JP2006063130A - Reinforcing fiber prepreg and method for producing the reinforcing fiber prepreg - Google Patents

Reinforcing fiber prepreg and method for producing the reinforcing fiber prepreg Download PDF

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JP2006063130A
JP2006063130A JP2004245010A JP2004245010A JP2006063130A JP 2006063130 A JP2006063130 A JP 2006063130A JP 2004245010 A JP2004245010 A JP 2004245010A JP 2004245010 A JP2004245010 A JP 2004245010A JP 2006063130 A JP2006063130 A JP 2006063130A
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reinforcing fiber
release film
fiber prepreg
prepreg
sheet
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Mitsutaka Kato
光崇 加藤
Naoki Iwasaki
直樹 岩崎
Hiroyuki Takagishi
宏至 高岸
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Toray Industries Inc
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Toray Industries Inc
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a reinforcing fiber prepreg having good handleability, by preventing the reinforcing fiber prepreg from floating up from a release film and further preventing defects caused by wrinkles and adhesion deficiency of the prepreg from occurring, when formed into a cylinder, etc., by FRP molding, and to provide a method for producing the reinforcing fiber prepreg. <P>SOLUTION: This reinforcing fiber prepreg is produced by laying and arranging a sheet-like material containing water on a reinforcing fiber prepreg which is formed by impregnating a reinforcing fiber sheet with a matrix resin and then attaching a release film to at least one of its surfaces, so that the sheet-like material is laid and arranged to be adjacent to the release film. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、強化繊維複合材料の成形に使用される中間基材である強化繊維プリプレグおよび強化繊維プリプレグの製造方法に関し、特に、離型フィルムからの浮きや剥がれが少なく品位良好な強化繊維プリプレグおよび強化繊維プリプレグの製造方法に関する。   The present invention relates to a reinforcing fiber prepreg which is an intermediate base material used for molding a reinforcing fiber composite material and a method for producing the reinforcing fiber prepreg, and in particular, a reinforcing fiber prepreg having a good quality with less lifting and peeling from a release film. The present invention relates to a method for producing a reinforcing fiber prepreg.

強化繊維複合材料は、その優れた力学特性から、ゴルフシャフト、釣竿、およびテニスラケットなどに用いられる。強化繊維複合材料の中間基材として使用される強化繊維プリプレグは、その成形品をより軽量にするため、また十分な強度を発現するために、強化繊維の乱れのない、均一な品位のものが望まれる。   Reinforcing fiber composite materials are used for golf shafts, fishing rods, tennis rackets and the like because of their excellent mechanical properties. Reinforcing fiber prepreg used as an intermediate base material for reinforcing fiber composites has a uniform quality with no disturbance of reinforcing fibers in order to make the molded product lighter and to develop sufficient strength. desired.

強化繊維プリプレグは、例えば、複数本の強化繊維糸条を一方向に互いに並行かつシート状に引き揃えて、マトリックス樹脂を塗布した離型フィルムを、その樹脂塗布面が強化繊維糸条側を向くように強化繊維糸条の上側および下側に重ね合わせ、この重ね合せ体を加熱、加圧して離型フィルム上のマトリックス樹脂を強化繊維糸条に転移、含浸することによって製造されている。いわゆるホットメルト法と呼ばれる方法である。この場合、離型フィルムへのマトリックス樹脂の塗布は、上側あるいは下側の離型フィルムのいずれか、または両方に行われる。マトリックス樹脂が含浸された強化繊維プリプレグは、一般的に上、下いずれかの離型フィルムを剥ぎ、もう一方の離型フィルムに貼り付けた状態で、連続的にロール状に巻き取られ製品となるのが通例である。しかし、プリプレグに担持された離型フィルムは、樹脂を含浸する過程で、加熱、加圧されるため、離型フィルムは圧延された状態、すなわち張力が掛かり幾らか引き伸ばされた状態になり、この状態でロール状に巻き取られる。   The reinforcing fiber prepreg is, for example, a release film in which a plurality of reinforcing fiber yarns are aligned in parallel in one direction and in a sheet shape and a matrix resin is applied, and the resin application surface faces the reinforcing fiber yarn side. Thus, it is manufactured by superposing the reinforcing fiber yarns on the upper side and the lower side, and heating and pressurizing the laminated body to transfer and impregnate the matrix resin on the release film to the reinforcing fiber yarns. This is a so-called hot melt method. In this case, the matrix resin is applied to the release film on either or both of the upper and lower release films. Reinforcing fiber prepregs impregnated with a matrix resin are generally rolled up into a roll shape with either the upper or lower release film peeled off and affixed to the other release film. This is usually the case. However, since the release film carried on the prepreg is heated and pressurized in the process of impregnating the resin, the release film is in a rolled state, that is, a stretched state due to tension. It is wound up in a roll shape.

ここで、例えば強化繊維プリプレグを円筒などに成形する場合、通常、ロール上のプリプレグをある程度の大きさのシートに貼り付けられた下側の離型フィルムとともに切り出し、その後必要な形状に切り整え、芯体に巻付け、樹脂を硬化させる。このとき、芯体に巻き付けるまでにカットしたプリプレグは数時間程度放置されることが多く、ロール状に製造された際に張力がかかり、いくらか引き伸ばされた状態にある離型フィルムはその間に元に戻ろうとするが、プリプレグはこの離型フィルムの動きに追随できないため、部分的に離型フィルムからプリプレグが剥がれ、プリプレグ表面に凹凸が発生することがある(以下、このプリプレグ表面の凹凸を「浮き」と称す)。このような浮きが発生したプリプレグを芯体に巻き付けると、皺が発生したり、ボイドが発生する原因となり、得られる成形体の強度低下、品位不良の問題が起こる。   Here, for example, when molding the reinforcing fiber prepreg into a cylinder or the like, usually, the prepreg on the roll is cut out together with the lower release film attached to a sheet of a certain size, and then cut into a necessary shape, Wrap around the core and cure the resin. At this time, the prepreg cut before being wound around the core body is often left for several hours, and when it is manufactured in a roll shape, tension is applied, and the release film in a somewhat stretched state is in the meantime. Although the prepreg cannot follow the movement of the release film, the prepreg may be partially peeled off from the release film, resulting in unevenness on the prepreg surface (hereinafter, the unevenness on the prepreg surface is "). When the prepreg in which such a float is generated is wound around the core body, wrinkles or voids are generated, resulting in a decrease in strength and poor quality of the resulting molded body.

