産に好適である。
特開平10−128778号公報 特開2002−159613号公報 特開平10−95048号公報
Moreover, as a method of obtaining an FRP molded product from a prepreg, a method using an autoclave (see Patent Document 1), a method using a vacuum bag (see Patent Document 2), a compression molding method (see Patent Document 3), and the like. Are known. The compression molding method is a method in which the prepreg is placed in a mold, the mold is clamped, the inside of the mold is heated and pressurized, and then demolded. Since the molding time is relatively short, FRP molding is performed. Suitable for mass production of products.
JP-A-10-128778 JP 2002-159613 A JP-A-10-95048

しかしながら、圧縮成形法でFRP成形品を製造した場合、FRP成形品が金型の成形面に密着してしまい、脱型が困難となるという問題がある。このような問題は、強化繊維を含まない熱硬化性樹脂の成形時にも認められるものではあるが、連続した強化繊維で補強されているFRP成形品は、特に脱型が困難となる傾向がある。
このようにFRP成形品が金型の成形面に密着してしまうと、脱型に長時間を要し、圧縮成形法のメリットである生産性が損なわれてしまうえ、脱型時に使用する脱型ピンなどの治具がFRP成形品を変形させるなどして、得られるFRP成形品の外観が低下してしまう可能性もある。
However, when an FRP molded product is manufactured by the compression molding method, there is a problem that the FRP molded product is in close contact with the molding surface of the mold, making it difficult to remove the mold. Such a problem can be recognized even when molding a thermosetting resin that does not contain reinforcing fibers, but FRP molded products reinforced with continuous reinforcing fibers tend to be difficult to demold. .
If the FRP molded product adheres to the molding surface of the mold in this way, it takes a long time to remove the mold, and the productivity that is the merit of the compression molding method is impaired. A jig such as a mold pin may deform the FRP molded product, and the appearance of the obtained FRP molded product may be deteriorated.

本発明は上記事情に鑑みてなされたもので、プリプレグを金型内で圧縮成形した際の脱型が容易であって、外観の良好なFRP成形品を生産性よく製造できる方法を提供することを課題とする。   The present invention has been made in view of the above circumstances, and provides a method for easily producing an FRP molded article having a good appearance and capable of being easily demolded when the prepreg is compression molded in a mold. Is an issue.

本発明の製造方法は、強化繊維に熱硬化性樹脂を含浸したプリプレグを金型内で圧縮成形し、FRPからなる成形品を製造する方法であって、あらかじめ前記金型の成形面に、合成イソパラフィンを主成分とする溶剤にシリコーン樹脂が溶解した樹脂溶液を塗布し、前記シリコーン樹脂からなる皮膜を形成しておくことを特徴とする。   The production method of the present invention is a method for producing a molded product made of FRP by compression-molding a prepreg in which a reinforcing fiber is impregnated with a thermosetting resin in a mold. A resin solution in which a silicone resin is dissolved in a solvent containing isoparaffin as a main component is applied to form a film made of the silicone resin.

本発明によれば、プリプレグを金型内で圧縮成形した際の脱型が容易であって、外観の良好なFRP成形品を生産性よく製造できる。   ADVANTAGE OF THE INVENTION According to this invention, the mold release at the time of compression-molding a prepreg in a metal mold | die is easy, and it can manufacture the FRP molded article with a favorable external appearance with sufficient productivity.

以下、本発明を詳細に説明する。
本発明のFRP成形品の製造方法は、強化繊維に熱硬化性樹脂を含浸したプリプレグを金型内で圧縮成形するものである。
使用する強化繊維としては、特に制限はなく、炭素繊維、ガラス繊維、アラミド繊維、高強度ポリエステル繊維、ボロン繊維などが例示できるが、中でも炭素繊維は、比強度および比弾性に優れることから、航空機や自動車等の部材として最も好適である。
Hereinafter, the present invention will be described in detail.
In the method for producing an FRP molded product of the present invention, a prepreg obtained by impregnating a reinforcing fiber with a thermosetting resin is compression-molded in a mold.
The reinforcing fiber to be used is not particularly limited, and examples thereof include carbon fiber, glass fiber, aramid fiber, high-strength polyester fiber, and boron fiber. Among them, carbon fiber is excellent in specific strength and specific elasticity, so that And is most suitable as a member for automobiles and the like.

