JP3035618B2 - Fiber-reinforced thermoplastic resin sheet material and method for producing the same - Google Patents
Fiber-reinforced thermoplastic resin sheet material and method for producing the sameInfo
- Publication number
- JP3035618B2 JP3035618B2 JP2418525A JP41852590A JP3035618B2 JP 3035618 B2 JP3035618 B2 JP 3035618B2 JP 2418525 A JP2418525 A JP 2418525A JP 41852590 A JP41852590 A JP 41852590A JP 3035618 B2 JP3035618 B2 JP 3035618B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- reinforcing fiber
- fiber fabric
- impregnated
- fabric
- 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.)
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Description
【０００１】本発明は、強化繊維束に熱可塑性樹脂を均
一にかつ、十分に含浸せしめた繊維強化熱可塑性樹脂シ
ート製造方法に関する。The present invention relates to a method for producing a fiber-reinforced thermoplastic resin sheet in which a reinforcing fiber bundle is uniformly and sufficiently impregnated with a thermoplastic resin.
【０００２】炭素繊維、ガラス繊維等の強化繊維で補強
した熱可塑性複合材料は、強化繊維に由来する、優れた
力学的性質と樹脂の熱可塑性に由来する優れた成形性、
熱融着性及び短時間の成形性を兼ね備えた優れた材料と
してよく知られている。特に、高強度化、軽量化が要求
されつつある、スポーツ用品、日常品用として比較的低
温で賦型が可能な、繊維強化アクリル樹脂が提案されて
いる（米国特許４７７８７１７）。A thermoplastic composite material reinforced with reinforcing fibers such as carbon fiber and glass fiber has excellent mechanical properties derived from reinforcing fibers and excellent moldability derived from thermoplasticity of a resin.
It is well known as an excellent material having both heat fusion property and short-time moldability. In particular, high strength, light weight is being requested, sporting goods, capable of relatively shaping at a low temperature for the everyday objects, fiber reinforced acrylic resin has been proposed (U.S. Pat 47 7 8717).
【０００３】従来、このような材料を製造する方法とし
ては、下記の方法が用いられてきた。 （１）樹脂を軟化する温度にし、強化繊維ファブリック
に含浸する方法。 （２）メチルエチルケトン等の溶剤に樹脂を溶解し、こ
の溶液を強化繊維ファブリックに含浸した後、溶剤を揮
発する方法。Conventionally, the following method has been used as a method for producing such a material. (1) A method in which the temperature is set to soften the resin and the reinforcing fiber fabric is impregnated. (2) A method of dissolving a resin in a solvent such as methyl ethyl ketone, impregnating the solution with a reinforcing fiber fabric, and then evaporating the solvent.
【０００４】しかし（１）の方法では、樹脂の溶融粘度
が１０5 〜１０6 センチポイズと高く、完全に樹脂を繊
維に含浸することが困難であり、また高温高圧を必要と
するため、高価な装置が必要となる。また（２）の方法
では、溶剤を完全に揮発することが困難であり、材料中
に残留した溶剤はその力学的性質を低下させるばかりで
なく、回収できない溶剤は製造コストを引き上げる。However, in the method (1), the melt viscosity of the resin is as high as 10 5 to 10 6 centipoise, and it is difficult to completely impregnate the fiber with the resin. Equipment is required. Further, in the method (2), it is difficult to completely volatilize the solvent, and the solvent remaining in the material not only lowers its mechanical properties but also increases the production cost if the solvent cannot be recovered.
【０００５】そこで、本発明者らは、強化繊維ファブリ
ックにより強化されたアクリル系樹脂において、強化繊
維間の空隙がアクリル系樹脂で十分に満たされたシート
材料を効率的、連続的に製造する方法について鋭意検討
を行ない、本発明に到達した。[0005] Therefore, the present inventors have found that efficient in acrylic resin reinforced by reinforcing fibers fabric, a sheet <br/> materials voids are sufficiently filled with the acrylic resin among the reinforcing fibers, continuous The present inventors have conducted intensive studies on a method of manufacturing the semiconductor device and arrived at the present invention.
【０００６】本発明は、強化繊維ファブリックに、メタ
クリル酸アルキルエステル及び／又はアクリル酸アルキ
ルエステルとこれらに溶解する熱可塑性重合体を主成分
とし、粘度が１０〜１０ ４ センチポイズの範囲にあるア
クリル系硬化性樹脂組成物を含浸した、まだ硬化してい
ない繊維強化熱可塑性樹脂シート材料を第１の要旨と
し、粘度が１０〜１０４センチポイズの範囲にある常温
又は加熱硬化性アクリル系樹脂液と強化繊維ファブリッ
クとを接触させ、前記強化繊維ファブリックに前記樹脂
液が含浸した繊維強化アクリル系樹脂の前駆体としたの
ち、必要に応じ、これを室温及び／又は加熱して硬化さ
せることによる繊維強化熱可塑性樹脂シート材料の製造
方法であり、常温又は加熱硬化性アクリル系樹脂を使用
することを特徴とする。[0006] The present invention relates to a reinforcing fiber fabric,
Alkyl acrylate and / or alkyl acrylate
Luster and a thermoplastic polymer soluble in them
And, A viscosity in the range of 10 to 10 4 centipoise
Impregnated with a curable curable resin composition, not yet cured
No fiber reinforced thermoplastic resin sheet material with the first gist
And, contacting the reinforcing fiber fabric and at room temperature or heat curing acrylic resin solution having a viscosity in the range of 10 to 10 4 centipoise, precursor of the fiber-reinforced acrylic resin wherein the resin solution is impregnated into the reinforcing fiber fabric And , if necessary, a method for producing a fiber-reinforced thermoplastic resin sheet material by curing the sheet material at room temperature and / or by heating, wherein a room temperature or heat-curable acrylic resin is used. .