このような浮きを防止するため、長手方向の弾性伸び率、さらには塑性戻り率を低く抑えた離型フィルムを用いる技術が知られている(例えば、特許文献2参照)。しかしながら、圧延された離型フィルムは、程度は小さくともやはり再び元に戻ろうとするだけでなく、含浸時に加熱を受けることにより、含浸前に元々含有していた水分を放出するため、含浸前より収縮しようとする結果、浮きが生じ、十分な効果が得られなかった。   In order to prevent such floating, a technique using a release film in which the elastic elongation rate in the longitudinal direction and further the plastic return rate are kept low is known (for example, see Patent Document 2). However, the rolled release film not only tries to return to the original state even if the degree is small, but also releases the moisture originally contained before the impregnation by being heated during the impregnation. As a result of the contraction, floating occurred and a sufficient effect was not obtained.

また、離型フィルムの引き出し張力や強化繊維の張力を適正化することでの改善が提案されている(例えば、特許文献3参照)。しかしながら、やはり、離型フィルムは含浸の過程で、加熱、加圧により圧延された状態になるため、再びこれをシート状に切り出すと、離型フィルムが以前より収縮しようとする結果、浮きが生じ、期待した効果を得ることができない。
特開2000−61940号公報 特開平11−309716号公報
Moreover, the improvement by optimizing the drawer | drawing-out tension | tensile_strength of a release film and the tension | tensile_strength of a reinforcement fiber is proposed (for example, refer patent document 3). However, since the release film is in a state of being rolled by heating and pressurizing during the impregnation process, if the sheet is cut again into a sheet shape, the release film tends to shrink more than before, resulting in floating. Can't get the expected effect.
JP 2000-61940 A JP-A-11-309716

本発明の課題は、かかる従来技術の問題点を解決し、強化繊維プリプレグの離型フィルムからの浮きがなく、円筒などにFRP成形する際にプリプレグの皺や貼り付き不良による欠陥を発生しない取扱性の良好な強化繊維プリプレグおよび強化繊維プリプレグの製造方法を提供することにある。   The problem of the present invention is to solve the problems of the prior art, there is no floating from the release film of the reinforcing fiber prepreg, and handling that does not cause defects due to prepreg wrinkles or sticking defects when FRP molding into a cylinder or the like An object of the present invention is to provide a reinforcing fiber prepreg having good properties and a method for producing a reinforcing fiber prepreg.

本発明は上記課題を達成するため、以下の構成を採用する。すなわち、
(1)強化繊維シートにマトリックス樹脂が含浸され、少なくともその一表面に離型フィルムを貼り付けてなる強化繊維プリプレグに、含水したシート状物が前記離型フィルムに隣接するように重ねて配置されていることを特徴とする強化繊維プリプレグ。
The present invention adopts the following configuration in order to achieve the above object. That is,
(1) A reinforcing fiber sheet is impregnated with a matrix resin, and a hydrated fiber prepreg is formed by adhering a release film on at least one surface thereof. Reinforced fiber prepreg characterized by

(2)含水したシート状物の含水率が、強化繊維プリプレグの少なくとも一表面に貼り付ける離型フィルムの含水率より高いことを特徴とする前記(1)に記載の強化繊維プリプレグ。   (2) The reinforcing fiber prepreg according to (1) above, wherein the moisture content of the water-containing sheet is higher than the moisture content of the release film attached to at least one surface of the reinforcing fiber prepreg.

(3)含水したシート状物の含水率が6%以上であることを特徴とする前記(1)または(2)に記載の強化繊維プリプレグ。   (3) The reinforcing fiber prepreg according to (1) or (2) above, wherein the moisture content of the water-containing sheet is 6% or more.

(4)含水したシート状物の放水率が離型フィルムの放水率より高いことを特徴とする前記(1)〜(3)のいずれかに記載の強化繊維プリプレグ。   (4) The reinforcing fiber prepreg according to any one of (1) to (3), wherein the water content of the water-containing sheet is higher than that of the release film.

(5)含水したシート状物の放水率が1.2%以上であることを特徴とする前記(1)〜(4)のいずれかに記載の強化繊維プリプレグ。   (5) The reinforcing fiber prepreg according to any one of (1) to (4) above, wherein the water discharge rate of the water-containing sheet is 1.2% or more.

(6)強化繊維プリプレグがロール状またはシート状であることを特徴とする前記(1)〜(5)のいずれかに記載の強化繊維プリプレグ。   (6) The reinforcing fiber prepreg according to any one of (1) to (5), wherein the reinforcing fiber prepreg is in a roll shape or a sheet shape.

(7)強化繊維からなる強化繊維シートの上下両面に、少なくとも一方の面にマトリックス樹脂が塗布された離型フィルムを樹脂塗布面が強化繊維糸条側を向くように重ね合わせ、該重ね合わせ体を含浸ロールに通して強化繊維シートに離型フィルム上のマトリックス樹脂を転移、含浸する強化繊維プリプレグの製造方法において、マトリックス樹脂を含浸した後、強化繊維プリプレグに担持された離型フィルムに、含水したシート状物を隣接するように重ねて配置し、離型フィルムを加湿することを特徴とする強化繊維プリプレグの製造方法。   (7) On the upper and lower surfaces of the reinforcing fiber sheet made of reinforcing fibers, a release film having a matrix resin coated on at least one surface is superposed so that the resin coated surface faces the reinforcing fiber yarn side, and the superposed body In a method for producing a reinforced fiber prepreg in which a matrix resin on a release film is transferred to and impregnated into a reinforcing fiber sheet through an impregnation roll, after impregnating the matrix resin, the release film supported by the reinforcing fiber prepreg contains water. The manufacturing method of the reinforced fiber prepreg characterized by arrange | positioning the sheet-like thing piled up so that it may adjoin and humidifying a release film.

