JP2553206B2 - Method for manufacturing lightweight composite molded article - Google Patents

Method for manufacturing lightweight composite molded article

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Publication number
JP2553206B2
JP2553206B2 JP1317623A JP31762389A JP2553206B2 JP 2553206 B2 JP2553206 B2 JP 2553206B2 JP 1317623 A JP1317623 A JP 1317623A JP 31762389 A JP31762389 A JP 31762389A JP 2553206 B2 JP2553206 B2 JP 2553206B2
Authority
JP
Japan
Prior art keywords
resin
molding
expandable
mold
particles
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.)
Expired - Lifetime
Application number
JP1317623A
Other languages
Japanese (ja)
Other versions
JPH03180329A (en
Inventor
至郎 山本
正隆 井上
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Teijin Ltd
Original Assignee
Teijin Ltd
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Filing date
Publication date
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Priority to JP1317623A priority Critical patent/JP2553206B2/en
Publication of JPH03180329A publication Critical patent/JPH03180329A/en
Application granted granted Critical
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Description

【発明の詳細な説明】 [産業上の利用分野] 本発明は、少くとも硬化した成形樹脂からなり緻密な
表層部の間に多孔質層からなるコア部(芯部)が存在す
る軽量な複合成形物の製造方法に関する。
DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a lightweight composite in which a core portion (core portion) made of a porous layer is present between a dense surface layer portion made of at least a cured molding resin. The present invention relates to a method for manufacturing a molded product.

[従来の技術] 通常、合成樹脂成形物の一種である多孔質成形物は、
従来、工業的には発泡成形により製造されていた。これ
をサンドイッチ材等の軽量構造体にする方法としては、
発泡成形物をプリプレグ等で覆って成形するか、予め成
形した外殻中空体に発泡性樹脂を注入して発泡成形する
のが普通である。
[Prior Art] Usually, a porous molded article, which is a kind of synthetic resin molded article, is
Conventionally, it has been industrially produced by foam molding. As a method of making this a lightweight structure such as a sandwich material,
It is usual that the foamed molded product is covered with a prepreg or the like to be molded, or a foamable resin is injected into a preformed outer shell hollow body to carry out foamed molding.

近年、発泡膨張を用いた内圧成形が考案され(特開昭
63−162207号等)、更に、本発明者らは、発泡性樹脂粒
子と硬化性液状樹脂を使用し多孔質コア層と繊維補強樹
脂表面層とを同時に成形して複合成形物を得る新規な方
法を開発し、提案した(例えば特願平1−179830号、特
公平7−12613号参照)。
In recent years, internal pressure molding using foam expansion has been devised (Japanese Patent Laid-Open No. Sho
63-162207, etc.), and further, the present inventors have obtained a novel molded article by simultaneously molding a porous core layer and a fiber-reinforced resin surface layer using expandable resin particles and a curable liquid resin. A method was developed and proposed (see, for example, Japanese Patent Application Nos. 1-179830 and 7-12613).

[発明が解決しようとする課題] コア部芯が多孔質層からなり表層部が繊維補強樹脂複
合材料(FRP)により所定の形状に成形された複合成形
物を発泡性樹脂粒子等を用いて一体成形するこれらの成
形法は効率的で優れたものである。しかしながら、発泡
性樹脂粒子は、所定の温度まで、その温度に対して所定
の時間だけ膨張して、例えば金型内で若干時間膨張圧力
を保ち、以後、膨張圧力が低下するのが普通である。例
えば特開平1−255530号公報第8ページの第9図、第10
図はこの一例を示したものであり、この他でも、例えば
発泡性樹脂粒子(FMC−003・004)のカタログ等にもこ
の現象が記載されている。従って、これらの成形方法で
は、発泡性樹脂粒子、硬化性液状成形樹脂、成形物の形
態を適当に選ばないと、該樹脂粒子の膨張が終わっても
樹脂が硬化せず、発泡性樹脂粒子の膨張終了後収縮し始
めてから樹脂が硬化し、結果として樹脂が不足した部分
を含む成形物が得られる等の問題が生じる。この問題は
成形物の厚さが増えると、特に現われ易い。
[Problems to be Solved by the Invention] A core formed of a porous layer and a surface layer formed of a fiber reinforced resin composite material (FRP) into a predetermined shape is used to integrally form a composite molded article using expandable resin particles or the like. These molding methods for molding are efficient and excellent. However, it is usual that the expandable resin particles expand to a predetermined temperature for a predetermined time with respect to the temperature, and for example, maintain the expansion pressure for a while in the mold, and thereafter the expansion pressure decreases. . For example, JP-A-1-255530, page 9, FIG.
The figure shows one example of this, and besides this, this phenomenon is also described in, for example, the catalog of expandable resin particles (FMC-003.004). Therefore, in these molding methods, if the form of the expandable resin particles, the curable liquid molding resin and the molded product is not properly selected, the resin will not cure even after the expansion of the resin particles, and the expandable resin particles After the expansion is completed, the resin begins to shrink and then the resin is cured, resulting in a problem that a molded product including a resin-deficient portion is obtained. This problem is especially likely to occur as the thickness of the molded product increases.

[課題を解決するための手段] 本発明者らは、これらの問題を解決すべく鋭意研究の
結果、熱膨張性の発泡性樹脂粒子と共に非熱膨張性の軽
量弾性体粒子を併用することにより、上述の如き膨張圧
力の低下の問題を解消することができ、良好な成形品と
なし得ることを見い出し、本発明に到達した。
[Means for Solving the Problems] As a result of intensive studies to solve these problems, the present inventors have found that non-heat-expandable lightweight elastic particles are used in combination with heat-expandable expandable resin particles. The present invention has been completed by finding that the above-mentioned problem of a decrease in expansion pressure can be solved and a good molded product can be obtained.