プリプレグの形態も特に限定されず、一方向に引き揃えられた強化繊維を含むUDプリプレグ、製織された強化繊維を含む織物プリプレグなどを使用できる。また、得られるFRP成形品の外観の意匠性を高めるために、FPR成形品の表面を形成するプリプレグには強化繊維を織物の形態とし、FRP成形品の内部を構成するプリプレグには強化繊維を一方向に引き揃えた形態とするなど、複数の形態のプリプレグを併用することも可能である。   The form of the prepreg is not particularly limited, and a UD prepreg containing reinforcing fibers aligned in one direction, a woven prepreg containing woven reinforcing fibers, and the like can be used. In order to enhance the design of the appearance of the FRP molded product obtained, the prepreg forming the surface of the FPR molded product is made of reinforced fiber, and the prepreg constituting the inside of the FRP molded product is reinforced with the reinforcing fiber. It is also possible to use a plurality of prepregs in combination, for example, in a form that is aligned in one direction.

プリプレグに使用される熱硬化性樹脂にも特に制限はなく、例えば、エポキシ樹脂、不飽和ポリエステル樹脂、アクリル樹脂などが挙げられる。特に、FRP成形品として高強度のものを得るためには、エポキシ樹脂が好ましい。
エポキシ樹脂の例として、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、あるいはこれらを変性したエポキシ樹脂等が挙げられる。3官能以上の多官能性エポキシ樹脂としては、例えば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、あるいはこれらを変性したエポキシ樹脂やこれらのエポキシ樹脂をブロム化したブロム化エポキシ樹脂が挙げられる。また、これらエポキシ樹脂を1種単独で使用しても、2種以上を組み合わせて使用してもよい。
さらに熱硬化性樹脂は、硬化剤、離型剤、脱泡剤、紫外線吸収剤、充填材などの各種添加剤などを含有した熱硬化性樹脂組成物の形態で使用されても構わない。
There is no restriction | limiting in particular also in the thermosetting resin used for a prepreg, For example, an epoxy resin, unsaturated polyester resin, an acrylic resin etc. are mentioned. In particular, an epoxy resin is preferable in order to obtain a high-strength FRP molded product.
Examples of epoxy resins include bifunctional epoxy resins: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, fluorene type Examples thereof include epoxy resins and epoxy resins obtained by modifying them. Examples of the trifunctional or higher polyfunctional epoxy resin include phenol novolac type epoxy resin, cresol type epoxy resin, glycidylamine type epoxy resin such as tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol, tetraglycidylamine, tetrakis (glycidyloxy) Examples thereof include glycidyl ether type epoxy resins such as phenyl) ethane and tris (glycidyloxymethane), epoxy resins obtained by modifying these resins, and brominated epoxy resins obtained by brominating these epoxy resins. Moreover, these epoxy resins may be used individually by 1 type, or may be used in combination of 2 or more type.
Furthermore, the thermosetting resin may be used in the form of a thermosetting resin composition containing various additives such as a curing agent, a release agent, a defoaming agent, an ultraviolet absorber, and a filler.

次に、強化繊維および熱硬化性樹脂から構成されるプリプレグを用いてFRP成形品を製造する方法について具体的に説明する。
次に、強化繊維および熱硬化性樹脂から構成されるプリプレグを用いてFRP成形品を製造する方法について具体的に説明する。
まず、金型の成形面に付着している有機物、酸化物などの付着物をリムーバーで除去し、その後、有機溶剤により成形面を清浄な状態とする。リムーバーとしては、例えばフレコート(商品名、Loctite(株)製)などを使用でき、有機溶剤としては、アセトン、エチルメチルケトン等を好適に使用できる。
Next, a method for producing an FRP molded product using a prepreg composed of reinforcing fibers and a thermosetting resin will be specifically described.
Next, a method for producing an FRP molded product using a prepreg composed of reinforcing fibers and a thermosetting resin will be specifically described.
First, deposits such as organic substances and oxides adhering to the molding surface of the mold are removed with a remover, and then the molding surface is cleaned with an organic solvent. As the remover, for example, Frecoat (trade name, manufactured by Loctite Co., Ltd.) or the like can be used. As the organic solvent, acetone, ethyl methyl ketone, or the like can be suitably used.