(8)前記加湿は、強化繊維プリプレグに担持された離型フィルムの50%Rhでの含水率に対して70%〜130%の範囲となるように行われることを特徴とする前記(7)に記載の強化繊維プリプレグの製造方法。   (8) The humidification is performed so as to be in a range of 70% to 130% with respect to the moisture content at 50% Rh of the release film supported on the reinforcing fiber prepreg (7) The manufacturing method of the reinforced fiber prepreg of description.

本発明によれば、含水したシート状物を強化繊維プリプレグを担持している離型フィルムに隣接して配置することにより、強化繊維プリプレグの離型フィルムからの浮きがなく、強化繊維複合材料の成形の際にプリプレグの皺や貼り付き不良による欠陥を発生しない、成形に好適なプリプレグを提供できる。   According to the present invention, by placing the water-containing sheet adjacent to the release film carrying the reinforcing fiber prepreg, there is no lifting of the reinforcing fiber prepreg from the release film, and the reinforcing fiber composite material It is possible to provide a prepreg suitable for molding that does not cause defects due to defects or sticking of the prepreg during molding.

本発明の強化繊維プリプレグは、強化繊維シートにマトリックス樹脂が含浸され、少なくともその一表面に離型フィルムを貼り付けてなる強化繊維プリプレグに、含水したシート状物が前記離型フィルムに隣接するように重ねて配置されていることを特徴とするものである。   In the reinforcing fiber prepreg of the present invention, a reinforcing fiber prepreg is obtained by impregnating a reinforcing fiber sheet with a matrix resin and attaching a release film to at least one surface thereof, so that a water-containing sheet is adjacent to the release film. It is characterized by being arranged so as to overlap with each other.

この強化繊維プリプレグにおいては、含水したシート状物の含水率が、強化繊維プリプレグの少なくとも一表面に貼り付ける離型フィルムの含水率(通常2.5〜5.5%)より高いことが好ましく、また、含水したシート状物の含水率が6%以上であることがより好ましく、また、15%以下であることが好ましい。シート状物の含水率がこの範囲内であれば、プリプレグの水分率を適正な範囲に管理することが容易であり、また効果的に「浮き」を防止できる。   In this reinforcing fiber prepreg, the moisture content of the water-containing sheet is preferably higher than the moisture content of the release film (usually 2.5 to 5.5%) to be attached to at least one surface of the reinforcing fiber prepreg. Further, the water content of the water-containing sheet is more preferably 6% or more, and is preferably 15% or less. If the moisture content of the sheet-like material is within this range, it is easy to manage the moisture content of the prepreg within an appropriate range, and “float” can be effectively prevented.

ここで、含水率とは、シート状物で言えば、23℃、50%Rhの雰囲気下に24時間シート状物を放置したときのシート状物の重量当たりの水分重量率のことである。具体的には、23℃、50%Rhの雰囲気下にシート状物を24時間放置したときのシート状物の重量Aに対し、シート状物を130℃で2時間加熱したときのシート状物の重量をBとしたとき、その含水率は下記式(1)で求められる。なお、離型フィルムの場合も同様にして求められる。   Here, in terms of the sheet-like material, the moisture content is a moisture weight ratio per weight of the sheet-like material when the sheet-like material is left for 24 hours in an atmosphere of 23 ° C. and 50% Rh. Specifically, the sheet-like material when the sheet-like material is heated at 130 ° C. for 2 hours with respect to the weight A of the sheet-like material when it is left for 24 hours in an atmosphere of 23 ° C. and 50% Rh. Assuming that the weight of B is B, the water content is obtained by the following formula (1). In the case of a release film, it is obtained in the same manner.

含水率(%)={(A−B)/B}×100 ・・・(1)
また、この強化繊維プリプレグにおいては、含水したシート状物の放水率が、強化繊維プリプレグの離型フィルムの放水率(通常0.2〜0.3%)より高いことが、含水したシート状物からプリプレグに貼り付いた離型フィルムへ水分が移行しやすいので好ましく、また、含水したシート状物の放水率が1.2%以上であることがより好ましく、また、5%以下であることが好ましい。シート状物の含水率がこの範囲内であれば、プリプレグの水分率を適正な範囲に管理することが容易であり、また効果的に「浮き」を防止できる。
Moisture content (%) = {(A−B) / B} × 100 (1)
Further, in this reinforcing fiber prepreg, the water-containing sheet-like product has a water release rate higher than that of the release film of the reinforcing fiber prepreg (usually 0.2 to 0.3%). It is preferable because moisture easily moves from the film to the release film attached to the prepreg, and the water discharge rate of the water-containing sheet is more preferably 1.2% or more, and 5% or less. preferable. If the moisture content of the sheet-like material is within this range, it is easy to manage the moisture content of the prepreg within an appropriate range, and “float” can be effectively prevented.

ここで、放水率とは、シート状物で言えば、23℃、80%Rhから23℃、50%Rhの雰囲気に置いた時のシート状物当たりの水分の重量減少率のことである。具体的には23℃、80%Rhの雰囲気下にシート状物を24時間放置したときのシート状物の重量Cに対し、23℃、50%Rhの雰囲気下にシート状物を24時間放置したときのシート状物の重量をAとしたとき、その放水率は下記式(2)で求められる。重量Bは上記した通りシート状物を130℃で2時間加熱したときのシート状物重量である。なお、離型フィルムの場合も同様にして求められる。   Here, the water discharge rate is a weight reduction rate of moisture per sheet when placed in an atmosphere of 23 ° C. and 80% Rh to 23 ° C. and 50% Rh. Specifically, the sheet-like material is allowed to stand for 24 hours in an atmosphere of 23 ° C. and 50% Rh relative to the weight C of the sheet-like material when left for 24 hours in an atmosphere of 23 ° C. and 80% Rh. When the weight of the sheet-like material is A, the water discharge rate is obtained by the following formula (2). The weight B is the weight of the sheet material when the sheet material is heated at 130 ° C. for 2 hours as described above. In the case of a release film, it is obtained in the same manner.

放水率(%)={(C−A)/B}×100 ・・・(2)
また、この強化繊維プリプレグにおいては、強化繊維プリプレグをロール状に巻いても良いが、シート状のままであっても良く、本発明における効果が得られる。
Water discharge rate (%) = {(C−A) / B} × 100 (2)
In this reinforcing fiber prepreg, the reinforcing fiber prepreg may be wound in a roll shape, but may remain in a sheet shape, and the effect of the present invention can be obtained.

