JPH04499B2 - - Google Patents
Info
- Publication number
- JPH04499B2 JPH04499B2 JP61139270A JP13927086A JPH04499B2 JP H04499 B2 JPH04499 B2 JP H04499B2 JP 61139270 A JP61139270 A JP 61139270A JP 13927086 A JP13927086 A JP 13927086A JP H04499 B2 JPH04499 B2 JP H04499B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- prepreg
- roving
- roving prepreg
- weight
- 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
Links
- 229920005989 resin Polymers 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 28
- 229920002050 silicone resin Polymers 0.000 claims description 19
- 229920002545 silicone oil Polymers 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000003822 epoxy resin Substances 0.000 claims description 13
- 229920000647 polyepoxide Polymers 0.000 claims description 13
- 229920001187 thermosetting polymer Polymers 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229940099259 vaseline Drugs 0.000 claims description 5
- 239000004264 Petrolatum Substances 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 229940066842 petrolatum Drugs 0.000 claims description 4
- 235000019271 petrolatum Nutrition 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000000465 moulding Methods 0.000 description 7
- 229920000049 Carbon (fiber) Polymers 0.000 description 6
- 239000004917 carbon fiber Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 238000010420 art technique Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920003319 Araldite® Polymers 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- -1 amine compounds Chemical class 0.000 description 1
- 230000000181 anti-adherent effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 238000009730 filament winding Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
Description
〔技術分野〕
本発明は、粘着性が低く解舒性に優れたロービ
ンプリプレグ及びその製造法に関するものであ
る。
更に詳しくは、本発明は、柔軟性に富みボビン
への巻取が容易で、何よりもボビンからの解舒性
に優れ、しかも、成形物に良好な機械的特性を与
えるロービングプリプレグ及びその製造法に関す
るものである。
〔従来技術とその問題点〕
ロービングに未硬化の樹脂を含浸したプリプレ
グ、即ちロービングプリプレグは、プレス成形、
フイラメントワインデイング成形、プルトルージ
ヨン成形等に多く用いられている。
このロービングプリプレグは通常ボビンに巻取
られた形にて、流通、保存され、使用時には、こ
のボビンから解舒されて供される。しかしなが
ら、ロービングプリプレグはロービングに未硬化
の樹脂を含浸したプリプレグであるため粘着性が
あり、ボビンに巻取られた状態にて、ロービング
が互いに接着し、解舒性が極めて低いか、保存状
態によつては解舒不能となる。
このような状態を解決する手段として、樹脂組
成物にタルク粉やシリカ粉末などの無機粉末を加
える方法（従来技術Ａ）や、樹脂自体を硬いもの
にする方法（従来技術Ｂ）などがある。また、シ
リコーン油等を含む樹脂組成物の溶液をストラン
ドに含浸させる方法（従来技術Ｃ）も提案されて
いる（特開昭58−113226号公報、同58−113226号
公報）。
一方においてロービングプリプレグを用いた成
形物は、強度、弾性等の本来複合材料材の保有す
べき特性を備え、強化材繊維とマトリツクス樹脂
との接着性が高く層間剪断強度（ILSS）が高く、
ひいては機械的特性が優れたものでなければなら
ない。