ついで、清浄な状態の金型の成形面に、合成イソパラフィンを主成分とする溶剤にシリコーン樹脂が溶解した樹脂溶液を塗布する。また、ここで主成分とは50質量%以上のことを指し、溶剤として合成イソパラフィン以外のものが50質量%以下の範囲で含まれていてもよい。
合成イソパラフィンとは、化学式C2n+2で表される複数のパラフィンの混合物であり、無色透明の液体である。nとしては、好適には1〜10の整数である。
ここで、溶剤の主成分を合成イソパラフィンとすることにより、樹脂溶液を成形面に塗布する際の塗布性、作業性、取扱性が優れる。また、合成イソパラフィンは環境負荷が少ない点でも好ましい。さらに、溶剤としては、合成イソパラフィンとともに、酢酸エチルを併用することが好ましい。このように併用すると、揮発性の高い酢酸エチルの作用により、塗布後の乾燥が常温または低温加熱で速く進行し、作業性が向上する。
Next, a resin solution in which a silicone resin is dissolved in a solvent containing synthetic isoparaffin as a main component is applied to the molding surface of the mold in a clean state. Moreover, a main component means 50 mass% or more here, and things other than synthetic isoparaffin may be contained in the range of 50 mass% or less as a solvent.
Synthetic isoparaffin is a mixture of a plurality of paraffins represented by the chemical formula C n H 2n + 2 and is a colorless and transparent liquid. n is preferably an integer of 1 to 10.
Here, by using synthetic isoparaffin as the main component of the solvent, the coating property, workability, and handling property when applying the resin solution to the molding surface are excellent. Synthetic isoparaffins are also preferred because of their low environmental impact. Furthermore, it is preferable to use ethyl acetate together with the synthetic isoparaffin as the solvent. When used in combination as described above, due to the action of highly volatile ethyl acetate, drying after coating proceeds rapidly at room temperature or low temperature heating, and workability is improved.

シリコーン樹脂としては特に制限はないが、ジメチルポリキシロキサンの特長を活かしながら、メチル基の一部に各種有機基が導入された反応性シリコーン樹脂を用いることが好ましい。   Although there is no restriction | limiting in particular as a silicone resin, It is preferable to use the reactive silicone resin in which various organic groups were introduce | transduced into a part of methyl group, utilizing the characteristic of dimethylpolysiloxane.

合成イソパラフィンを主成分とする溶剤にシリコーン樹脂が溶解した樹脂溶液中におけるシリコーン樹脂の濃度は、1〜20質量%が好適である。
また、シリコーン樹脂が合成イソパラフィンを主成分とする溶剤に溶解した市販の樹脂溶液としては、例えば信越化学(株)製「SEPA COAT SP」があり、このような市販品も使用できる。
The concentration of the silicone resin in the resin solution in which the silicone resin is dissolved in the solvent mainly composed of synthetic isoparaffin is preferably 1 to 20% by mass.
Further, as a commercially available resin solution in which a silicone resin is dissolved in a solvent containing synthetic isoparaffin as a main component, there is “SEPA COAT SP” manufactured by Shin-Etsu Chemical Co., Ltd., and such a commercially available product can also be used.

樹脂溶液を成形面に塗布し、皮膜を形成する具体的方法としては、室温の成形面に樹脂溶液を塗布して、そのまま3〜24時間程度放置する方法、140〜150℃程度に加熱された金型に樹脂溶液を塗布する方法のいずれでもよい。室温の成形面に樹脂溶液を塗布する方法によれば、溶剤の蒸発速度が遅いため、得られるFRP成形品の表面の光沢が優れる。一方、加熱された金型に樹脂溶液を塗布する方法によれば、塗布後10〜30分間程度で皮膜の形成が完了するため、FRP成形品の生産性がより優れる。よって、目的に応じて、樹脂溶液を成形面に塗布する際の成形面の温度を決定すればよい。
また、樹脂溶液を成形面に塗布する具体的方法としては、刷毛塗り法、スプレー法などが挙げられ、その塗布量としては、最終的に形成される皮膜の厚さが2〜10μmとなる範囲が好ましい。
As a specific method of applying the resin solution to the molding surface and forming a film, a method of applying the resin solution to the molding surface at room temperature and leaving it for about 3 to 24 hours, heated to about 140 to 150 ° C. Any method of applying a resin solution to a mold may be used. According to the method of applying the resin solution to the molding surface at room temperature, the gloss of the surface of the obtained FRP molded product is excellent because the evaporation rate of the solvent is slow. On the other hand, according to the method of applying the resin solution to the heated mold, the formation of the film is completed in about 10 to 30 minutes after the application, so that the productivity of the FRP molded product is more excellent. Therefore, what is necessary is just to determine the temperature of the molding surface at the time of apply | coating a resin solution to a molding surface according to the objective.
Further, specific methods for applying the resin solution to the molding surface include a brush coating method, a spray method, and the like, and the coating amount is within a range in which the thickness of the finally formed film is 2 to 10 μm. Is preferred.