上記のような強化繊維プリプレグは、次のような方法によって製造できる。すなわち、強化繊維からなる強化繊維シートの上下両面に、少なくとも一方の面にマトリックス樹脂が塗布された離型フィルムを樹脂塗布面が強化繊維糸条側を向くように重ね合わせ、該重ね合わせ体を含浸ロールに通して強化繊維シートに離型フィルム上のマトリックス樹脂を転移、含浸する強化繊維プリプレグの製造方法において、マトリックス樹脂を含浸した後、強化繊維プリプレグに担持された離型フィルムに、含水したシート状物を隣接するように重ねて配置し、離型フィルムを加湿することを特徴とする方法からなる。   The reinforcing fiber prepreg as described above can be produced by the following method. That is, on both the upper and lower surfaces of a reinforcing fiber sheet made of reinforcing fibers, a release film having a matrix resin coated on at least one surface is superposed so that the resin-coated surface faces the reinforcing fiber yarn side, In the manufacturing method of the reinforcing fiber prepreg in which the matrix resin on the release film is transferred to and impregnated into the reinforcing fiber sheet through the impregnating roll, after impregnating the matrix resin, the release film supported on the reinforcing fiber prepreg is hydrated. It consists of a method characterized in that sheet-like materials are arranged so as to be adjacent to each other and the release film is humidified.

すなわち、強化繊維プリプレグに担持された離型フィルムは、含浸の過程において、加熱され、元の状態から水分が蒸発した状態になり、さらに、加圧によって圧延され、張力が掛かり、幾らか引き伸ばされた状態にあるが、これに含水したシート状物を隣接するように配置することによって、離型フィルムは元の含水状態に近づき、引き伸ばされた状態から解放されて、後でシート状に切り出されても離型フィルムの収縮しようとする力が働かなくなる結果、プリプレグの離型フィルムからの浮きが抑えられるようになる。   In other words, the release film carried on the reinforcing fiber prepreg is heated in the impregnation process to be in a state where moisture has evaporated from the original state, and further, rolled by pressure, applied with tension, and stretched somewhat. The release film approaches the original water-containing state by placing the water-containing sheet-like material adjacent to this, and is released from the stretched state and later cut into a sheet-like shape. However, as a result of the fact that the force to shrink the release film does not work, the prepreg is prevented from being lifted from the release film.

また、この強化繊維プリプレグの製造方法においては、前記加湿が、強化繊維プリプレグに担持された離型フィルムの50%Rhでの含水率に対して70%〜130%の範囲となるように行われることが好ましい。この範囲に加湿されれば、プリプレグの品質品位をほとんど低下することなく効果的に「浮き」を防止できる。   Further, in this method for producing a reinforced fiber prepreg, the humidification is performed so that the moisture content is within a range of 70% to 130% with respect to the moisture content at 50% Rh of the release film supported on the reinforced fiber prepreg. It is preferable. When humidified within this range, it is possible to effectively prevent “floating” without substantially reducing the quality of the prepreg.

以下に、本発明の望ましい実施の形態について、図面を参照しながら説明する。   Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings.

図1は本発明の一実施態様に係る強化繊維プリプレグの製造方法を示している。複数個のパッケージ1、1、・・・から繰り出される複数本の強化繊維糸条2、2、・・・は、引揃えロール3、4を経て張力を掛けられた後、コーム5に通じて一方向に互いに並行に引き揃えられた強化繊維シート6となる。強化繊維シート6は、上側の離型フィルムのロール体7、および下側の離型フィルムのロール体11からそれぞれ繰り出された上側離型フィルム10、下側離型フィルム14に挟み込まれるように、導入ロール8、12を介して導入される。上側離型フィルム10、下側離型フィルム14の少なくともいずれかには、マトリックス樹脂を塗布し、その樹脂塗布面が強化繊維シート6を向くように上側離型フィルム10、下側離型フィルム14を重ね合わせ、これらはヒータ15で予熱された後、加熱された含浸ロール16、17間に通され、上側離型フィルム10および/または下側離型フィルム14上のマトリックス樹脂の強化繊維糸条への転移、含浸が行われる。これにより一方向強化繊維プリプレグが得られるが、マトリックス樹脂の転移、含浸後は、上側の離型フィルム20は強化繊維プリプレグ21から剥ぎ取り上側の離型フィルムのロール体23として巻き取られ、強化繊維プリプレグ21は下側の離型フィルムごとロール状に、強化繊維プリプレグ21が外側になるように連続して巻き取り、一方向強化繊維プリプレグのロール体22とする。ここで、含浸後の一方向強化繊維プリプレグ21には、含浸後に、含水したシート状物25が下側の離型フィルムに隣接するように導入され、強化繊維プリプレグと共に強化繊維プリプレグのロール体22として巻き取られる。   FIG. 1 shows a method for producing a reinforcing fiber prepreg according to an embodiment of the present invention. A plurality of reinforcing fiber yarns 2, 2,... Fed out from a plurality of packages 1, 1,... Are tensioned through the alignment rolls 3, 4, and then lead to a comb 5. The reinforcing fiber sheets 6 are aligned in parallel in one direction. The reinforcing fiber sheet 6 is sandwiched between the upper release film 10 and the lower release film 14 that are fed out from the upper release film roll body 7 and the lower release film roll body 11, respectively. It is introduced through introduction rolls 8 and 12. A matrix resin is applied to at least one of the upper release film 10 and the lower release film 14, and the upper release film 10 and the lower release film 14 so that the resin application surface faces the reinforcing fiber sheet 6. These are preheated by a heater 15 and then passed between heated impregnating rolls 16 and 17 to reinforce matrix fiber reinforced fiber yarns on the upper release film 10 and / or the lower release film 14. Transfer to and impregnation. As a result, a unidirectional reinforcing fiber prepreg is obtained. After the matrix resin is transferred and impregnated, the upper release film 20 is peeled off from the reinforcing fiber prepreg 21 and wound up as a roll body 23 of the upper release film. The fiber prepreg 21 is rolled up in a roll shape together with the lower release film so that the reinforcing fiber prepreg 21 is on the outer side to obtain a roll body 22 of the unidirectional reinforcing fiber prepreg. Here, after impregnation, the hydrated sheet prepreg 21 is introduced into the unidirectional reinforcing fiber prepreg 21 so that the water-containing sheet 25 is adjacent to the lower release film, and the reinforcing fiber prepreg roll body 22 together with the reinforcing fiber prepreg. Rolled up as