すなわち、本発明は、少なくとも硬化した成形樹脂に
より所定の形状に形成された表層部、多孔質のコア部、
及び表層部とコア部との間に介在する分離層、を有する
軽量複合成形物を製造するに当り、 (a)成形用の型内に、熱膨脹後の発泡性樹脂粒子及び
非熱膨脹性軽量弾性粒子を実質的に通さないが硬化性の
液状成形樹脂は通す分離層を設置すること、 (b)分離層に囲まれた、成形後に多孔質コア部となる
領域に、発泡性樹脂粒子と非熱膨脹性軽量弾性粒子と、
更に必要に応じ硬化性の液状成形樹脂と、を存在させる
こと、 (c)必要に応じ(型内の適量の液状成形樹脂が存在し
ない場合は)、型内に液状の硬化性樹脂を導入するこ
と、 (d)型の所定領域を十分高い温度まで加熱すること及
び/又は上記硬化性樹脂の反応熱による温度上昇によ
り、発泡性樹脂粒子を加熱発泡させて体積膨脹を生じさ
せ、これにより分離層を型の内面に対して押しつけると
ともに硬化性の液状成形樹脂を分離応に浸透させて、表
層部に至らせること、 (e)上記液状成形樹脂を硬化させて成形すること、そ
して、 (f)得られた複合成形物を型から取り出すこと、 を特徴とする軽量複合成形物の製造方法である。
That is, the present invention is a surface layer portion formed in a predetermined shape by at least a cured molding resin, a porous core portion,
And (a) a lightweight composite molded article having a separation layer interposed between the surface layer section and the core section. (A) In the molding die, expandable resin particles after thermal expansion and non-heat-expandable lightweight elasticity A separation layer is provided that does not allow particles to pass through substantially, but allows a curable liquid molding resin to pass therethrough. (B) In the region surrounded by the separation layer, which will be the porous core after molding, the non-expandable resin particles Heat-expandable lightweight elastic particles,
Furthermore, if necessary, a curable liquid molding resin is allowed to exist, and (c) if necessary (when an appropriate amount of the liquid molding resin is not present in the mold), a liquid curable resin is introduced into the mold. By heating a predetermined region of the type (d) to a sufficiently high temperature and / or increasing the temperature by the reaction heat of the curable resin, the expandable resin particles are heated and foamed to cause volume expansion, thereby separating. Pressing the layer against the inner surface of the mold and penetrating the curable liquid molding resin to the separation layer to reach the surface layer portion; (e) curing and molding the liquid molding resin; and (f) ) Taking out the obtained composite molded article from the mold, a method for producing a lightweight composite molded article.

本発明では、発泡性樹脂粒子の熱による発泡膨張を利
用して成形物に内圧を生じさせながら複合成形物の成形
を行うに際して、この膨張により発泡性樹脂粒子と共存
する軽量弾性体粒子を圧縮し、樹脂の硬化が進まないう
ちに膨張した発泡性樹脂粒子が収縮し始めたら、系内の
圧力変化(圧力低下)に応じてこの軽量弾性体粒子を膨
張(復元)させて全体としての膨脹力を補おうとするも
のである。例えば、硬化未完了のサンドイッチ材の多孔
質の孔の幾つかを軽量弾性体粒子で充填しておき、成形
初期の段階では該粒子を圧縮し、発泡性樹脂粒子による
他の孔が収縮し始めて金型内の圧力が低下した際にこれ
を膨張させて圧力を補おうとするものである。
In the present invention, when the composite molded article is molded while the internal pressure is generated in the molded article by utilizing the foaming expansion of the expandable resin particles due to the heat, the expansion of the lightweight elastic particles coexisting with the expandable resin particles is caused by the expansion. However, if the expandable resin particles begin to contract before the resin cures, the lightweight elastic particles expand (restore) according to the pressure change (pressure drop) in the system and the overall expansion. It tries to supplement the power. For example, some of the porous holes of the uncured sandwich material are filled with lightweight elastic particles, and the particles are compressed in the initial stage of molding, and other holes due to the expandable resin particles start to shrink. When the pressure inside the mold is reduced, it is expanded to try to supplement the pressure.

従って、コア部では発泡性樹脂粒子からなる熱膨張体
と粒子状軽量弾性体とは均等に分散し、混在しているこ
とが望ましい。例えば、熱膨張性の発泡性樹脂を小粒子
(バルーン)とし、軽量弾性体を発泡成形した小粒子と
し、両者を均一な混合物とすることは好ましい実施態様
である。
Therefore, in the core portion, it is desirable that the thermal expansion body made of expandable resin particles and the particulate lightweight elastic body are evenly dispersed and mixed. For example, it is a preferred embodiment that the heat-expandable expandable resin is used as small particles (balloons), the lightweight elastic body is used as foam-molded small particles, and both are made into a uniform mixture.

ここで用いる発泡性樹脂粒子としては、加熱により体
積が少なくとも2倍、好ましくは3倍、更に好ましくは
6倍以上に増大するものであり、成形に使用する樹脂等
に溶解しないものである。また、発泡空間部に液状樹脂
が入らないように、発泡が独立気泡となるものが好まし
い。かかる発泡性樹脂粒子の素材としては、例えばポリ
ウレタン、フェノール、ポリウレア、メラミン、ポリイ
ミド等の硬化型フォームやその前駆体、ポリ塩化ビニ
ル、ポリ塩化ビニリデン、ポリスチレン、ポリエチレ
ン、PPO、ポリアミド、ポリカーボネート、PBT、ポリイ
ミド等の熱可塑性樹脂が挙げられる。かかる発泡性樹脂
粒子の発泡は発泡剤分解法、溶剤揮散法、化学反応法、
気体混入法等いずれの方法も適用できる。この中で発泡
剤分解法や溶媒揮散法が好ましく用いられる。
The expandable resin particles used here have a volume that increases by at least 2 times, preferably 3 times, and more preferably 6 times or more by heating, and do not dissolve in the resin or the like used for molding. Further, it is preferable that the foam is closed cells so that the liquid resin does not enter the foam space. Examples of the material of the expandable resin particles include polyurethane, phenol, polyurea, melamine, and curable foams such as polyimide and precursors thereof, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyethylene, PPO, polyamide, polycarbonate, PBT, A thermoplastic resin such as polyimide can be used. Foaming of the expandable resin particles is performed by a foaming agent decomposition method, a solvent volatilization method, a chemical reaction method,
Any method such as a gas mixing method can be applied. Of these, the blowing agent decomposition method and the solvent volatilization method are preferably used.