このようにして成形面に皮膜を形成した後、金型内にプリプレグを配置する。このとき、プリプレグにはあらかじめ切込みを入れておいてもよいし、予備賦形したプリフォームの形態で配置してもよい。
プリプレグを金型内に配置した後、金型を型締めし、加熱、加圧して圧縮成形する。そして、型開きし、FRP成形品を取り出す。
Thus, after forming a film | membrane on a molding surface, a prepreg is arrange | positioned in a metal mold | die. At this time, the prepreg may be cut in advance, or may be arranged in the form of a preformed preform.
After the prepreg is placed in the mold, the mold is clamped, and heated and pressed to perform compression molding. Then, the mold is opened and the FRP molded product is taken out.

圧縮成形での加熱温度には制限はなく、熱硬化性樹脂の種類などに応じて決定すればよいが、高温であるほど成形時間を短くできるため、加熱温度は120℃以上が好ましく、140℃以上がさらに好ましい。しかしながら、温度が高すぎると金型の冷却に非常に時間がかかり生産性が低下するし、十分に冷却しないうちに金型に次のプリプレグを配置すると、熱硬化性樹脂が金型内全体に行き渡らないうちに硬化が始まってしまい、得られるFRP成形品が所望の形状とならない場合がある。よって、加熱温度は200℃以下が好ましく、180℃以下がさらに好ましい。
また、加圧の程度にも制限はないが、高圧であるほど得られるFRP成形品は表面のピンホールや内部のボイドが低減される傾向がある。よって、プリプレグに加わる圧力が0.5MPa以上であることが好ましく、1MPa以上であることがさらに好ましい。また、上限が50MPaであれば、十分にFRP成形品の表面のピンホールや内部のボイドを低減できる。
The heating temperature in compression molding is not limited and may be determined according to the type of thermosetting resin. However, since the molding time can be shortened as the temperature is higher, the heating temperature is preferably 120 ° C. or higher, and 140 ° C. The above is more preferable. However, if the temperature is too high, it takes a very long time to cool the mold and the productivity is reduced.If the next prepreg is placed in the mold before it is sufficiently cooled, the thermosetting resin will spread throughout the mold. Curing begins before it reaches the end, and the resulting FRP molded product may not have the desired shape. Therefore, the heating temperature is preferably 200 ° C. or lower, and more preferably 180 ° C. or lower.
Further, the degree of pressurization is not limited, but the FRP molded product obtained with higher pressure tends to reduce surface pinholes and internal voids. Therefore, the pressure applied to the prepreg is preferably 0.5 MPa or more, and more preferably 1 MPa or more. Moreover, if an upper limit is 50 MPa, the pinhole and the internal void of the surface of a FRP molded product can fully be reduced.

このように、金型の成形面に、合成イソパラフィンを主成分とする溶剤にシリコーン樹脂が溶解した樹脂溶液を塗布し、シリコーン樹脂からなる皮膜を形成してから、プリプレグを金型内に配置して圧縮成形することにより、FRP成形品が金型の成形面に密着せず、型開き後の脱型を容易に短時間で行うことができる。また、容易に脱型できるので、脱型時における脱型ピンの使用により、FRP成形品を変形させてしまうなどの不都合が起こらない。よって、外観の良好なFRP成形品を生産性よく製造できる。   In this way, a resin solution in which a silicone resin is dissolved in a solvent containing synthetic isoparaffin as a main component is applied to the molding surface of the mold to form a film made of silicone resin, and then the prepreg is placed in the mold. By performing compression molding, the FRP molded product does not adhere to the molding surface of the mold, and demolding after the mold opening can be easily performed in a short time. Further, since the mold can be easily removed, there is no inconvenience such as deformation of the FRP molded product due to the use of the release pin at the time of release. Therefore, an FRP molded product having a good appearance can be manufactured with high productivity.