ロービングプリプレグの樹脂組成物に無機粉末
を加える前記従来技術Ａの方法は、その量を３〜
10重量％も加えないと粘着防止の効果はなく、こ
のような大量の無機粉末の添加は、成形物の
ILSSを低下させるのみでなく、炭素繊維を強化
材とする場合、成形物の外観を悪くする。
樹脂自体を硬いものにする前記従来技術Ｂの方
法は、樹脂成分に高分子の成分を添加し、ロービ
ングプリプレグの粘着性を低下させるものである
が、これによるとロービングプリプレグ自体が硬
くなりドレープ性に欠けるため、巻取時に折れた
り、成形金型への供給が円滑に行えない等の問題
を有する。
ロービングプリプレグ（ストランドプリプレ
グ）にシリコーン油含有樹脂組成物溶液を含浸す
る前記従来技術Ｃの方法は溶剤を用いるためこの
方法によると、シリコーン油が樹脂組成物層内部
にまで入つて含まれることになるので、プリプレ
グの表面の粘着性低下ひいては解舒性が必ずしも
十分良好ではない。強いて解舒性を高めようとす
ると、シリコーン油の添加量が多くなり、成形物
の機械的特性の低下を惹起する。
〔発明の目的〕
本発明の目的は、ボビンに巻取られた状態のロ
ービングプリプレグの解舒性が良好で、しかも、
成形金型に対するドレープ性が良く、成形した
後、成形物に優れた機械的特性を与えることので
きるロービングプリプレグを提供することにあ
る。
〔発明の構成〕
本発明の構成は下記の通りである。
〔第１発明〕
繊維束に熱硬化性樹脂を含浸したロービングプ
リプレグにおいて、実質上その表面のみに該ロー
ビングプリプレグに対し0.1〜1.5重量％のシリコ
ーン樹脂、シリコーン油及びワセリンの一種又は
二種以上が、無溶剤法にて付与されて存在してい
る低粘着性ロービングプリプレグ。
〔第２発明〕
繊維束に熱硬化性樹脂を含浸したロービングプ
リプレグの製造に当り、ロービングプリプレグに
樹脂を含浸させた後その表面に該ロービングプリ
プレグに対し0.1〜1.5重量％のシリコーン樹脂、
シリコーン油及びワセリンの一種又は二種以上を
無溶剤法にて付与することを特徴とする実質上そ
の表面のみにシリコーン樹脂等が存在している低
粘着性ロービングプリプレグの製造法。
本発明のロービングプリプレグに用いる繊維束
は、炭素繊維、ガラス繊維、金属被覆炭素繊維な
どの無機繊維、芳香族ポリアミドなどの有機繊維
等の既知の強化繊維の束であり、構成本数は特に
制限されないが、通常500〜24000フイラメントの
ものが用いられる。
炭素繊維としては、従来知られているアクリル
系、レーヨン系、ピツチ系などが挙げられ、その
グレードには特に制限がない。
マトリツクス成分である熱硬化性樹脂は、繊維
強化複合材料のマトリツクス樹脂として使われて
いる通常の樹脂、例えば不飽和ポリエステル樹
脂、フエノール樹脂、エポキシ樹脂、ポリイミド
樹脂、ビスマレイミド樹脂等を主成分とするもの
であるが、特に優れた機械的特性を与え、成形性
も良好なことからエポキシ樹脂が好ましい。
硬化剤としては、それぞれのマトリツクス樹脂
に適合した既知のものが使用されうる。
特にエポキシ樹脂にあつては、フエノール・ノ
ボラツク型エポキシ樹脂、ビスフエノール型エポ
キシ樹脂、テトラグリシジルアミン型エポキシ樹
脂及びこれらの変成樹脂等の単独又は混合樹脂が
用いられる。
エポキシ樹脂の硬化剤及び硬化促進剤成分とし
てはジシアンジアミド、ジアミノジフエニルスル
ホン等のアミン系化合物、イミダゾール系化合
物、ポリアミド系化合物、酸無水物系硬化剤、３
−（３，４−ジクロルフエニル）−１，１−ジメチ
ル尿素などが使用される。
他の成分として、粘度調整剤（例えばシリカ微
粉末等の無機充填剤）、ニトリルゴム等も用いら
れる。
樹脂組成物の具体的配合比を例示すると下記の
通りである。フエノール・ノボラツク型エポキシ
樹脂50〜80重量％、ビスフエノールＡ型エポキシ
樹脂20〜50重量％とを含む樹脂混合物100重量％
に対し、硬化剤成分としてジシアンジアミド及び
３−（３，４−ジクロルフエニル）−１，１−ジメ
チル尿素を各々0.5〜６重量部配合する。樹脂組
成物は、必要により粘度調整剤を加え、粘度が30
〜300ポイズ（80℃）となるように調製する。ロ
ービングプリフレグにおける樹脂含有率は20〜50
重量％特に25〜35重量％が成形物の物性の点から
好ましい。
本発明において、ロービングプリプレグの表面
に付与されるシリコーン樹脂、シリコーン油又は
ワセリンはロービングプリプレグに対し、0.1〜
1.5重量％が成形物の機械的特性を低下させるこ
となくプリプレグに非粘着性を付与させるのに必
要であり、特に0.2〜１重量％が好ましい。付与
量が1.5重量超では成形物の機械的特性が低下し、
0.1重量部未満ではプリプレグの巻取時の解舒性
と成形金型に対するドレープ性が不良となり、本
発明の目的が達成されない。従来一般に、ロービ
ングプリプレグの製造法は、熱硬化性樹脂を溶剤
に溶解した樹脂溶液に繊維束を浸漬して含浸し、
次いで乾燥することにより行われる。
これに対し、本発明の方法は、この熱硬化性樹
脂含浸ロービングプリプレグの表面に特定微量の
シリコーン樹脂、シリコーン油又はワセリンを溶
剤を用いることなく付与し、プリプレグに非粘着
性を与えるものである。
本発明においては、シリコーン樹脂、シリコー
ン油又はワセリンは無溶剤で付与することが重要
であり、このように無溶剤で付与するとプリプレ
グの表面のみにシリコーン樹脂等を存在させるこ
とができ、0.1〜1.5重量％の量で低粘着性ひいて
は良好な解舒性を与えることができる。
本発明において無溶剤にてロービングプリプレ
グ表面に0.1〜1.5重量％のシリコーン樹脂、シリ
コーン油又はワセリンを付与する方法としては、
ローラー転写法、スプレー法、リツプ法等が採用