本発明方法の一実施態様においては、発泡性樹脂粒子
は微細な粒子にして軽量弾性粒子とともに液状硬化樹脂
と均一に混合させて用いられる。この場合には微細にな
ればなるほど得られる成形物の品質が高まるので好まし
い。かかる発泡性樹脂粒子としては、例えば加熱により
発泡してマイクロカプセル化する低沸点炭化水素を内包
したポリ塩化ビニリデン粒子等が特に好適に使用され
る。
In one embodiment of the method of the present invention, the expandable resin particles are used in the form of fine particles, which are uniformly mixed with the liquid curable resin together with the lightweight elastic particles. In this case, the finer the particles, the better the quality of the obtained molded product, which is preferable. As such expandable resin particles, for example, polyvinylidene chloride particles containing low-boiling hydrocarbons which are foamed by heating to be microencapsulated are particularly preferably used.

また、軽量弾性体粒子は予め発泡成形した粒子、例え
ばポリエチレン、ポリプロピレン、ポリウレタン等の気
泡を含む軽量粒子であって、これを圧縮した場合に縮小
し圧力を解放しない場合にほぼ原形に戻るが熱によって
さらに発泡膨張することのない粒子である。また、当然
であるが、該粒子は弾性の中空バルーン等であってもよ
い。この弾性粒子は比重が0.5以下のものが好ましい。
In addition, the lightweight elastic particles are particles that have been previously foam-molded, for example, lightweight particles containing bubbles such as polyethylene, polypropylene, polyurethane, etc. The particles do not expand and expand further. Also, as a matter of course, the particles may be elastic hollow balloons or the like. The elastic particles preferably have a specific gravity of 0.5 or less.

さらに、これらに非弾性の非膨張性中空体粒子を混合
することもできる。軽量の多孔質体を得る上で、このよ
うな非弾性の中空体粒子は安価で便利なものである。経
済性も考慮すると、このような中空体粒子としてガラス
バルーン、シラスバルーン等が好ましい。
Further, it is possible to mix these with non-elastic non-expandable hollow particles. Such inelastic hollow body particles are inexpensive and convenient for obtaining a lightweight porous body. In consideration of economical efficiency, glass balloons, shirasu balloons and the like are preferable as the hollow particles.

一方、液状成形樹脂としては熱硬化性の液状樹脂が好
ましく、エポキシ樹脂、不飽和ポリエステル樹脂、ジシ
クロペンタジエン樹脂、非発泡性ウレタン樹脂等一般に
よく知られている液状成形樹脂が好ましく用いられる。
なお、ここで言う「成形樹脂」とは反応により硬化樹脂
となる樹脂原料(組成物)を包含する。
On the other hand, as the liquid molding resin, a thermosetting liquid resin is preferable, and generally well-known liquid molding resin such as epoxy resin, unsaturated polyester resin, dicyclopentadiene resin, non-foaming urethane resin is preferably used.
The term "molding resin" as used herein includes a resin raw material (composition) that becomes a cured resin by a reaction.

一方、分離層としては、熱膨張後の発泡性樹脂粒子及
び軽量弾性粒子を実質的に通さず硬化性液状成形樹脂は
通す分離機能を有する部分が少なくともその一部又は全
部を構成し、残りは上記液状成形樹脂をも通さない材料
からなるものを用いる。
On the other hand, as the separation layer, a portion having a separating function that allows the curable liquid molding resin to pass substantially without passing through the expandable resin particles and the lightweight elastic particles after thermal expansion constitutes at least a part or all of the remaining part. A material that is impermeable to the liquid molding resin is used.

かかる分離層の分離機能を構成するものとしては、繊
維シート及び/又は多孔質シートが挙げられる。繊維シ
ートとしては、各種天然繊維、合成繊維、金属繊維、炭
素又はセラミックス等の無機繊維等の織布、編み物、組
み物、不織布、紙等が用いられる。多孔質シートとして
は連通気孔を有する膜又はフイルム状のものであり、ポ
リウレタン、ポリスチレンあるいはポリプロピレン等の
フォームシートや延伸、抽出又は凝固法などでつくるポ
リプロピレンあるいはポリスルフォン等の多孔膜が用い
られる。その目開きは、使用する軽量弾性粒子、発泡性
樹脂粒子の種類やその発泡性に応じて選択される。この
分離層にそれ自体補強機能を有するガラス繊維、炭素繊
維、アラミド繊維等のシートを用いることもできる。こ
れらのシートは、表面に色彩や模様を施したものでもよ
い。さらにこの分離層として容易に目的成形物の形状に
合せるように伸縮性を有する材料を選択することもでき
る。また、分離層の一部を液状成形樹脂を通さない材料
で構成することも可能である。例えば、分離機能を有す
る部分を構成する材料とは異なった材料とつなぎ合わせ
る以外に、分離機能を有する繊維シート及び/又は多孔
質シートの一部を予め樹脂等でその目開きを封止処理し
たもの、繊維シートがポリプロピレン繊維など加熱処理
により融着させ得る場合にはその一部を融着処理により
目開きをつぶしもの、一部にフイルム等を貼付けたもの
なども使用できる。
A fiber sheet and / or a porous sheet are mentioned as what constitutes the separation function of such a separation layer. As the fibrous sheet, woven fabric, knitted fabric, braided fabric, non-woven fabric, paper and the like of various natural fibers, synthetic fibers, metal fibers, inorganic fibers such as carbon or ceramics are used. The porous sheet is a film or a film having open pores, and a foam sheet of polyurethane, polystyrene, polypropylene or the like, or a porous film of polypropylene, polysulfone or the like produced by a stretching, extraction or coagulation method is used. The openings are selected according to the types of the lightweight elastic particles and the expandable resin particles used and the expandability thereof. A sheet of glass fiber, carbon fiber, aramid fiber or the like, which itself has a reinforcing function, can be used for this separation layer. These sheets may have their surfaces colored or patterned. Further, as the separating layer, a material having elasticity can be selected so as to easily match the shape of the target molded product. It is also possible to form a part of the separation layer with a material that does not allow the liquid molding resin to pass through. For example, in addition to joining with a material different from the material forming the part having the separating function, a part of the fiber sheet and / or the porous sheet having the separating function is preliminarily sealed with a resin or the like to open its openings. In the case where the fibrous sheet can be fused by heat treatment such as polypropylene fiber, it is also possible to use a portion of which the openings are closed by fusion treatment or a portion of which a film or the like is attached.