なお、シリコーン樹脂からなる皮膜を形成する前に、金型の成形面を粗面化処理しておくと、皮膜の耐久性が向上するとともに、皮膜とFRP成形品との有効接触面積が大きくなるために、脱型がより容易になる。
粗面化処理としては、サンドブラスト処理、酸などの薬品による処理が例示できる。粗面化の程度としては、♯3000〜♯400仕上げが好ましく、より好ましくは、♯1000〜♯800仕上げである。
If the molding surface of the mold is roughened before forming the coating film made of silicone resin, the durability of the coating film is improved and the effective contact area between the coating film and the FRP molded product is increased. Therefore, demolding becomes easier.
Examples of the surface roughening treatment include sand blast treatment and treatment with chemicals such as acids. As the degree of roughening, # 3000 to # 400 finishing is preferable, and # 1000 to # 800 finishing is more preferable.

以下、本発明について実施例を挙げて具体的に説明するが、本発明はこれにより限定されるものでない。なお、各評価は下記の通り実施し、表中には略号(○、×)で評価結果を記載した。
1)FRP成形品の脱型性 ○:圧縮成形後のFRP成形品を金型から取り出す際に、FRP成形品が金型の成形面に密着せず、容易に取り出すことができる。
×:圧縮成形後のFRP成形品を金型から取り出す際に、FRP成形品が金型の成形面に密着し、容易には取り出すことができない。
2)FRPの外観
○:圧縮成形後のFRP成形品に脱型ピンを使用したことによる変形や割れがない。
×:圧縮成形後のFRP成形品に脱型ピンを使用したことによる変形や割れが認められる。
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited by this. In addition, each evaluation was implemented as follows and described the evaluation result by abbreviation ((circle), x) in the table | surface.
1) Demoldability of FRP molded product ○: When the FRP molded product after compression molding is taken out from the mold, the FRP molded product does not adhere to the molding surface of the mold and can be easily taken out.
X: When the FRP molded product after compression molding is taken out from the mold, the FRP molded product adheres to the molding surface of the mold and cannot be easily removed.
2) Appearance of FRP ○: There is no deformation or cracking due to the use of a demolding pin in the FRP molded product after compression molding.
X: Deformation and cracking due to the use of a demolding pin in the FRP molded product after compression molding are observed.