【０００７】本発明においては、粘度が１０〜１０４セ
ンチポイズの範囲にある、アクリル系樹脂液と強化繊維
ファブリックとを接触し、前記の強化繊維ファブリック
に前記樹脂液が含浸した、繊維強化アクリル系樹脂前駆
体としたのち、常温及び／又は加熱により硬化させ、繊
維強化アクリル系樹脂シートを得る際に下記の操作を順
次行なうことが好ましい。 （Ａ）常温又は加熱硬化性アクリル系樹脂と硬化触媒と
からなる樹脂組成物と強化繊維ファブリックとを連続的
に接触させ、強化繊維ファブリックに該組成物が付着し
た付着物を得ること。 （Ｂ）前記付着物を連続方向に張力をかけつつ、上下か
ら通気性の少ないフィルムで挟持しつつ、移送するこ
と。 （Ｃ）前記フィルムに挟持した状態で１対以上のローラ
ーにより付着物の厚みを減少することによって押圧を加
え、樹脂組成物が強化繊維ファブリックの横断面にわた
って含浸すると同時に、付着物中に散在している気泡を
余剰の樹脂とともに、フィルムの両端より外へ流出せし
めた含浸物を得ること。 （Ｄ）前記、含浸物中の樹脂の硬化後、フィルムを剥離
して、硬化したシート状物を得ること。[0007] In the present invention, the viscosity is in the range of 10 to 10 4 centipoise, contacting the reinforcing fiber fabric and an acrylic resin solution, the resin solution is impregnated into the reinforcing fiber fabric, fiber reinforced acrylic After forming the resin precursor, the resin precursor is cured at room temperature and / or heat, and the following operation is preferably performed in order to obtain a fiber-reinforced acrylic resin sheet. (A) A resin composition comprising a room-temperature or heat-curable acrylic resin and a curing catalyst is brought into continuous contact with a reinforcing fiber fabric to obtain an adhering substance in which the composition adheres to the reinforcing fiber fabric. (B) transferring the attached matter while applying tension in a continuous direction and sandwiching the film from above and below with a film having low air permeability. (C) Pressing by reducing the thickness of the deposit with one or more rollers while sandwiching the film, the resin composition is impregnated over the cross section of the reinforcing fiber fabric, and is simultaneously scattered in the deposit. To obtain an impregnated material in which air bubbles are allowed to flow out from both ends of the film together with excess resin. (D) After the resin in the impregnated material is cured, the film is peeled off to obtain a cured sheet.
【０００８】本発明によれば、前記の（Ａ）項におい
て、樹脂組成を適正化することにより強化繊維ファブリ
ック中に含浸するのに十分な粘度を付与されており、
（Ｂ）、（Ｃ）項において、前記付着物にフィルム越し
に押圧を加えることにより強化繊維ファブリックの空隙
が前記樹脂組成物で完全に満たされた状態が実現され、
かつ、硬化の妨げとなる酸素を含む気泡が完全に除去さ
れる。また適当な張力が付与されることにより、含浸物
は、その内部の樹脂のかたより、強化繊維ファブリック
のしわがない状態で維持され、さらに、（Ｄ）項に記載
した方法により樹脂組成物が硬化し、強化繊維ファブリ
ックと一体化がなされる。（Ａ）項で使用される樹脂組
成物が低粘度組成物であり、かつ非反応性の溶剤を含ま
ないため、前記（１）、（２）の方法に比べ容易に完全
含浸がなされ、かつ空孔がない製品が得られる。According to the present invention, in the above item (A), a sufficient viscosity for impregnating the reinforcing fiber fabric is provided by optimizing the resin composition;
In (B) and (C), a state in which the voids of the reinforcing fiber fabric are completely filled with the resin composition is realized by applying a pressure to the attached matter through a film,
In addition, oxygen-containing air bubbles that hinder curing are completely removed. Also, by applying an appropriate tension, the impregnated material is maintained in a state in which the reinforcing fiber fabric has no wrinkles due to the resin inside thereof, and the resin composition is cured by the method described in (D). And is integrated with the reinforced fiber fabric. Since the resin composition used in the section (A) is a low-viscosity composition and does not contain a non-reactive solvent, the resin composition can be completely impregnated more easily than the methods (1) and (2), and A product without voids is obtained.