また、上記分離層の外側に重ねて補強用の繊維シート
やプリフォームを併用してもよい。この場合は補強用繊
維シートやプリフォームの目開きは自由に選択でき、例
えば一方向繊維配列プリプレグや三次元織物や編み物の
プリフォームも使用できる。
Further, a reinforcing fibrous sheet or preform may be used in combination on the outside of the separation layer. In this case, the openings of the reinforcing fiber sheet and the preform can be freely selected, and for example, a unidirectional fiber array prepreg, a three-dimensional woven fabric or a knit preform can be used.

また、分離層及び/又は補強用の繊維シートやプリフ
ォームを予めプリプレグの形で樹脂処理しておくことも
該分離層が本発明で目的とする分離機能を失わない限り
可能である。
It is also possible to subject the separation layer and / or the reinforcing fiber sheet or preform to a resin treatment in advance in the form of a prepreg, as long as the separation layer does not lose the separation function intended by the present invention.

なお、平板や表裏のある面状の成形物を製造する場
合、分離層を型の内面の一方の側だけに設置することも
できる。このケースでは、他の側は、分離層を設けない
場合や分離層の代わりに液状成形樹脂も通さないフィル
ム等の材料を設置する場合などがあるが、目的に応じて
選択すればよい。例えば、自動二輪車のカウリングの場
合、表面側に印刷したフイルムを設置し、裏面側にガラ
ス繊維の分離層を用いることで、成形後表面側を塗装し
デカールを貼る作業を簡略化できる。
In the case of producing a flat plate or a flat shaped product having front and back surfaces, the separation layer may be provided only on one side of the inner surface of the mold. In this case, the other side may be provided with no separation layer or may be provided with a material such as a film that does not pass the liquid molding resin instead of the separation layer, but it may be selected according to the purpose. For example, in the case of a cowling for a motorcycle, by installing a printed film on the front surface side and using a glass fiber separation layer on the back surface side, it is possible to simplify the work of painting the front surface side and applying decals after molding.

本発明方法では、このような分離層によって発泡性樹
脂粒子、非膨張性の軽量弾性粒子及び液状成形樹脂から
なる組成物を囲んだ(挟み込んだ)状態にて成型用の型
内で発泡性樹脂粒子を熱膨張させ、それによる圧力によ
って内圧成形することで多孔質コアを形成させるが、分
離層内の領域に、予め成形した多孔質のコア材や中空ガ
ラスビーズ等を併存させてもよい。
In the method of the present invention, the composition comprising the expandable resin particles, the non-expandable lightweight elastic particles and the liquid molding resin is surrounded (sandwiched) by such a separating layer, and the foaming resin is molded in the molding die. Although a porous core is formed by thermally expanding the particles and molding by internal pressure by the pressure generated by the particles, a preformed porous core material, hollow glass beads, or the like may coexist in the region within the separation layer.

以下、工程を追って、熱膨張性の発泡性樹脂粒子と非
熱膨張性の軽量弾性粒子とを併用して成形することを最
大の特徴とする、本発明方法を詳細に説明する。
In the following, the method of the present invention, which is characterized by the combined use of thermally expandable expandable resin particles and non-thermally expandable lightweight elastic particles, will be described in detail in the order of steps.

本発明方法によれば、まず成形用の型を用意する。こ
の型は、成形温度等に応じて、材料を選択する。所謂狭
義の金型、木型、樹脂型等のうちから適宜選択して使用
される、型の内面に沿って、上述の分離層となるシート
を設置する。該分離層用シートの他に、補強繊維シート
を別途重ねるか、又は、分離層自体を補強繊維で構成す
るのが好ましい。
According to the method of the present invention, a mold for molding is first prepared. The material of this mold is selected according to the molding temperature and the like. A sheet to be the above-mentioned separation layer is installed along the inner surface of the mold, which is used by appropriately selecting from a so-called narrowly defined mold, wooden mold, resin mold and the like. In addition to the separation layer sheet, a reinforcing fiber sheet is preferably stacked separately, or the separation layer itself is preferably composed of reinforcing fibers.

この型は、ガス・液抜き用のノズルを持ち、このノズ
ルと型本体との間に、軽量弾性粒子と発泡性樹脂粒子を
通さず液状の成形樹脂を通す装置(フィルター)を設け
ている。この型の内部に、軽量弾性粒子と発泡性樹脂粒
子と、必要に応じガラスバルーン等と、硬化性樹脂の混
合物を入れ、空間を残して型を閉じる。この際、型内を
真空することが好ましい。次に、型内に適量の樹脂が存
在しない場合は、この型内に液状の硬化性樹脂を導入す
る。好ましくは該樹脂が溢流することを確めて導入を止
める。型の上方のノズルを開いたまま加熱し、発泡性樹
脂粒子を膨張させると、分離層は型の内面に押しつけら
れ、かつ液状の樹脂は分離層内に浸透しその一部は外側
の成形物表層部に至る。そして液状の硬化性樹脂をノズ
ルから溢流させながら硬化させる。必要ならば途中で溢
流を止めるためノズルを閉じる。
This mold has a nozzle for discharging gas and liquid, and a device (filter) for passing the liquid molding resin without passing the lightweight elastic particles and the expandable resin particles is provided between the nozzle and the mold body. A mixture of lightweight elastic particles, expandable resin particles, and optionally a glass balloon, and a curable resin is put inside the mold, and the mold is closed leaving a space. At this time, it is preferable to vacuum the inside of the mold. Next, when an appropriate amount of resin is not present in the mold, a liquid curable resin is introduced into the mold. Preferably, the introduction is stopped by making sure that the resin overflows. When the expandable resin particles are expanded by heating with the nozzle above the mold open, the separation layer is pressed against the inner surface of the mold, and the liquid resin penetrates into the separation layer and part of it is the outer molding. To the surface layer. Then, the liquid curable resin is cured while overflowing from the nozzle. If necessary, close the nozzle to stop the overflow on the way.