<実施例1>
プリプレグ(三菱レイヨン(株)製)を290×290mmに切り出し、これを繊維方向が0°/90°/0°/90°/0°/90°/0°/90°/0°/90°/0°/90°となるように計12枚積層し、プリプレグ積層体を準備した。
プリプレグは、以下のようにして作製した。
エポキシ樹脂組成物(三菱レイヨン製耐熱変性エポキシ樹脂 100部、エピコート828 20部、PDMU 5部、DICY 10部)を離型紙上に樹脂目付け54g/mで均一に塗布し樹脂層を形成した。この樹脂層を三菱レイヨン(株)製炭素繊維(TR50S)を繊維目付けが250g/mになるように一方向に引きそろえたシート状物の両面に貼り付けた後、ローラーで加熱及び加圧してエポキシ樹脂組成物を炭素繊維に含浸させて、樹脂含有率30%のプリプレグを作成した。
一方、クロム鍍金された300×300mmの平板用金型の成形面の付着物を、フレコート(商品名、Loctite(株)製)で除去し、ついで、成形面をアセトンで洗浄して清浄にした。
ついで、この金型を140℃に加熱し、その成形面に、信越化学(株)製「SEPA COAT SP」を塗布し、30分間保持して焼き付け、シリコーン樹脂からなる厚さ3μmの皮膜を形成した。
なお、信越化学(株)製「SEPA COAT SP」は、酢酸エチルと合成イソパラフィンからなる溶剤(1:1の質量比)に反応性シリコーン樹脂が3質量%の濃度で溶解した樹脂溶液である。また、合成イソパラフィンは、比重(20℃)=0.8、粘度(20℃)=1mPa・sec、沸点=95〜155℃、引火点=7℃、発火点200℃以上の特性を有し、水には不溶なものである。
そして、先に準備したプリプレグ積層体を金型内に置き、直ちに金型を締め、7MPaの圧力を5分間加え続けた後型開きし(加熱温度は140℃を維持)、脱型ピンを使用して平板状のFRP成形品を脱型し取り出した。
<Example 1>
A prepreg (Mitsubishi Rayon Co., Ltd.) is cut into 290 × 290 mm, and the fiber direction is 0 ° / 90 ° / 0 ° / 90 ° / 0 ° / 90 ° / 0 ° / 90 ° / 0 ° / 90 °. A total of 12 sheets were laminated so as to be / 0 ° / 90 ° to prepare a prepreg laminate.
The prepreg was produced as follows.
An epoxy resin composition (100 parts of heat-modified epoxy resin manufactured by Mitsubishi Rayon, 20 parts of Epicoat 828, 5 parts of PDMU, 10 parts of DICY) was uniformly applied onto the release paper at a resin basis weight of 54 g / m 2 to form a resin layer. This resin layer was applied to both sides of a sheet-like material in which carbon fiber (TR50S) manufactured by Mitsubishi Rayon Co., Ltd. was aligned in one direction so that the fiber basis weight was 250 g / m 2 , and then heated and pressurized with a roller. The carbon fiber was impregnated with the epoxy resin composition to prepare a prepreg with a resin content of 30%.
On the other hand, the deposits on the molding surface of the chrome-plated 300 × 300 mm flat plate mold were removed with Frecote (trade name, manufactured by Loctite Co., Ltd.), and then the molding surface was cleaned with acetone to be cleaned. .
Next, this mold was heated to 140 ° C., and “SEPA COAT SP” manufactured by Shin-Etsu Chemical Co., Ltd. was applied to the molding surface, and baked by holding for 30 minutes to form a 3 μm thick film made of silicone resin. did.
“SEPA COAT SP” manufactured by Shin-Etsu Chemical Co., Ltd. is a resin solution in which a reactive silicone resin is dissolved at a concentration of 3% by mass in a solvent (1: 1 mass ratio) composed of ethyl acetate and synthetic isoparaffin. Synthetic isoparaffin has properties of specific gravity (20 ° C.) = 0.8, viscosity (20 ° C.) = 1 mPa · sec, boiling point = 95 to 155 ° C., flash point = 7 ° C., ignition point 200 ° C. or more, It is insoluble in water.
Then, place the prepared prepreg laminate in the mold, immediately tighten the mold, continue to apply 7 MPa pressure for 5 minutes, then open the mold (heating temperature is maintained at 140 ° C), and use the demolding pin The flat FRP molded product was removed from the mold.

<比較例1〜8>
金型の成形面に、信越化学(株)製「SEPA COAT SP」の代わりに表1に示す離型剤を塗布し、30分間保持して焼き付けた以外は、実施例1と同様にしてFRP成形品を得た。
なお、使用したプリプレグ、その積層構成はいずれも実施例1と同様である。また、圧縮成形時の加熱温度(140℃)、圧力(7MPa)、保持時間(5分間)も、いずれも実施例1と同じである。
<Comparative Examples 1-8>
FRP was applied in the same manner as in Example 1 except that the release agent shown in Table 1 was applied to the molding surface of the mold instead of “SEPA COAT SP” manufactured by Shin-Etsu Chemical Co., Ltd., and held and baked for 30 minutes. A molded product was obtained.
Note that the prepreg used and the laminated configuration thereof are the same as those in Example 1. Also, the heating temperature (140 ° C.), pressure (7 MPa), and holding time (5 minutes) during compression molding are all the same as in Example 1.