上記において、含水したシート状物は、水分を保有できる構造のシート状物であれば特に制限はなく、熱可塑性樹脂あるいは熱硬化性樹脂からなる樹脂フィルムや、特に水分を保有しやすいように多孔性の樹脂フィルムのものが好ましい。また合成繊維、半合成繊維や天然繊維などからなる織物、編物、不織布などの布帛からなるシート状物であっても構わない。また、例えば、紙は水分を含有しやすく、かつ放出も容易であるため好ましく用いられる。   In the above, the water-containing sheet-like material is not particularly limited as long as it is a sheet-like material having a structure capable of holding moisture, and is a resin film made of a thermoplastic resin or a thermosetting resin, or particularly porous so as to easily hold moisture. The resin film is preferable. Further, it may be a sheet-like product made of a fabric such as a woven fabric, a knitted fabric or a non-woven fabric made of synthetic fiber, semi-synthetic fiber or natural fiber. Further, for example, paper is preferably used because it easily contains moisture and is easily released.

上記において、強化繊維糸条とは、例を挙げると炭素繊維糸条、ガラス繊維糸条、アラミド繊維糸条のような高強度、高弾性率繊維の糸条である。なかでも、比強度、比弾性率に優れたFRPを得ることができる炭素繊維糸条であるのが好ましい。そのような炭素繊維糸条としては、たとえば、ポリアクリロニトリル系繊維やピッチ系繊維等を原料繊維とする、単繊維数が1,000〜100,000本程度のものを用いることができる。   In the above, the reinforcing fiber yarn is a yarn of high strength and high elasticity fiber such as carbon fiber yarn, glass fiber yarn, and aramid fiber yarn. Especially, it is preferable that it is a carbon fiber yarn which can obtain FRP excellent in specific strength and specific elastic modulus. As such a carbon fiber yarn, for example, one having about 1,000 to 100,000 single fibers using polyacrylonitrile fiber or pitch fiber as a raw fiber can be used.

また、本発明では、強化繊維に含浸する樹脂は熱硬化性樹脂、熱可塑性樹脂いずれでも良いが、とりわけ強度や耐熱性の点で優れることから熱硬化性樹脂が好ましく選択される。熱硬化性樹脂には特に制限はないが、成形体を製造するに当たり大がかりな装置を必要としない点で加熱により硬化できる樹脂が好ましく用いられ、また得られたFRPの強度を高められる点でエポキシ樹脂が好ましく選択できる。エポキシ樹脂には硬化剤が含まれている樹脂組成物であってもよい。   In the present invention, the resin impregnated in the reinforcing fiber may be either a thermosetting resin or a thermoplastic resin, but a thermosetting resin is preferably selected because it is particularly excellent in terms of strength and heat resistance. There is no particular limitation on the thermosetting resin, but a resin that can be cured by heating is preferably used because it does not require a large-scale apparatus for producing a molded body, and an epoxy can be used in order to increase the strength of the obtained FRP. A resin can be preferably selected. The epoxy resin may be a resin composition containing a curing agent.

上記離型フィルムとしては、一般的に工業用フィルムとして知られる樹脂フィルムに表面を離型処理をしたものを用いることができる。また表面を離型処理した離型紙を用いることも好ましい。   As the release film, a resin film generally known as an industrial film and having a surface subjected to a release treatment can be used. It is also preferable to use a release paper whose surface has been release-treated.

図2、および図3は本発明の一実施態様に係る強化繊維プリプレグを示している。   2 and 3 show a reinforcing fiber prepreg according to an embodiment of the present invention.

上記したように、製造された強化繊維プリプレグは、図2に示したようにシート状のものであっても良く、この場合、離型フィルム32に担持された強化繊維プリプレグ31は、離型フィルム32に隣接するように含水したシート状物33を配置している。   As described above, the produced reinforcing fiber prepreg may be in the form of a sheet as shown in FIG. 2. In this case, the reinforcing fiber prepreg 31 supported by the release film 32 is a release film. A sheet-like material 33 containing water is disposed so as to be adjacent to 32.

また、上記したように製造された強化繊維プリプレグは、図3に示したようにロール状に巻いても良く、この場合、離型フィルム42に担持された強化繊維プリプレグ41は強化繊維プリプレグのロール体23としてなるが、含水したシート状物43は離型フィルム42の内側に隣接するように外側の強化繊維プリプレグ41と共に巻き込まれて配置している。   Further, the reinforcing fiber prepreg manufactured as described above may be wound in a roll shape as shown in FIG. 3, and in this case, the reinforcing fiber prepreg 41 supported on the release film 42 is a roll of reinforcing fiber prepreg. Although it becomes the body 23, the water-containing sheet-like material 43 is wound and arranged with the outer reinforcing fiber prepreg 41 so as to be adjacent to the inside of the release film.

このような強化繊維プリプレグでは、離型フィルムから剥離した浮きが少なく、例えば長径が3mm以上の浮きであれば、10個/m2以下となりうる結果、成形品の品位を良好にすることが可能となる。 In such a reinforced fiber prepreg, there is little lift off from the release film. For example, if the float has a major axis of 3 mm or more, it can be 10 pieces / m 2 or less. As a result, the quality of the molded product can be improved. It becomes.