この際、コア部の軽量弾性粒子は発泡性樹脂粒子の発
泡により生ずる圧力により一たん縮小するが、発泡が頂
点をすぎ発泡した粒子の縮小が生じるとそれを補うよう
に軽量弾性粒子が膨張し、成形物に樹脂の不足部を生ず
るのを防止するように働く。
At this time, the lightweight elastic particles in the core portion are simply contracted due to the pressure generated by the foaming of the expandable resin particles, but when the expansion goes past the apex and the expanded particles contract, the lightweight elastic particles expand to compensate for them. , It works to prevent the lack of resin in the molded product.

それとともに樹脂は硬化するが、樹脂の硬化後に冷却
して、型より成形物を取り出す。液状の硬化性樹脂は例
えば補強繊維シートに多量に含ませておき、樹脂の導入
を省略することもできる。
Along with that, the resin hardens, but after the resin hardens, it is cooled and the molded product is taken out from the mold. The liquid curable resin may be included in the reinforcing fiber sheet in a large amount, for example, and the introduction of the resin may be omitted.

[発明の効果] 上述の如き本発明方法により、良好な表面を持った、
軽量のハニカム材等の構造材料として有用な複合成形物
が得られる。すなわち、発泡性樹脂粒子を加熱膨張させ
て内圧を発生させる成形において、該発泡性樹脂粒子及
びマトリックスとなる硬化性樹脂の収縮がおきても成形
物表面や特定部分に硬化樹脂が不足することもなく、成
形工程や成形物の品質安定性も良好である。
[Effects of the Invention] The method of the present invention as described above has a good surface,
A composite molded article useful as a structural material such as a lightweight honeycomb material can be obtained. That is, in the molding in which the expandable resin particles are heated and expanded to generate an internal pressure, even if the expandable resin particles and the curable resin serving as the matrix contract, the cured resin may be insufficient on the surface of the molded product or a specific portion. In addition, the molding process and the quality stability of the molded product are good.

本発明方法の当初の目的は、発泡性樹脂粒子等の、成
形完了前の収縮の発生に対する対策であった。しかしな
がら、本発明方法を現実に実施してみると、驚くべきこ
とに、ガラスバルーン等中空体の無機中空体を添加して
成形する場合よりむしろ成形物の軽量化がはかれている
ことが判った。これは、一般に軽量弾性粒子として用い
るポリプロピレン発泡体等の比重が無機中空体より低比
重であるからと考えられる。また、多少の反発力を軽量
弾性粒子に残存している成形物でも、コア部に存在する
樹脂の硬化が完了すれば、その中に包蔵される軽量弾性
粒子は成形物の変形等の問題を起こさないことも確認さ
れた。
The original purpose of the method of the present invention was to prevent shrinkage of expandable resin particles and the like before the completion of molding. However, when the method of the present invention is actually carried out, it is surprisingly found that the weight of the molded article is reduced rather than the case where the inorganic hollow body such as a glass balloon is added and molded. It was It is considered that this is because the specific gravity of the polypropylene foam or the like generally used as the lightweight elastic particles is lower than that of the inorganic hollow body. Further, even in a molded product in which a small amount of repulsive force remains in the lightweight elastic particles, when the curing of the resin existing in the core portion is completed, the lightweight elastic particles contained therein cause problems such as deformation of the molded product. It was also confirmed that it would not happen.

[実施例] 次に、本発明の実施例及び比較例をあげて説明する
が、本発明はこれにより限定されるものではない。な
お、特に断りのないかぎり、各例中の「部」は重量部で
ある。
[Examples] Next, examples and comparative examples of the present invention will be described, but the present invention is not limited thereto. In addition, "part" in each example is a weight part unless there is particular notice.

実施例1 シェル(株)製のエポキシ樹脂「エピコート807」100
部と硬化剤「エポメートYLH007」31部と混合した。これ
を液状硬化性樹脂Aとする。
Example 1 Epoxy Coat 807, an epoxy resin manufactured by Shell Co., Ltd. 100
Parts and 31 parts of the curing agent "Epomate YLH007". This is a liquid curable resin A.

一方、ポリプロピレンに分散剤、発泡剤(フレオン1
2)及び水を加え、加熱、加圧し、これを低圧帯に放出
して発泡粒子(ビーズ)を得た。この粒子は、内部に多
数の気泡を含むが更に加熱しても実際上の発泡はなく、
かつ圧縮により縮小し圧力の解除によって復元する軽量
弾性粒子であった。
On the other hand, polypropylene has a dispersant and a foaming agent (Freon 1
2) and water were added, heated and pressurized, and this was discharged into the low pressure zone to obtain expanded particles (beads). This particle contains many bubbles inside, but there is no actual foaming when heated further,
Moreover, it was a lightweight elastic particle that contracted by compression and restored by release of pressure.

次に、上記の液状硬化性樹脂A100部中に発泡性樹脂粒
子として松本油脂製薬(株)製の発泡性バルーン「マイ
クロスフェアーF−30D」を44部、上記の軽量弾性粒子
(ポリプロピレンビーズ)を10部混合した。得られたも
のを発泡性樹脂混合物Bとする。
Next, 44 parts of expandable balloon "Microsphere F-30D" manufactured by Matsumoto Yushi-Seiyaku Co., Ltd. as expandable resin particles in 100 parts of the above liquid curable resin A and the above lightweight elastic particles (polypropylene beads). Were mixed in 10 parts. Let the obtained thing be the foamable resin mixture B.

分離層として、ポリエチレンテレフタレート繊維とポ
リプロピレンの繊維で作られた長繊維不織布「ユニセ
ル」を用い、後述の金型の内寸に合わせてやや小さ目の
袋を作った。この分離層の袋の中に発泡性樹脂混合物B
を詰めた。
As the separation layer, a long-fiber non-woven fabric "UNICEL" made of polyethylene terephthalate fiber and polypropylene fiber was used, and a slightly smaller bag was made according to the inner size of the mold described later. The foamable resin mixture B is placed in a bag of this separation layer.
Packed.