【０００９】以下、本発明の詳細を具体的に説明する。
本発明に用いる強化繊維ファブリックとは、高弾性、高
強度の繊維からなる織布、一方向繊維束、チョップ、ラ
ンダムストランドマット、又はこれらを組み合せたもの
であって、繊維としては、炭素繊維、ガラス繊維、ボロ
ン繊維、炭化ケイ素繊維、アルミナ繊維、金属繊維等の
無機繊維、アラミド繊維、ポリエチレン繊維、ポリイミ
ド繊維等の有機繊維が使用される。これらの２種以上の
繊維を組み合せて用いることもできる。また、これらの
強化繊維と樹脂との密着性を改良するため、各種の表面
処理を施すこともできる。Hereinafter, the present invention will be described in detail.
The reinforcing fiber fabric used in the present invention is a high elasticity, a woven fabric made of high-strength fibers, a unidirectional fiber bundle, a chop, a random strand mat, or a combination thereof, and as the fibers, carbon fibers, Inorganic fibers such as glass fibers, boron fibers, silicon carbide fibers, alumina fibers, and metal fibers, and organic fibers such as aramid fibers, polyethylene fibers, and polyimide fibers are used. These two or more kinds of fibers can be used in combination. Various surface treatments can also be applied to improve the adhesion between these reinforcing fibers and the resin.
【００１０】本発明に用いる常温または加熱硬化性アク
リル系樹脂は、メタクリル酸アルキルエステル及び／又
はアクリル酸アルキルエステルとこれらに溶解する熱可
塑性重合体を主成分とするアクリル系硬化性樹脂組成物
であり、硬化触媒及び必要に応じて硬化促進剤を加える
ことにより、常温及び／又は加熱により硬化物を得るこ
とができる。硬化触媒としては、ベンゾイルパーオキサ
イド、メチルエチルケトンパーオキサイド等の有機過酸
化物が用いられる。硬化促進剤としては、ナフテン酸コ
バルト、オクチル酸コバルト等の金属石鹸やジメチルト
ルイジン等の芳香族３級アミン等が用いられる。得られ
た硬化物は、耐無機酸、耐有機酸、耐アルカリの耐薬品
性、耐候性等に優れた特徴を持つ、成形性に優れた熱可
塑性樹脂である。The room-temperature or heat-curable acrylic resin used in the present invention is an alkyl methacrylate and / or an alkyl methacrylate.
Is an acrylic curable resin composition containing, as a main component, an alkyl acrylate and a thermoplastic polymer soluble therein, by adding a curing catalyst and, if necessary, a curing accelerator, at room temperature and / or by heating. A cured product can be obtained. Organic peroxides such as benzoyl peroxide and methyl ethyl ketone peroxide are used as the curing catalyst. As the curing accelerator, metal soaps such as cobalt naphthenate and cobalt octylate, and aromatic tertiary amines such as dimethyl toluidine are used. The obtained cured product is a thermoplastic resin excellent in moldability and having characteristics such as chemical resistance such as inorganic acid resistance, organic acid resistance, and alkali resistance, and weather resistance.
【００１１】また、前記の組成物以外に、樹脂の特性を
改善するための種々の添加剤、例えば、耐熱剤、耐候
剤、帯電防止剤、潤滑剤、離型剤、染料、顔料、消泡
剤、脱酸素剤、難燃剤および各種フィラーなどを含有さ
せてもよい。In addition to the above-mentioned composition, various additives for improving the properties of the resin, for example, heat-resistant agents, weathering agents, antistatic agents, lubricants, release agents, dyes, pigments, defoamers An agent, an oxygen scavenger, a flame retardant, and various fillers may be contained.
【００１２】本発明の前記（Ａ）項において、強化繊維
ファブリックに樹脂組成物を連続的に接触させ、強化繊
維ファブリックに樹脂組成物が付着した付着物を得る方
法には特に制限はないが、例えば下記の方法が用いられ
る。 （１）組成物の浴中に強化繊維ファブリックを浸漬又は
通過させる方法。 （２）１対以上のロールの上に樹脂だまりを設け、その
中を強化繊維ファブリックを通過させる方法。 （３）樹脂組成物をフィルム上に所定の目付の塗膜と
し、その上に強化繊維ファブリックを重ねる方法。In the above item (A) of the present invention, there is no particular limitation on the method for continuously contacting the resin composition with the reinforcing fiber fabric to obtain an adhered substance having the resin composition adhered to the reinforcing fiber fabric. For example, the following method is used. (1) A method of dipping or passing a reinforcing fiber fabric into a bath of the composition. (2) A method in which a resin pool is provided on at least one pair of rolls, and a reinforcing fiber fabric is passed through the pool. (3) A method in which a resin composition is formed into a coating film having a predetermined basis weight on a film, and a reinforcing fiber fabric is laminated thereon.
【００１３】樹脂組成物の付着量は、前記の（Ｃ）項の
方法でロール間の間隙を調節することで強化繊維ファブ
リックの分率が１０〜７０容量％に制御することができ
る。本発明において、前記（Ｂ）項で付着物を挟持する
フィルムには、重合の妨げとなる酸素を透過しづらいも
のであればよく、例えばポリエステルフィルム、ポリエ
チレンフィルムなどの合成樹脂フィルム、表面にシリコ
ン膜を塗布した離型紙などが例示される。The amount of the resin composition adhered can be controlled by adjusting the gap between the rolls by the method described in the above item (C) so that the fraction of the reinforcing fiber fabric is 10 to 70% by volume. In the present invention, the film for sandwiching the deposits in the above item (B) may be any film that does not easily transmit oxygen that hinders polymerization, such as a synthetic resin film such as a polyester film or a polyethylene film, and a silicon film on the surface. Examples include release paper coated with a film.