以下に実施例と比較例を用いて本発明について具体的に説明する。   Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

実施例1
図1に示した装置を用いて強化繊維プリプレグを製造した。マトリックス樹脂にはエポキシ樹脂を用い、炭素繊維には、引張強度4.5GPa、引張弾性率230GPa、繊度0.80g/m、フィラメント数12000本/束の炭素繊維束を用い、離型フィルムには、上質紙を基材にプリプレグ貼り付け面に離型処理が施された含水率2.8%、放水率0.3%で幅1080mmの離型紙を上側、下側に用いた。マトリックス樹脂はこの上側、下側の離型紙のプリプレグ貼り付け面に塗布し、これを前記炭素繊維束を引き揃えた炭素繊維シートに上下から挟み込み、加熱した含浸ロール16、17で繊維にマトリックス樹脂を含浸、離型紙から転移した後、含水率3%、放水率0.4%、幅1000mmの上質紙を下側の離型紙に隣接するように配置し、共に巻き込んで、繊維重量含有率80%、プリプレグ目付188g/m2の幅1000mmの強化繊維プリプレグを得た。製造されたプリプレグにおける離型紙の水分率は1.6%であり、50%Rhの含水率2.8%に対して58%になった。
Example 1
A reinforcing fiber prepreg was produced using the apparatus shown in FIG. An epoxy resin is used for the matrix resin, a carbon fiber bundle having a tensile strength of 4.5 GPa, a tensile elastic modulus of 230 GPa, a fineness of 0.80 g / m, and a filament number of 12,000 pieces / bundle is used for the carbon fiber. A release paper having a water content of 2.8%, a water discharge rate of 0.3%, and a width of 1080 mm was used on the upper side and the lower side. The matrix resin is applied to the prepreg attachment surfaces of the upper and lower release papers, and is sandwiched from above and below by the carbon fiber sheet in which the carbon fiber bundles are aligned, and the matrix resin is applied to the fibers by heated impregnating rolls 16 and 17. After being impregnated and transferred from the release paper, a high-quality paper having a water content of 3%, a water discharge rate of 0.4%, and a width of 1000 mm is disposed adjacent to the lower release paper and wound together to obtain a fiber weight content of 80%. %, A reinforcing fiber prepreg having a prepreg weight per unit area of 188 g / m 2 and a width of 1000 mm was obtained. The moisture content of the release paper in the produced prepreg was 1.6%, which was 58% with respect to the moisture content of 2.8% of 50% Rh.

この強化繊維プリプレグを再び長さ1000mmに下側離型紙とともにシート状に切り出し、共に巻き込んだ上質紙を除いて、23℃、50%Rhの雰囲気に1時間放置したときのプリプレグ表面上の長径3mm以上の浮きの数を数えたところ、浮きは8個/m2であった。 This reinforcing fiber prepreg was cut again into a sheet with a lower release paper having a length of 1000 mm, and the major axis on the surface of the prepreg when left in an atmosphere of 23 ° C. and 50% Rh for 1 hour, excluding the high-quality paper wound together, was 3 mm. When the number of the above floats was counted, the floats were 8 / m 2 .

このプリプレグを用いて芯体への巻き付けを行ったところ、プリプレグに皺など発生することなく作業でき、ボイドを発生させず成形できた。   When this prepreg was wound around the core, the prepreg could be worked without generating wrinkles or the like, and could be molded without generating voids.

実施例2
実施例1において、下側の離型フィルムに含水率2.5%、放水率0.2%の離型紙を用い、含水したシート状物には含水率4%、放水率0.8%の上質紙を用いた以外は実施例1と同じにして強化繊維プリプレグを製造した。製造されたプリプレグにおける離型紙の水分率は1.8%であり、50%Rhの含水率2.5%に対して72%になった。このプリプレグの浮きの数を実施例1と同様に数えたところ、浮きの数は6個/m2であった。このプリプレグを用いて芯体への巻き付けを行ったところ、プリプレグに皺など発生することなく作業でき、ボイドを発生させず成形できた。
Example 2
In Example 1, a release paper having a water content of 2.5% and a water discharge rate of 0.2% was used for the lower release film, and the water content was 4% and the water discharge rate was 0.8%. A reinforcing fiber prepreg was produced in the same manner as in Example 1 except that fine paper was used. The moisture content of the release paper in the produced prepreg was 1.8%, which was 72% against a moisture content of 2.5% of 50% Rh. When the number of floats of this prepreg was counted in the same manner as in Example 1, the number of floats was 6 / m 2 . When this prepreg was wound around the core, the prepreg could be worked without generating wrinkles or the like, and could be molded without generating voids.

実施例3
実施例2において、含水したシート状物には含水率6.5%、放水率0.8%のクラフト紙を用いた以外は実施例2と同じにして強化繊維プリプレグを製造した。製造されたプリプレグにおける離型紙の水分率は1.95%であり、50%Rhの含水率2.5%に対して78%になった。このプリプレグの浮きの数を実施例1と同様に数えたところ、浮きの数は4個/m2であった。このプリプレグを用いて芯体への巻き付けを行ったところ、プリプレグに皺など発生することなく作業でき、ボイドを発生させず成形できた。
Example 3
In Example 2, a reinforced fiber prepreg was produced in the same manner as in Example 2 except that kraft paper having a water content of 6.5% and a water discharge rate of 0.8% was used as the water-containing sheet. The moisture content of the release paper in the produced prepreg was 1.95%, which was 78% with respect to the moisture content of 2.5% of 50% Rh. When the number of floats of this prepreg was counted in the same manner as in Example 1, the number of floats was 4 / m 2 . When this prepreg was wound around the core, the prepreg could be worked without generating wrinkles or the like, and could be molded without generating voids.

実施例4
実施例1において、含水したシート状物には含水率7.2%、放水率0.9%のクラフト紙を用い、下側の離型フィルムには含水率4%、放水率0.3%の離型紙を用いた以外は実施例1と同じにして強化繊維プリプレグを製造した。製造されたプリプレグにおける離型紙の水分率は3.3%であり、50%Rhの含水率4%に対して82.5%になった。このプリプレグの浮きの数を実施例1と同様に数えたところ、浮きの数は2個/m2であった。このプリプレグを用いて芯体への巻き付けを行ったところ、プリプレグに皺など発生することなく作業でき、ボイドを発生させず成形できた。
Example 4
In Example 1, kraft paper having a moisture content of 7.2% and a water discharge rate of 0.9% was used for the water-containing sheet, and the moisture content of the lower release film was 4% and the water discharge rate was 0.3%. A reinforced fiber prepreg was produced in the same manner as in Example 1 except that this release paper was used. The moisture content of the release paper in the produced prepreg was 3.3%, which was 82.5% with respect to the moisture content of 4% of 50% Rh. When the number of floats of this prepreg was counted in the same manner as in Example 1, the number of floats was 2 / m 2 . When this prepreg was wound around the core, the prepreg could be worked without generating wrinkles or the like, and could be molded without generating voids.