一方、アルミニウムの板2枚の間に、「テフロン」の
枠を挟んだ金型を作成した。この金型には上下の端にノ
ズルを設けた。金型一杯の大きなガラスクロス6枚と、
長さを金型に合せ幅をノズルを覆うサイズにした短冊状
ガラスクロス8枚とを作り、大きなガラスクロスを用い
て、ガラスクロス/発泡性樹脂混合物Bの袋詰め/ガラ
スクロスの順で重ね合せるよう金型に入れた。一方、小
さなガラスクロスを重ねてノズルを覆う位置つまり金型
の上下端を埋めた。そして、上方のノズルを用いて金型
内部を吸引し真空にした。次いで、液状硬化性樹脂Aを
下方のノズルより金型内部へ圧入し、上方のノズルから
樹脂が溢れることを確認した。しばらく放置してから金
型を70℃の温水浴中に入れ加熱して発泡性バルーンを発
泡膨張させ、内圧が正になってからノズルを微開した。
内圧を6kg/cm2を保ちながら液状硬化性樹脂を抜きつつ
硬化させた。
On the other hand, a mold in which a "Teflon" frame was sandwiched between two aluminum plates was prepared. Nozzles were provided at the upper and lower ends of this mold. 6 large glass cloths full of molds,
Eight strip-shaped glass cloths, each of which has a length matched with a mold and a width that covers the nozzle, are made, and a large glass cloth is used to stack the glass cloth / foamable resin mixture B in a bag / glass cloth in this order. I put it in the mold to match. On the other hand, a small glass cloth was overlapped to fill the position covering the nozzle, that is, the upper and lower ends of the mold. Then, the upper nozzle was used to suck the inside of the mold to create a vacuum. Next, the liquid curable resin A was pressed into the mold from the lower nozzle, and it was confirmed that the resin overflowed from the upper nozzle. After leaving it for a while, the mold was placed in a hot water bath at 70 ° C. to heat the foamable balloon to expand and expand, and after the internal pressure became positive, the nozzle was slightly opened.
While the internal pressure was kept at 6 kg / cm 2 , the liquid curable resin was removed and cured.

1時間後に温水浴から取りだし、冷却して金型から成
形物を取りだした。かくして、表面層がガラス繊維強化
エポキシ樹脂、内層(コア部)が気泡含有エポキシ樹脂
である軽量で良好なサンドイッチ状構造材が得られた。
この操作を繰返した結果も全て同様で、成形物平均比重
は0.52であった。
After 1 hour, the molded product was taken out of the hot water bath, cooled, and taken out of the mold. Thus, a lightweight and good sandwich-like structural material having the glass fiber reinforced epoxy resin as the surface layer and the bubble-containing epoxy resin as the inner layer (core portion) was obtained.
The results of repeating this operation were all the same, and the average specific gravity of the molded product was 0.52.

比較のため、上記ポリプロピレンビーズの代わりに、
旭硝子製の中空ガラスビーズQ−Cell 575を22部用い
たものは中央部に樹脂の足りないものが30%でき、成形
物の平均比重は0.62であった。
For comparison, instead of the polypropylene beads,
In the case of using 22 parts of the hollow glass beads Q-Cell 575 manufactured by Asahi Glass, 30% of the resin lacked in the central part, and the average specific gravity of the molded product was 0.62.

(なお、ポリプロピレンビーズ10部と中空ガラスビーズ
Q−Cell 575 22部は、同じ容積である。) 実施例2 実施例1と同様にして液状硬化性樹脂Aを準備した。
但し、樹脂の総量は575部である。一方、軽量弾性粒子
であるポリプロピレンビーズPB−MG15Pを入手した。こ
の粒子は嵩比重約0.05g/cm3であり、これを8部準備し
た。一方、発泡性樹脂粒子である松本油脂製薬(株)製
の発泡性バルーン「マツモトマイクロスフェアーF−30
D」を48部準備した。
(Note that 10 parts of polypropylene beads and 22 parts of hollow glass beads Q-Cell 575 have the same volume.) Example 2 Liquid curable resin A was prepared in the same manner as in Example 1.
However, the total amount of resin is 575 parts. On the other hand, polypropylene beads PB-MG15P, which are lightweight elastic particles, were obtained. The particles had a bulk specific gravity of about 0.05 g / cm 3 , and 8 parts of this was prepared. On the other hand, expandable resin particles Matsumoto Yushi-Seiyaku Co., Ltd. expandable balloon "Matsumoto Microsphere F-30"
48 copies of "D" were prepared.

一方、最大幅120mm、最大長さ350mm、最大厚さ14mm
の、舵状のモデルを作る雄型2個の金型を作成した。金
型の上下にはそれぞれノズルを設けた。この金型の内寸
に合わせたガラスクロス6葉も準備した。分離層として
ポリエステル系不織布「ユニセルBT−0404」を金型内寸
に合わせて袋状となし、これに上記のポリプロピレンビ
ーズと発泡性バルーンを収め、シールした。
On the other hand, maximum width 120 mm, maximum length 350 mm, maximum thickness 14 mm
I made two male molds to make a rudder model. Nozzles were provided above and below the mold. Six leaves of glass cloth were also prepared according to the inner dimensions of this mold. As a separation layer, a polyester non-woven fabric "UNICEL BT-0404" was formed into a bag according to the inner size of the mold, and the polypropylene beads and the expandable balloon were placed in the bag and sealed.

ポリプロピレンビーズ8部と発泡性バルーン48部とを
収めた袋を中心に、上下をガラスクロスで覆い、金型に
収めて金型を閉じた。この金型内部を真空に引き、上記
の液状硬化性樹脂A(エポキシ系樹脂)を下方のノズル
から圧入し、上方のノズルから溢れさせた。
A bag containing 8 parts of polypropylene beads and 48 parts of a foamable balloon was placed at the center of the bag, and the top and bottom were covered with a glass cloth. The bag was housed in a mold and the mold was closed. The inside of the mold was evacuated, the liquid curable resin A (epoxy resin) was press-fitted from the lower nozzle, and overflowed from the upper nozzle.