【００１４】本発明の前記（Ｃ）項で含浸物を得るため
に使用する１対以上のローラーは（Ｃ）項を満足するも
のであればよく、金属製、合成樹脂製、合成ゴム製、木
製、あるいはそれらを組合せたものを使用することがで
きるが、樹脂成分が付着した際、腐食しない材質である
ことが好ましい。At least one pair of rollers used to obtain the impregnated material in the above item (C) of the present invention may be any roller satisfying item (C), and may be made of metal, synthetic resin, synthetic rubber, or the like. Wood or a combination thereof can be used, but it is preferable that the material does not corrode when the resin component adheres.
【００１５】本発明においてローラー対で付与する押圧
は、前記付着物の厚みを減少せしめる程度に加えること
が重要であり、この条件を満足しない場合には、強化繊
維ファブリック中への樹脂成分の十分な含浸が実現され
ないし、強化繊維ファブリック中に含まれていた空気に
由来する気泡が十分に除去されない。前記付着物の厚み
の減少は、前記付着物の１０〜８０％の範囲が適当であ
り、減少が小さすぎる場合には、前記のような未含浸、
気泡の残留の原因となり、大きすぎる場合は繊維方向の
乱れ、損傷を生じるため好ましくない。In the present invention, it is important that the pressure applied by the pair of rollers is applied to such an extent that the thickness of the deposit is reduced. If this condition is not satisfied, the sufficient amount of the resin component in the reinforcing fiber fabric can be obtained. Impregnation is not realized, and air bubbles derived from air contained in the reinforcing fiber fabric are not sufficiently removed. The thickness of the deposit is suitably reduced in the range of 10 to 80% of the deposit.
If the size is too large, it is not preferable because it causes turbulence and damage in the fiber direction.
【００１６】本発明において、強化繊維ファブリックの
連続方向に付与する張力は、強化繊維ファブリックの形
態を維持できる程度に十分、強く、樹脂成分の含浸を阻
害しない程度に十分、弱い範囲の張力が望ましい。In the present invention, the tension applied in the continuous direction of the reinforcing fiber fabric is desirably sufficient and strong enough to maintain the shape of the reinforcing fiber fabric, and sufficient and weak enough not to hinder the impregnation of the resin component. .
【００１７】この前記の張力を付与する方法は、既存の
方法を用いればよく、例えば、一対以上のロール間に挟
持し張力を付与する方法、強化繊維ファブリックを供給
する際の抵抗または、樹脂浴または、含浸ロール通過時
の抵抗により張力を付与する方法等が挙げられる。As the method of applying the tension, an existing method may be used, for example, a method of applying tension by sandwiching between a pair of rolls or more, a resistance when supplying a reinforcing fiber fabric, or a resin bath. Alternatively, a method of imparting tension by resistance when passing through an impregnating roll or the like may be used.
【００１８】本発明における、前記（Ｄ）項における樹
脂成分を硬化する工程は、樹脂成分の性質から室温に放
置したままでもよいが、シート外部への熱の流出を防ぐ
ため断熱材でおおう、あるいは防爆型のオーブン中で加
熱する等して、硬化を促進することも可能である。In the step of curing the resin component in the above item (D) in the present invention, the resin component may be left at room temperature due to the nature of the resin component. However, the resin is covered with a heat insulating material to prevent heat from flowing out of the sheet. Alternatively, curing can be promoted by heating in an explosion-proof oven or the like.
【００１９】本発明で得られるシート状物はそのままで
種々の用途に利用できるが、例えば各種樹脂板に熱融
着、あるいは接着して米国特許４７７８７１７に記載さ
れている熱賦型可能なサンドイッチ板に加工することも
可能であるし、また、適当な長さ巾に切断して、あるい
は連続した状態で硬化する。また重合が完結する前にフ
ィルムを剥離して数枚重ねたものを同様に硬化すること
も可能である。また切断して、所望の配列・分散状態と
して、加熱・加圧する等の成形方法を適用し成形品を得
ることも可能である。The sheet-like material obtained by the present invention can be used as it is for various applications. For example, a heat-moldable sandwich plate described in US Pat. It is also possible to cut into a suitable length and width, or to cure in a continuous state. Before the polymerization is completed, the film may be peeled off and a plurality of films may be similarly cured. It is also possible to obtain a molded article by applying a molding method such as heating and pressurizing to obtain a desired arrangement and dispersion state by cutting.