Figure 2006327103
Figure 2006327103

離型剤1:Chemtrend社製モノコートE268NC
シリコーン樹脂成分を含まない溶剤タイプ(スプレー缶)
離型剤2:ダイキン工業(株)社製ダイフリーME810
水性溶剤に、樹脂成分としてフッ素系樹脂を含む。
離型剤3:ダイキン工業(株)社製ダイフリーGW1051
水性溶剤に、樹脂成分としてフッ素系樹脂とシリコーン樹脂とを含む。
離型剤4:ダイキン工業(株)社製ダイフリーGW1070
水性溶剤に、樹脂成分としてフッ素系樹脂とシリコーン樹脂とを含む。
離型剤5:ダイキン工業(株)社製ダイフリーGA6010
樹脂成分として、フッ素系樹脂とシリコーン樹脂とを含む代替フロンタイプ(スプレー
缶)。
離型剤6:Chemtrend社製ケムリースSU−5
水性溶剤に、樹脂成分としてフッ素系樹脂とシリコーン樹脂とを含む。
離型剤7:ナガセケムテックス(株)製モールドリリースQZ−13
溶剤を含まないワックスタイプ。
離型剤8:Rocktite社製(旧Dextor)Frekote 44NC
シリコーン樹脂成分を含まない溶剤タイプ(スプレー缶)。
Mold release agent 1: Chemtend monocoat E268NC
Solvent type that does not contain silicone resin component (spray can)
Release agent 2: Die Free ME810 manufactured by Daikin Industries, Ltd.
The aqueous solvent contains a fluorine-based resin as a resin component.
Release agent 3: Daikin Industries, Ltd. Die Free GW1051
The aqueous solvent contains a fluorine resin and a silicone resin as resin components.
Release agent 4: Daikin Industries, Ltd. Die Free GW1070
The aqueous solvent contains a fluorine resin and a silicone resin as resin components.
Release agent 5: Daifree GA6010 manufactured by Daikin Industries, Ltd.
Alternative fluorocarbon type (spray can) containing fluorine resin and silicone resin as resin components.
Mold release agent 6: Chemtrend Chem-5 SU-5
The aqueous solvent contains a fluorine resin and a silicone resin as resin components.
Release agent 7: Mold release QZ-13 manufactured by Nagase ChemteX Corporation
Wax type without solvent.
Mold release agent 8: manufactured by Rocktit (former Dextor) Frekote 44NC
Solvent type that does not contain silicone resin component (spray can).

Claims (1)

強化繊維に熱硬化性樹脂を含浸したプリプレグを金型内で圧縮成形し、繊維強化樹脂複合材料からなる成形品を製造する方法であって、
あらかじめ前記金型の成形面に、合成イソパラフィンを主成分とする溶剤にシリコーン樹脂が溶解した樹脂溶液を塗布し、前記シリコーン樹脂からなる皮膜を形成しておくことを特徴とする成形品の製造方法。
A method for producing a molded article made of a fiber-reinforced resin composite material by compression-molding a prepreg in which a reinforcing fiber is impregnated with a thermosetting resin in a mold,
A method for producing a molded article, wherein a resin solution in which a silicone resin is dissolved in a solvent containing synthetic isoparaffin as a main component is applied in advance to a molding surface of the mold, and a film made of the silicone resin is formed. .
JP2005156187A 2005-05-27 2005-05-27 Method of manufacturing molded article of fiber-reinforced resin composite material Pending JP2006327103A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2015025592A1 (en) * 2013-08-22 2017-03-02 アイカSdkフェノール株式会社 Manufacturing method of resin molding
WO2019189369A1 (en) * 2018-03-28 2019-10-03 三菱ケミカル株式会社 Fiber-reinforced composite material molding apparatus and method for manufacturing fiber-reinforced composite material molded article
CN113071030A (en) * 2021-03-25 2021-07-06 东莞市凯文化工有限公司 Hole sealing release agent and preparation method thereof
US11325325B2 (en) * 2016-10-31 2022-05-10 Mitsubishi Chemical Corporation Method for manufacturing fiber reinforced plastic molded body

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2015025592A1 (en) * 2013-08-22 2017-03-02 アイカSdkフェノール株式会社 Manufacturing method of resin molding
US11325325B2 (en) * 2016-10-31 2022-05-10 Mitsubishi Chemical Corporation Method for manufacturing fiber reinforced plastic molded body
WO2019189369A1 (en) * 2018-03-28 2019-10-03 三菱ケミカル株式会社 Fiber-reinforced composite material molding apparatus and method for manufacturing fiber-reinforced composite material molded article
CN113071030A (en) * 2021-03-25 2021-07-06 东莞市凯文化工有限公司 Hole sealing release agent and preparation method thereof
CN113071030B (en) * 2021-03-25 2023-03-17 东莞市凯文化工有限公司 Hole sealing release agent and preparation method thereof

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