液状硬化性樹脂Aの注入した金型を70℃の温浴に入
れ、発泡性バルーンを発泡膨張させ、余分の液状硬化性
樹脂を流出させた。流出が続くうちにノズルを閉じた。
1時間保持後、温水浴から取りだし、冷却して成形物を
取りだしたところ、比重0.8の良好な複合成形物が得ら
れた。
The mold into which the liquid curable resin A had been poured was placed in a hot bath at 70 ° C., the expandable balloon was expanded and expanded, and the excess liquid curable resin was caused to flow out. The nozzle was closed while the outflow continued.
After holding for 1 hour, the molded product was taken out from the warm water bath, cooled, and taken out. As a result, a good composite molded product having a specific gravity of 0.8 was obtained.

比較のため、ポリプロピレンビーズの代わりに、旭硝
子製の中空ガラスビーズM28を24部用いたものを用い
て、同様に成形したところ、成形物の一番肉厚の部分の
表面は硬化樹脂が不足していた。(このガラスビーズ量
は、体積基準でポリプロピレンビーズと同じである。) また、ポリプロピレンビーズ及び松本油脂製薬(株)
製の発泡性バルーンの代わりに、ポリスチレンの膨張ビ
ーズのみを用いたものも同様に成形した。得られた成形
物は一番厚い部分の表面の樹脂が不足していた。
For comparison, instead of polypropylene beads, using 24 parts of Asahi Glass hollow glass beads M28, when molded in the same manner, the surface of the thickest part of the molded product lacked cured resin Was there. (The amount of this glass beads is the same as that of polypropylene beads on a volume basis.) Polypropylene beads and Matsumoto Yushi-Seiyaku Co., Ltd.
Instead of the expandable balloon made of polystyrene, a product using only expanded beads of polystyrene was similarly molded. The obtained molded product lacked the resin on the surface of the thickest part.

実施例3 根上工業製イソシアネートC−46を100部、東洋ゴム
製ソフランR1109−50FSを80部の割合で混合した原料を
用いて第1の金型で発泡体を成形した。得られた発泡成
形物をコア材とする。
Example 3 A foam was molded with a first mold using a raw material prepared by mixing 100 parts of NEOJI KOGYO ISocyanate C-46 and 80 parts of Toyo Rubber Soflan R1109-50FS. The foamed molded product thus obtained is used as the core material.

一方、実施例1と同様に、「エピコート807」と「エ
ポメートYLH006」とを重量比100対31の割合で混合した
硬化性液状樹脂を調製した。
On the other hand, in the same manner as in Example 1, a curable liquid resin was prepared by mixing "Epicoat 807" and "Epomate YLH006" at a weight ratio of 100: 31.

実施例1と同様に分離層としてポリエチレンテレフタ
レートとポリプロピレンの繊維で作った長繊維不織布
「ユニセルBT4040」を用い、これで上記コア材を中心
に、実施例1と同様のポリプロピレンビーズ10部、実施
例1と同様の松本油脂製薬(株)製の発泡性バルーン
「マイクロフェアー」F−30D 44部を包み込んで第2
の金型の内寸に合わせてやや小さ目の袋を作成した。
As in Example 1, a long-fiber non-woven fabric "UNICEL BT4040" made of polyethylene terephthalate and polypropylene fibers was used as a separation layer, and 10 parts of polypropylene beads similar to those in Example 1, centering on the core material, were used. The same as No. 1, Matsumoto Yushi-Seiyaku Co., Ltd., expandable balloon "Microfair" F-30D 44 parts wrapped around
I made a slightly smaller bag according to the inner size of the mold.

この包みをさらに日東紡製のガラスクロスWE−181−1
00BVで包み込み、これを第2の金型(複合成形物の成形
用金型)に収めた。この金型に設けた上方のノズルから
内部を吸引して金型内部を真空にした。次いで、上記液
状硬化性樹脂を下方のノズルより導入し、上方のノズル
から溢れることを確認した。
This package is further made by Nitto Bosh glass cloth WE-181-1.
It was wrapped with 00BV and placed in a second mold (mold for molding a composite molded product). The inside of the mold was evacuated by sucking the inside from the upper nozzle provided in this mold. Next, it was confirmed that the liquid curable resin was introduced from the lower nozzle and overflowed from the upper nozzle.

その後、実施例1と全く同様にしてこの第2の金型を
温水浴に入れ、余分の樹脂を上方のノズルから抜きなが
ら、硬化させた。1時間後に温水浴から取りだし、冷却
して金型から成形物を取りだした。かくして、表面層が
ガラス繊維強化エポキシ樹脂、内層(コア)がポリウレ
タンフォーム、軽量粒子類及び硬化したエポキシ樹脂か
らなる軽量で良好なサンドイッチ状構造材が得られた。
Then, the second mold was placed in a warm water bath in exactly the same manner as in Example 1 and cured while removing excess resin from the upper nozzle. After 1 hour, the molded product was taken out of the hot water bath, cooled, and taken out of the mold. Thus, a lightweight and good sandwich-like structural material having a glass fiber reinforced epoxy resin as the surface layer, polyurethane foam as the inner layer (core), lightweight particles and cured epoxy resin was obtained.