【００２０】以下に実施例を挙げて本発明をさらに具体
的に説明する。下記例中の『部』は『重量部』を意味す
る。 実施例１ 熱可塑性重合体として、重合平均分子量９５０００のメ
タクリル酸メチルホモポリマー１９部、メタクリル酸メ
チル８１部、硬化促進剤として、ジメチル−ｐ−トルイ
ジン０．８部からなるアクリル系樹脂混合液（Ｂ型粘度
計、２０℃、９０センチポイズ）に硬化触媒として、ベ
ンゾイルパーオキシドを樹脂液１００部に対して、１重
量部添加し、常温硬化型アクリル系樹脂液を調整した。
強化繊維ファブリックとして、炭素繊維６０００本を集
束してなる炭素繊維トウ（三菱レイヨン製パイロフィル
ＴＲ４０）を製織（９本／インチ経緯糸とも）してな
る炭素繊維織布を用意した。これらから以下の工程を経
て、シート状物を得た。以下図１により説明する。上記
織布１をドクターナイフ２の直前でポリエステルフィル
ム５上に供給される樹脂成分３とローラー対４直前で接
触させ付着物とする一方、上から重ねたポリエステルフ
ィルム６とともに移送し（５．０ｍ／分）、間隙を０．
４mmとしたローラ４で含浸し、次いで間隙を０．３５mm
に設定したローラー７でさらに含浸を進めた。これを押
切りカッター８で３００mm長に切断し、平坦なガラス板
上にこれを２６℃の室温中に４０分放置し、硬化を行な
った。Hereinafter, the present invention will be described more specifically with reference to examples. “Parts” in the following examples means “parts by weight”. Example 1 An acrylic resin mixed solution comprising 19 parts of a methyl methacrylate homopolymer having a polymerization average molecular weight of 95,000 as a thermoplastic polymer, 81 parts of methyl methacrylate, and 0.8 part of dimethyl-p-toluidine as a curing accelerator ( 1 part by weight of benzoyl peroxide as a curing catalyst was added to a B-type viscometer (20 ° C., 90 centipoise) as a curing catalyst to 100 parts of the resin solution to prepare a room temperature-curable acrylic resin solution.
As a reinforcing fiber fabric, a carbon fiber woven fabric prepared by weaving (both 9 / inch warp yarns) a carbon fiber tow (Pyrofil TR40 manufactured by Mitsubishi Rayon) formed by bundling 6000 carbon fibers was prepared. From these, a sheet-like material was obtained through the following steps. This will be described below with reference to FIG. The woven fabric 1 is brought into contact with the resin component 3 supplied onto the polyester film 5 immediately before the doctor knife 2 and immediately before the roller pair 4 to form an adhered substance, and is transferred together with the polyester film 6 stacked from above (5.0 m). / Min) with a gap of 0.
Impregnated with roller 4 of 4mm, then the gap was 0.35mm
The impregnation was further promoted with the roller 7 set to. This was cut into a length of 300 mm with a press cutter 8, and the plate was left on a flat glass plate at a room temperature of 26 ° C. for 40 minutes to be cured.
【００２１】得られたシート状物の炭素繊維含有率は、
４７％であり、長さ方向、巾方向に切断した厚み約０．
３５mmの薄片の端面を研磨して光学顕微鏡観察を行なっ
たところ炭素繊維トウ中への樹脂の含浸は良好であっ
た。樹脂部にボイドはみられなかった。次にこのシート
状物を９０mm角に切断、積層し、２５０℃に設定した平
金型で５kg／cm2 の圧力で一体化し、外観の良好な２．
５mm厚の成形品を得た。これから切り出した試験片に対
して、ＡＳＴＭ Ｄ−７９０に準じた曲げ試験、同Ｄ−
２３４４に準じた層間せん断試験を実施したところ曲げ
強度６０kg／mm2 、曲げ弾性率６ton/mm2 、層間せん断
強度４kg／mm2 と、すぐれた特性を示した。The carbon fiber content of the obtained sheet is
47%, and a thickness of about 0.4% cut in the length and width directions.
When the end face of the 35 mm flake was polished and observed with an optical microscope, the impregnation of the resin into the carbon fiber tow was good. No void was found in the resin part. Next, the sheet was cut into a 90 mm square, laminated, and integrated with a flat mold set at 250 ° C. at a pressure of 5 kg / cm 2 to obtain a good appearance.
A molded product having a thickness of 5 mm was obtained. A bending test according to ASTM D-790 was performed on a test piece cut out from the test piece.
When an interlaminar shear test according to 2344 was performed, excellent properties were exhibited, such as a flexural strength of 60 kg / mm 2 , a flexural modulus of 6 ton / mm 2 , and an interlaminar shear strength of 4 kg / mm 2 .
【００２２】実施例２ 実施例１と同様の方法で得られた含浸物を５０℃の乾燥
機中硬化した。（１０分間）得られたシート状物の炭素
繊維含有率は、４７％であり、長さ方向、巾方向に切断
した厚み約０．３５mmの薄片の端面を研磨して光学顕微
鏡観察を行なったところ炭素繊維トウ中への樹脂の含浸
は良好であった。樹脂部にボイドはみられなかった。Example 2 The impregnated product obtained in the same manner as in Example 1 was cured in a dryer at 50 ° C. (10 minutes) The carbon fiber content of the obtained sheet was 47%, and the end face of a thin piece having a thickness of about 0.35 mm cut in the length direction and the width direction was polished and observed with an optical microscope. However, the impregnation of the resin into the carbon fiber tow was good. No void was found in the resin part.