実施例5
実施例4において、含水したシート状物には含水率7.9%、放水率1.3%のクラフト紙を用いた以外は実施例4と同じにして強化繊維プリプレグを製造した。この時製造されたプリプレグにおける離型紙の水分率は3.6%であり、50%Rhの含水率4%に対して90%になった。このプリプレグの浮きの数を実施例1と同様に数えたところ、浮きの数は0個/m2であった。このプリプレグを用いて芯体への巻き付けを行ったところ、プリプレグに皺など発生することなく作業でき、ボイドを発生させず成形できた。
Example 5
In Example 4, a reinforced fiber prepreg was produced in the same manner as in Example 4 except that kraft paper having a water content of 7.9% and a water discharge rate of 1.3% was used as the water-containing sheet. The moisture content of the release paper in the prepreg produced at this time was 3.6%, which was 90% with respect to the moisture content of 4% of 50% Rh. When the number of floats of this prepreg was counted in the same manner as in Example 1, the number of floats was 0 / m 2 . When this prepreg was wound around the core, the prepreg could be worked without generating wrinkles or the like, and could be molded without generating voids.

実施例6
実施例1において、マトリックス樹脂を含浸、転移し、上側の離型紙を剥離した後、1m長さごとにシート状にカットし、そのシートの下側に含水した長さ1mのシート状物が接するように、すなわち、下側の離型紙に隣接するように含水したシート状物を隣接させて強化繊維プリプレグシートを製造した。この時、含水したシート状物は実施例5と同じ含水率7.9%、放水率1.3%で幅1100mmのクラフト紙を用い、離型紙には実施例5と同じ含水率4%、放水率0.3%で幅1080mmの離型紙を用いた。この時製造されたプリプレグにおける離型紙の水分率は4.4%であり、50%Rhの含水率4%に対して110%になった。このプリプレグの浮きの数を実施例1と同様に数えたところ、浮きの数は0個/m2であった。このプリプレグを用いて芯体への巻き付けを行ったところ、プリプレグに皺など発生することなく作業でき、ボイドを発生させず成形できた。
Example 6
In Example 1, after impregnating and transferring the matrix resin and peeling off the upper release paper, it is cut into a sheet shape every 1 m length, and a sheet-like material having a length of 1 m containing water is in contact with the lower side of the sheet. In other words, a reinforcing fiber prepreg sheet was manufactured by adjoining a sheet-like material containing water so as to be adjacent to the lower release paper. At this time, the water-containing sheet was kraft paper having a water content of 7.9%, a water discharge rate of 1.3% and a width of 1100 mm as in Example 5, and the release paper had a water content of 4% as in Example 5. A release paper having a water discharge rate of 0.3% and a width of 1080 mm was used. The moisture content of the release paper in the prepreg produced at this time was 4.4%, which was 110% with respect to the moisture content of 4% of 50% Rh. When the number of floats of this prepreg was counted in the same manner as in Example 1, the number of floats was 0 / m 2 . When this prepreg was wound around the core, the prepreg could be worked without generating wrinkles or the like, and could be molded without generating voids.

比較例1
実施例1において、含水したシート状物を用いず強化繊維プリプレグを製造した。このプリプレグの浮きの数を実施例1と同様に数えたところ、浮きの数は420個/m2であった。
Comparative Example 1
In Example 1, a reinforced fiber prepreg was produced without using a water-containing sheet. When the number of floats of this prepreg was counted in the same manner as in Example 1, the number of floats was 420 / m 2 .

このプリプレグを用いて芯体への巻き付けを行ったところ、プリプレグに皺が発生し、成形品中にボイドが発生した。   When this prepreg was wound around the core, wrinkles were generated in the prepreg, and voids were generated in the molded product.

Figure 2006063130
Figure 2006063130

本発明は、ゴルフシャフトや釣竿などのスポーツ、レジャー用途向けにだけでなく航空機用途や土木建築などの一般産業用途などにも応用することができるが、その応用範囲が、これらに限られるものではない。   The present invention can be applied not only to sports and leisure applications such as golf shafts and fishing rods but also to general industrial applications such as aircraft applications and civil engineering construction, but the application range is not limited to these. Absent.

本発明の一形態に係る強化繊維プリプレグの製造方法を実施する装置の概略側面図である。It is a schematic side view of the apparatus which enforces the manufacturing method of the reinforced fiber prepreg which concerns on one form of this invention. 本発明の一形態に係る強化繊維プリプレグの例を示す概略正面図である。It is a schematic front view which shows the example of the reinforced fiber prepreg which concerns on one form of this invention. 本発明の一形態に係る強化繊維プリプレグの例を示す概略斜視図である。It is a schematic perspective view which shows the example of the reinforced fiber prepreg which concerns on one form of this invention.

符号の説明Explanation of symbols

1:強化繊維束のパッケージ
2:強化繊維束
3:引揃えロール
4:引揃えロール
5:コーム
6:強化繊維シート
7:上側の離型フィルムのロール体
8:導入ロール
9:導入ロール
10:上側の離型フィルム
11:下側の離型フィルムのロール体
12:導入ロール
13:導入ロール
14:下側の離型フィルム
15:ヒータ
16:含浸ロール
17:含浸ロール
18:引取ロール
19:引取ロール
20:上側の離型フィルム
21:強化繊維プリプレグ
22:強化繊維プリプレグ材のロール体
23:上側の離型フィルムのロール体
24:含水したシート状物のロール体
25:含水したシート状物
31:強化繊維プリプレグ
32:離型フィルム
33:含水したシート状物
41:強化繊維プリプレグ
42:離型フィルム
43:含水したシート状物
1: Reinforcing fiber bundle package 2: Reinforcing fiber bundle 3: Draw roll 4: Draw roll 5: Comb 6: Reinforcing fiber sheet 7: Roll body of upper release film 8: Introducing roll 9: Introducing roll 10: Upper release film 11: Roll body of lower release film 12: Introduction roll 13: Introduction roll 14: Lower release film 15: Heater 16: Impregnation roll 17: Impregnation roll 18: Take-up roll 19: Take-up Roll 20: Upper release film 21: Reinforcing fiber prepreg 22: Roll body of reinforcing fiber prepreg material 23: Roll body of upper release film 24: Roll body of water-containing sheet 25: Water-containing sheet 31 : Reinforced fiber prepreg 32: Release film 33: Water-containing sheet-like material 41: Reinforced fiber prepreg 42: Release film 43: Hydrated Sheet-like material