されうるが、付与量を均一にコントロールするに
はローラー転写法が好ましい。
シリコーン樹脂、シリコーン油、ワセリンが固
形の場合は加熱し、液状にして付与される。
シリコーン樹脂、シリコーン油はアクリル樹
脂、ポリエステル樹脂、ウレタン樹脂などで変成
したものも含まれ、分子中にメトキシ基、水酸基
を有するものが特に好ましい。シリコーン樹脂
は、室温で固形のものであり、かかるものとして
は、KR216、KR213、KR206（以上信越化学工業
社製）、SH−6018（東レシリコーン社製）等があ
る。また、シリコーン油は室温で液状、グリース
状のものであり、例えばTSR−165（東芝シリコ
ーン社製）KF69、KS64、KS69、KR213、
KS63W（以上信越化学工業社製）等である。
〔発明の効果〕
本発明のロービングプリプレグは、下表に示す
ようにそれ自体のピール強度が小で、したがつて
解舒性が良好であり、かつそれから得られる成形
物の機械的特性の低下も少なく有用な物である。
[Technical Field] The present invention relates to a rovin prepreg with low adhesiveness and excellent unwinding properties, and a method for producing the same. More specifically, the present invention provides a roving prepreg that is highly flexible, easy to wind up on a bobbin, has excellent unwinding properties from the bobbin, and provides molded products with good mechanical properties, and a method for producing the same. It is related to. [Prior art and its problems] Prepreg in which roving is impregnated with uncured resin, that is, roving prepreg, is produced by press molding,
It is widely used for filament winding molding, pultrusion molding, etc. This roving prepreg is usually distributed and stored in the form of being wound around a bobbin, and when used, it is unwound from the bobbin and provided. However, since roving prepreg is a prepreg in which the roving is impregnated with uncured resin, it is sticky, and when wound on a bobbin, the rovings adhere to each other, resulting in extremely low unwinding properties or storage conditions. Eventually, it becomes impossible to unravel. As means for solving this situation, there are a method of adding inorganic powder such as talc powder or silica powder to the resin composition (prior art technique A), and a method of making the resin itself hard (prior art technique B). Furthermore, a method (prior art C) in which a strand is impregnated with a solution of a resin composition containing silicone oil or the like has been proposed (Japanese Unexamined Patent Publications Nos. 58-113226 and 1982-113226). On the other hand, molded products using roving prepreg have properties such as strength and elasticity that composite materials should possess, and have high interlaminar shear strength (ILSS) due to high adhesion between reinforcing fibers and matrix resin.
Furthermore, it must have excellent mechanical properties. In the method of the prior art A, which adds inorganic powder to the resin composition of the roving prepreg, the amount thereof is 3 to 3.