【００２３】実施例３ 熱可塑性重合体として、重合平均分子量４２０００のメ
タクリル酸メチル／メタクリル酸−ｎ−ブチル＝６０／
４０（モル比）からなる共重合物２９重量部、メタクリ
ル酸メチル３９重量部、アクリル酸−２−エチルヘキシ
ル３２重量部と硬化促進剤として、ジメチル−ｐ−トル
イジン１．０重量部からなる樹脂液（Ｂ型粘度計、２０
℃、１３０センチポイズ）に硬化触媒として、ベンゾイ
ルパーオキサイドを樹脂液１００重量部に対して、１重
量部添加し、常温硬化型アクリル系樹脂液を調整したほ
かは、実施例１と同様の方法でシートを得た。得られた
シート状物の炭素繊維含有率は、５０％であり、長さ方
向、巾方向に切断した厚み約０．３５mmの薄片の端面を
研磨して光学顕微鏡観察を行なったところ炭素繊維トウ
中への樹脂の含浸は良好であった。樹脂部にボイドはみ
られなかった。Example 3 As a thermoplastic polymer, methyl methacrylate / n-butyl methacrylate having a polymerization average molecular weight of 42,000 = 60 /
Resin liquid consisting of 29 parts by weight of a copolymer consisting of 40 (molar ratio), 39 parts by weight of methyl methacrylate, 32 parts by weight of 2-ethylhexyl acrylate and 1.0 part by weight of dimethyl-p-toluidine as a curing accelerator (B-type viscometer, 20
(C, 130 centipoise) As a curing catalyst, 1 part by weight of benzoyl peroxide was added to 100 parts by weight of the resin liquid, and a room temperature-curable acrylic resin liquid was adjusted. I got a sheet. The obtained sheet-like material had a carbon fiber content of 50%. The end face of a thin piece having a thickness of about 0.35 mm cut in the length and width directions was polished and observed with an optical microscope. The impregnation of the resin therein was good. No void was found in the resin part.
【００２４】比較例１ 実施例１で用いた炭素繊維織布を実施例１で用いた樹脂
を重合固化した樹脂板をメチルエチルケトンに溶解した
樹脂溶液（樹脂濃度１０重量％、溶液粘度１００センチ
ポイズ）に浸漬・乾燥をくりかえし、炭素繊維含有率５
０％のシート状物を得た。これを長さ方向、巾方向に切
断し薄片の端面を研磨して光学顕微鏡で、観察したとこ
ろ、溶剤残留のためと考えられるポイドが多数観察され
た。次に、このシート状物から実施例１と同様の方法
で、曲げ試験、層間せん断試験を行ったところ、曲げ強
度４０kg／mm2 、曲げ弾性率４ton/mm2 、層間せん断強
度２．５kg／mm2 と低調であった。Comparative Example 1 A resin plate obtained by polymerizing and solidifying the resin used in Example 1 with the carbon fiber woven fabric used in Example 1 was dissolved in methyl ethyl ketone to a resin solution (resin concentration 10% by weight, solution viscosity 100 centipoise). Repeated immersion and drying, carbon fiber content 5
0% of a sheet was obtained. This was cut in the length direction and the width direction, and the end face of the flake was polished and observed with an optical microscope. As a result, a large number of poids considered to be due to residual solvent were observed. Next, a bending test and an interlaminar shear test were performed on the sheet in the same manner as in Example 1. The flexural strength was 40 kg / mm 2 , the flexural modulus was 4 ton / mm 2 , and the interlaminar shear strength was 2.5 kg / mm. It was weak and mm 2.
【００２５】比較例２ 実施例１で用いた炭素繊維織布を実施例１で用いた樹脂
を重合固化した樹脂板（０．３mm厚）を重ね、平金型中
に投入した。これを熱プレス（２４０℃、２０kg／c
m2 ）中で１時間保持した後、圧力を保ったまま室温に
冷却した。得られたシート状物を切断し、端面を研磨
し、光学顕微鏡で観察したところ、すべての炭素繊維ト
ウ内部に樹脂の未含浸の部分が観察された。次に実施例
１に記した方法により、曲げ試験、層間せん断試験を実
施したところ、曲げ強度３０kg／mm2 、曲げ弾性率３to
n/mm2 、層間せん断強度１．５kg／mm2 と低調であっ
た。Comparative Example 2 A resin plate (thickness: 0.3 mm) obtained by polymerizing and solidifying the resin used in Example 1 with the carbon fiber woven fabric used in Example 1 was put into a flat mold. This is hot pressed (240 ° C, 20kg / c
After holding for 1 hour in m 2 ), the mixture was cooled to room temperature while maintaining the pressure. The obtained sheet was cut, the end face was polished, and observed with an optical microscope. As a result, unimpregnated portions of the resin were observed inside all the carbon fiber tows. Next, a bending test and an interlaminar shear test were performed by the method described in Example 1. The bending strength was 30 kg / mm 2 , and the flexural modulus was 3 to.
n / mm 2 and interlaminar shear strength of 1.5 kg / mm 2 were low.
【図１】本発明の実施例で使用する装置の概略図であ
る。FIG. 1 is a schematic diagram of an apparatus used in an embodiment of the present invention.