Claims (8)

強化繊維シートにマトリックス樹脂が含浸され、少なくともその一表面に離型フィルムを貼り付けてなる強化繊維プリプレグに、含水したシート状物が前記離型フィルムに隣接するように重ねて配置されていることを特徴とする強化繊維プリプレグ。 The reinforcing fiber sheet is impregnated with a matrix resin, and a hydrated fiber prepreg is formed by adhering a release film on at least one surface of the reinforcing fiber sheet so that the water-containing sheet is placed adjacent to the release film. Reinforced fiber prepreg characterized by. 含水したシート状物の含水率が、強化繊維プリプレグの少なくとも一表面に貼り付ける離型フィルムの含水率より高いことを特徴とする請求項1に記載の強化繊維プリプレグ。 2. The reinforcing fiber prepreg according to claim 1, wherein the moisture content of the water-containing sheet is higher than the moisture content of the release film attached to at least one surface of the reinforcing fiber prepreg. 含水したシート状物の含水率が6%以上であることを特徴とする請求項1または2に記載の強化繊維プリプレグ。 The reinforcing fiber prepreg according to claim 1 or 2, wherein the moisture content of the water-containing sheet is 6% or more. 含水したシート状物の放水率が離型フィルムの放水率より高いことを特徴とする請求項1〜3のいずれかに記載の強化繊維プリプレグ。 The reinforcing fiber prepreg according to any one of claims 1 to 3, wherein the water content of the water-containing sheet is higher than that of the release film. 含水したシート状物の放水率が1.2%以上であることを特徴とする請求項1〜4のいずれかに記載の強化繊維プリプレグ。 The reinforcing fiber prepreg according to any one of claims 1 to 4, wherein the water discharge rate of the water-containing sheet is 1.2% or more. 強化繊維プリプレグがロール状またはシート状であることを特徴とする請求項1〜5のいずれかに記載の強化繊維プリプレグ。 6. The reinforcing fiber prepreg according to claim 1, wherein the reinforcing fiber prepreg is in a roll shape or a sheet shape. 強化繊維からなる強化繊維シートの上下両面に、少なくとも一方の面にマトリックス樹脂が塗布された離型フィルムを樹脂塗布面が強化繊維糸条側を向くように重ね合わせ、該重ね合わせ体を含浸ロールに通して強化繊維シートに離型フィルム上のマトリックス樹脂を転移、含浸する強化繊維プリプレグの製造方法において、マトリックス樹脂を含浸した後、強化繊維プリプレグに担持された離型フィルムに、含水したシート状物を隣接するように重ねて配置し、離型フィルムを加湿することを特徴とする強化繊維プリプレグの製造方法。 On both the upper and lower surfaces of the reinforcing fiber sheet made of reinforcing fibers, a release film having a matrix resin coated on at least one surface is superposed so that the resin coated surface faces the reinforcing fiber yarn side, and the superposed body is impregnated roll In the manufacturing method of the reinforced fiber prepreg, in which the matrix resin on the release film is transferred to and impregnated into the reinforcing fiber sheet, after impregnating the matrix resin, the release film supported by the reinforcing fiber prepreg is in a sheet form containing water A method for producing a reinforced fiber prepreg, characterized in that an object is placed so as to be adjacent to each other and the release film is humidified. 前記加湿は、前記離型フィルムの50%Rhでの含水率に対して70%〜130%の範囲となるように行われることを特徴とする請求項7に記載の強化繊維プリプレグの製造方法。 The said humidification is performed so that it may become the range of 70%-130% with respect to the moisture content in 50% Rh of the said release film, The manufacturing method of the reinforced fiber prepreg of Claim 7 characterized by the above-mentioned.
JP2004245010A 2004-08-25 2004-08-25 Reinforcing fiber prepreg and method for producing the reinforcing fiber prepreg Pending JP2006063130A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009537691A (en) * 2006-05-22 2009-10-29 アドバンスト コンポジッツ グループ リミテッド Molding material
WO2018181983A1 (en) * 2017-03-31 2018-10-04 三菱ケミカル株式会社 Prepreg sheet, method for manufacturing same, skin material-provided unitary layer, method for manufacturing article molded from fiber-reinforced composite material, and article molded from fiber-reinforced composite material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009537691A (en) * 2006-05-22 2009-10-29 アドバンスト コンポジッツ グループ リミテッド Molding material
WO2018181983A1 (en) * 2017-03-31 2018-10-04 三菱ケミカル株式会社 Prepreg sheet, method for manufacturing same, skin material-provided unitary layer, method for manufacturing article molded from fiber-reinforced composite material, and article molded from fiber-reinforced composite material
JPWO2018181983A1 (en) * 2017-03-31 2019-04-04 三菱ケミカル株式会社 Prepreg sheet, manufacturing method thereof, unit layer with skin material, manufacturing method of fiber reinforced composite material molded product, and fiber reinforced composite material molded product
CN110461918A (en) * 2017-03-31 2019-11-15 三菱化学株式会社 Prepreg, its manufacturing method, the elementary layer with surface layer material, the manufacturing method of fibre reinforced composites molded product and fibre reinforced composites molded product
CN110461918B (en) * 2017-03-31 2022-06-28 三菱化学株式会社 Prepreg and method for producing same, cell layer with skin material, fiber-reinforced composite material molded article, and method for producing same
US11421089B2 (en) 2017-03-31 2022-08-23 Mitsubishi Chemical Corporation Prepreg sheet, method for manufacturing same, unit layer with a covering material, method for manufacturing fiber-reinforced composite, and fiber-reinforced composite

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