Claims (3)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】少なくとも硬化した成形樹脂により所定の
形状に形成された表層部、多孔質のコア部、及び表層部
とコア部との間に介在する分離層を有する軽量複合成形
物を製造するに当り、 (a)成形用の型内に、熱膨脹後の発泡性樹脂粒子及び
非熱膨脹性軽量弾性粒子を実質的に通さないが硬化性の
液状成形樹脂は通す分離層を設置すること、 (b)分離層に囲まれた、成形後に多孔質コア部となる
領域に、発泡性樹脂粒子と非熱膨脹性軽量弾性粒子と硬
化性の液状成形樹脂との混合物を存在させること、 (c)型の所定の領域を十分高い温度まで加熱すること
及び/又は上記硬化性樹脂の反応熱による温度上昇によ
り、発泡性樹脂粒子を加熱発泡させて体積膨脹を生じさ
せ、これにより分離層を型の内面に対して押しつけると
ともに硬化性の液状成形樹脂を分離層に浸透させて、表
層部に至らせること、 (d)上記液状成形樹脂を硬化させて成形すること、そ
して、 (e)得られた複合成形物を型から取り出すこと、 を特徴とする軽量複合成形物の製造方法。
1. A lightweight composite molded article having a surface layer portion formed in a predetermined shape from a cured molding resin, a porous core portion, and a separation layer interposed between the surface layer portion and the core portion is manufactured. In this regard, (a) a separating layer is provided in the mold for molding, in which the expandable resin particles after thermal expansion and the non-heat-expandable lightweight elastic particles are substantially impervious but the curable liquid molding resin is impervious. b) The presence of a mixture of the expandable resin particles, the non-heat-expandable lightweight elastic particles and the curable liquid molding resin in a region surrounded by the separation layer to be a porous core portion after molding, (c) type By heating a predetermined region of the resin to a sufficiently high temperature and / or increasing the temperature by the reaction heat of the curable resin, the expandable resin particles are heated and foamed to cause volume expansion, whereby the separation layer forms the inner surface of the mold. Pressed against and hard Of a water-soluble molding resin into the separation layer to reach the surface layer portion, (d) curing of the above-mentioned molding resin for molding, and (e) taking out the obtained composite molded product from the mold. A method for producing a lightweight composite molded article, comprising:
【請求項2】少なくとも硬化した成形樹脂により所定の
形状に形成された表層部、多孔質のコア部、及び表層部
とコア部との間に介在する分離層を有する軽量複合成形
物を製造するに当り、 (a)成形用の型内に、熱膨脹後の発泡性樹脂粒子及び
非熱膨脹性軽量弾性粒子を実質的に通さないが硬化性の
液状成形樹脂は通す分離層を設置すること、 (b)分離層に囲まれた、成形後に多孔質コア部となる
領域に、発泡性樹脂粒子と非熱膨脹性軽量弾性粒子とを
存在させること、 (c)次いで、型に液状の硬化性樹脂を導入すること、 (d)型の所定領域を十分高い温度まで加熱すること及
び/又は上記硬化性樹脂の反応熱による温度上昇によ
り、発泡性樹脂粒子を加熱発泡させて体積膨脹を生じさ
せ、これにより分離層を型の内面に対して押しつけると
ともに硬化性の液状成形樹脂を分離層に浸透させて、表
層部に至らせること、 (e)上記液状成形樹脂を硬化させて成形すること、そ
して、 (f)得られた複合成形物を型から取り出すこと、 を特徴とする軽量複合成形物の製造方法。
2. A lightweight composite molded article having a surface layer portion formed in a predetermined shape by at least a cured molding resin, a porous core portion, and a separation layer interposed between the surface layer portion and the core portion is manufactured. In this regard, (a) a separating layer is provided in the mold for molding, in which the expandable resin particles after thermal expansion and the non-heat-expandable lightweight elastic particles are substantially impervious but the curable liquid molding resin is impervious. b) allowing the expandable resin particles and the non-heat-expandable lightweight elastic particles to be present in a region surrounded by the separation layer, which becomes the porous core portion after molding, (c) and then adding a liquid curable resin to the mold. By introducing, heating a predetermined region of the (d) type to a sufficiently high temperature, and / or increasing the temperature by the reaction heat of the curable resin, the expandable resin particles are heated and foamed to cause volume expansion, and To push the separation layer against the inner surface of the mold. Baking and allowing a curable liquid molding resin to penetrate into the separation layer to reach the surface layer portion, (e) curing and molding the above liquid molding resin, and (f) the obtained composite molding And removing from the mold.
【請求項3】分離層の外側に、補強用繊維質シートを重
ね合せて成形することを特徴とする請求項(1)又は請
求項(2)に記載の製造方法。
3. The manufacturing method according to claim 1, wherein a reinforcing fibrous sheet is superposed on the outer side of the separation layer and is molded.
JP1317623A 1989-12-08 1989-12-08 Method for manufacturing lightweight composite molded article Expired - Lifetime JP2553206B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP1317623A JP2553206B2 (en) 1989-12-08 1989-12-08 Method for manufacturing lightweight composite molded article

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1317623A JP2553206B2 (en) 1989-12-08 1989-12-08 Method for manufacturing lightweight composite molded article

Publications (2)

Publication Number Publication Date
JPH03180329A JPH03180329A (en) 1991-08-06
JP2553206B2 true JP2553206B2 (en) 1996-11-13

Family

ID=18090239

Family Applications (1)

Application Number Title Priority Date Filing Date
JP1317623A Expired - Lifetime JP2553206B2 (en) 1989-12-08 1989-12-08 Method for manufacturing lightweight composite molded article

Country Status (1)

Country Link
JP (1) JP2553206B2 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6805646B2 (en) 2000-08-29 2004-10-19 Tsubakimoto Chain Co. Double-sided meshing type silent chain
US7476170B2 (en) 2004-06-15 2009-01-13 Tsubakimoto Chain Co. Double-sided silent chain
US7771304B2 (en) 2005-11-11 2010-08-10 Tsubakimoto Chain Co. Double-sided engagement type silent chain

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9920071D0 (en) * 1999-08-24 1999-10-27 Btg Int Ltd Carbon composite manufacturing techniques
WO2022209455A1 (en) * 2021-03-30 2022-10-06 東レ株式会社 Flat lightweight member and method for producing same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6805646B2 (en) 2000-08-29 2004-10-19 Tsubakimoto Chain Co. Double-sided meshing type silent chain
US7476170B2 (en) 2004-06-15 2009-01-13 Tsubakimoto Chain Co. Double-sided silent chain
US7771304B2 (en) 2005-11-11 2010-08-10 Tsubakimoto Chain Co. Double-sided engagement type silent chain

Also Published As

Publication number Publication date
JPH03180329A (en) 1991-08-06

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