１ 強化繊維ファブリック ２ ドクターナイフ ３ 樹脂 ４ ローラー対 ５ ポリエステルフィルム ６ ポリエステルフィルム ７ ローラー対 ８ 押し切りカッター DESCRIPTION OF SYMBOLS 1 Reinforced fiber fabric 2 Doctor knife 3 Resin 4 Roller pair 5 Polyester film 6 Polyester film 7 Roller pair 8 Push cutter
───────────────────────────────────────────────────── フロントページの続き (72)発明者 荒川 宗和 愛知県名古屋市東区砂田橋４丁目１番60 号 三菱レイヨン株式会社 商品開発研 究所内 (72)発明者 小西 偉夫 愛知県名古屋市東区砂田橋４丁目１番60 号 三菱レイヨン株式会社 商品開発研 究所内 (56)参考文献 特表 平３−500665（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B29C 70/06 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Munekazu Arakawa 4-160 Sunadabashi, Higashi-ku, Nagoya City, Aichi Prefecture Mitsubishi Rayon Co., Ltd. Product Development Laboratory (72) Inventor Takeo Konishi 4 Sunadabashi, Higashi-ku, Nagoya City, Aichi Prefecture No. 1-60, Mitsubishi Rayon Co., Ltd. Product Development Laboratory (56) References Special Table Heisei 3-500665 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B29C 70/06
Claims (6)
アルキルエステル及び／又はアクリル酸アルキルエステ
ルとこれらに溶解する熱可塑性重合体を主成分とし、粘
度が１０〜１０ ４ センチポイズの範囲にあるアクリル系
硬化性樹脂組成物を含浸した、まだ硬化していない繊維
強化熱可塑性樹脂シート材料。1. A methacrylic acid is added to a reinforcing fiber fabric.
Alkyl ester and / or alkyl acrylate
And a thermoplastic polymer that dissolves in
Acrylic the degree is in the range of 10 to 10 4 centipoise
Uncured fiber impregnated with curable resin composition
Reinforced thermoplastic sheet material .
化物と硬化促進剤が含有されている請求項１記載のまだ
硬化していない繊維強化熱可塑性樹脂シート材料。2. An organic peracid is added to the acrylic curable resin composition.
2. The composition according to claim 1, further comprising a compound and a curing accelerator.
Uncured fiber reinforced thermoplastic sheet material .
にある常温又は加熱硬化性アクリル系樹脂液と強化繊維
ファブリックとを接触させ、前記強化繊維ファブリック
に前記樹脂液を含浸させることを特徴とする請求項１記
載の繊維強化熱可塑性樹脂シート材料の製造方法。3. contacting the viscosity normal temperature or heat-curable acrylic resin liquid in the range of 10 to 10 4 centipoise and reinforcing fibers fabric, characterized in that impregnating the resin liquid to the reinforcing fiber fabric Claim 1
A method for producing the fiber-reinforced thermoplastic resin sheet material described above.
にある常温又は加熱硬化性アクリル系樹脂液と強化繊維
ファブリックとを接触させ、前記強化繊維ファブリック
に前記樹脂液が含浸した繊維強化アクリル系樹脂を得る
際、下記の操作を順次行なうことを特徴とする繊維強化
熱可塑性樹脂シート材料の製造方法； （Ａ）常温又は加熱硬化性アクリル系樹脂と硬化触媒と
からなる樹脂組成物と強化繊維ファブリックとを連続的
に接触させ、強化繊維ファブリックに該組成物が付着し
た付着物を得ること。 （Ｂ）前記付着物を連続方向に張力をかけつつ、上下か
ら通気性の少ないフィルムで挟持しつつ、移送するこ
と。 （Ｃ）前記フィルムに挟持した状態で１対以上のローラ
ーにより付着物の厚みを減少することによって押圧を加
え、樹脂組成物が強化繊維ファブリックの横断面にわた
って含浸すると同時に、付着物中に散在している気泡を
余剰の樹脂とともに、フィルムの両端より外へ流出せし
めた含浸物を得ること。Wherein viscosity of contacting the reinforcing fiber fabric at room temperature or heat-curable acrylic resin liquid in the range of 10 to 10 4 centipoise, fiber reinforced acrylic resin wherein the resin solution is impregnated into the reinforcing fiber fabric when the Ru obtained, method for producing a fiber-reinforced thermoplastic resin sheet material, characterized in that sequentially carried out the following operations; enhanced (a) and resin composition comprising a room temperature or heat curing acrylic resin and a curing catalyst fibers Contacting the fabric with the fabric continuously to obtain a deposit of the composition adhering to the reinforcing fiber fabric. (B) transferring the attached matter while applying tension in a continuous direction and sandwiching the film from above and below with a film having low air permeability. (C) Pressing by reducing the thickness of the deposit with one or more rollers while sandwiching the film, the resin composition is impregnated over the cross section of the reinforcing fiber fabric, and is simultaneously scattered in the deposit. To obtain an impregnated material in which air bubbles are allowed to flow out from both ends of the film together with excess resin.
にある常温又は加熱硬化性アクリル系樹脂液と強化繊維
ファブリックとを接触させ、前記強化繊維ファブリック
に前記樹脂液が含浸した繊維強化アクリル系樹脂の前駆
体としたのち、これを室温及び／又は加熱により硬化さ
せることを特徴とする繊維強化熱可塑性樹脂シート材料
の製造方法。5. A viscosity contacting the reinforcing fiber fabric at room temperature or heat-curable acrylic resin liquid in the range of 10 to 10 4 centipoise, fiber reinforced acrylic resin wherein the resin solution is impregnated into the reinforcing fiber fabric A method for producing a fiber-reinforced thermoplastic resin sheet material, comprising curing the precursor at room temperature and / or heating after the precursor of the above.
にある常温又は加熱硬化性アクリル系樹脂液と強化繊維
ファブリックとを接触させ、前記強化繊維ファブリック
に前記樹脂液が含浸した繊維強化アクリル系樹脂の前駆
体としたのち、これを室温及び／又は加熱により硬化
し、熱賦型可能な繊維強化アクリル系樹脂シート材を得
る際、下記の操作を順次行なうことを特徴とする繊維強
化熱可塑性樹脂シート材料の製造方法； （Ａ）常温又は加熱硬化性アクリル系樹脂と硬化触媒と
からなる樹脂組成物と強化繊維ファブリックとを連続的
に接触させ、強化繊維ファブリックに該組成物が付着し
た付着物を得ること。 （Ｂ）前記付着物を連続方向に張力をかけつつ、上下か
ら通気性の少ないフィルムで挟持しつつ、移送するこ
と。 （Ｃ）前記フィルムに挟持した状態で１対以上のローラ
ーにより付着物の厚みを減少することによって押圧を加
え、樹脂組成物が強化繊維ファブリックの横断面にわた
って含浸すると同時に、付着物中に散在している気泡を
余剰の樹脂とともに、フィルムの両端より外へ流出せし
めた含浸物を得ること。 （Ｄ）前記、含浸物中の樹脂の硬化後、フィルムを剥離
して、硬化したシート状物を得ること。6. A viscosity contacting the reinforcing fiber fabric at room temperature or heat-curable acrylic resin liquid in the range of 10 to 10 4 centipoise, fiber reinforced acrylic resin wherein the resin solution is impregnated into the reinforcing fiber fabric And then curing the same at room temperature and / or heating to obtain a heat-moldable fiber-reinforced acrylic resin sheet material, wherein the following operations are sequentially performed to obtain a fiber-reinforced thermoplastic resin: A method for producing a sheet material; (A) a resin composition comprising a room-temperature or heat-curable acrylic resin and a curing catalyst and a reinforcing fiber fabric are continuously brought into contact with each other, and an adhering substance obtained by adhering the composition to the reinforcing fiber fabric To get (B) transferring the attached matter while applying tension in a continuous direction and sandwiching the film from above and below with a film having low air permeability. (C) Pressing is applied by reducing the thickness of the deposit with one or more rollers while being sandwiched between the films, so that the resin composition is impregnated over the cross section of the reinforcing fiber fabric and is simultaneously scattered in the deposit. To obtain an impregnated material in which air bubbles are allowed to flow out from both ends of the film together with excess resin. (D) After the resin in the impregnated material is cured, the film is peeled off to obtain a cured sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2418525A JP3035618B2 (en) | 1990-12-28 | 1990-12-28 | Fiber-reinforced thermoplastic resin sheet material and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2418525A JP3035618B2 (en) | 1990-12-28 | 1990-12-28 | Fiber-reinforced thermoplastic resin sheet material and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04226740A JPH04226740A (en) | 1992-08-17 |
| JP3035618B2 true JP3035618B2 (en) | 2000-04-24 |
Family
ID=18526357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2418525A Expired - Lifetime JP3035618B2 (en) | 1990-12-28 | 1990-12-28 | Fiber-reinforced thermoplastic resin sheet material and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3035618B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021178982A (en) * | 2014-01-10 | 2021-11-18 | 小松マテーレ株式会社 | Fiber-reinforced resin material and fiber-reinforced resin molding using the same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2981652B1 (en) * | 2011-10-21 | 2015-03-27 | Arkema France | COMPOSITIONS VIA IN-SITU POLYMERIZATION OF METHACRYLIC THERMOPLASTIC RESINS |
| FR2993581B1 (en) * | 2012-07-18 | 2016-01-22 | Arkema France | IMPREGNATION PROCESS FOR A FIBROUS SUBSTRATE, LIQUID (METH) ACRYLIC SYRUP FOR THE IMPREGNATION PROCESS, ITS POLYMERIZATION PROCESS AND STRUCTURE PRODUCT OBTAINED THEREFROM |
| WO2014111129A1 (en) * | 2013-01-15 | 2014-07-24 | Arkema France | Multilayer composite composition, its manufacturing process, and article obtained thereof |
| CN108495866B (en) | 2015-12-28 | 2021-03-02 | 雅马哈株式会社 | Resin composition for FRP, FRP sheet and molded product |
-
1990
- 1990-12-28 JP JP2418525A patent/JP3035618B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021178982A (en) * | 2014-01-10 | 2021-11-18 | 小松マテーレ株式会社 | Fiber-reinforced resin material and fiber-reinforced resin molding using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04226740A (en) | 1992-08-17 |
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