There is no anti-adhesive effect unless 10% by weight is added, and adding such a large amount of inorganic powder can cause molded products to
Not only does it reduce ILSS, but when carbon fiber is used as a reinforcing material, it also worsens the appearance of the molded product. The method of prior art B, which makes the resin itself hard, involves adding a polymer component to the resin component to reduce the stickiness of the roving prepreg. This causes problems such as breakage during winding and difficulty in supplying the material to the mold. The method of Prior Art C, which impregnates a roving prepreg (strand prepreg) with a silicone oil-containing resin composition solution, uses a solvent. Therefore, the adhesiveness of the surface of the prepreg decreases, and the unwinding property is not necessarily sufficiently good. If an attempt is made to improve the unwinding property, the amount of silicone oil added increases, causing a decrease in the mechanical properties of the molded product. [Object of the Invention] The object of the present invention is to provide a roving prepreg that is wound on a bobbin and has good unwinding properties, and
It is an object of the present invention to provide a roving prepreg that has good drapability with respect to a molding die and can impart excellent mechanical properties to a molded product after being molded. [Structure of the Invention] The structure of the present invention is as follows. [First invention] In a roving prepreg in which a fiber bundle is impregnated with a thermosetting resin, 0.1 to 1.5% by weight of one or more of silicone resin, silicone oil, and petrolatum is added to substantially only the surface of the roving prepreg. , a low-tack roving prepreg that is applied using a solvent-free method. [Second invention] In producing a roving prepreg in which a fiber bundle is impregnated with a thermosetting resin, after impregnating the roving prepreg with the resin, 0.1 to 1.5% by weight of a silicone resin based on the roving prepreg is applied to the surface of the roving prepreg,
A method for producing a low-tack roving prepreg in which a silicone resin or the like is present substantially only on the surface thereof, characterized by applying one or more of silicone oil and vaseline by a solvent-free method. The fiber bundle used in the roving prepreg of the present invention is a bundle of known reinforcing fibers such as carbon fiber, glass fiber, inorganic fiber such as metal-coated carbon fiber, and organic fiber such as aromatic polyamide, and the number of fibers is not particularly limited. However, those with 500 to 24,000 filaments are usually used. Examples of the carbon fiber include conventionally known acrylic, rayon, and pitch type carbon fibers, and there is no particular restriction on the grade thereof. The thermosetting resin that is the matrix component is mainly composed of ordinary resins used as matrix resins for fiber-reinforced composite materials, such as unsaturated polyester resins, phenolic resins, epoxy resins, polyimide resins, and bismaleimide resins. However, epoxy resin is preferred because it provides particularly excellent mechanical properties and good moldability. As the curing agent, known curing agents that are compatible with each matrix resin can be used. In particular, for epoxy resins, phenol-novolac type epoxy resins, bisphenol type epoxy resins, tetraglycidylamine type epoxy resins, and modified resins thereof may be used alone or in combination. As curing agents and curing accelerator components for epoxy resins, amine compounds such as dicyandiamide and diaminodiphenylsulfone, imidazole compounds, polyamide compounds, acid anhydride curing agents, 3
-(3,4-dichlorophenyl)-1,1-dimethylurea and the like are used. Other components that may be used include viscosity modifiers (for example, inorganic fillers such as fine silica powder), nitrile rubber, and the like. Examples of specific blending ratios of the resin composition are as follows. 100% by weight of a resin mixture containing 50-80% by weight of a phenolic novolac type epoxy resin and 20-50% by weight of a bisphenol A-type epoxy resin.
dicyandiamide and 3-(3,4-dichlorophenyl)-1,1-dimethylurea are each added in an amount of 0.5 to 6 parts by weight as curing agent components. If necessary, add a viscosity modifier to the resin composition until the viscosity is 30.
Adjust to ~300 poise (80℃). Resin content in roving purifreg is 20-50
% by weight, particularly preferably 25 to 35% by weight from the viewpoint of physical properties of the molded product. In the present invention, the amount of silicone resin, silicone oil, or petrolatum applied to the surface of the roving prepreg is 0.1 to
1.5% by weight is necessary to impart non-stick properties to the prepreg without reducing the mechanical properties of the molded article, and 0.2 to 1% by weight is particularly preferred. If the applied amount exceeds 1.5 weight, the mechanical properties of the molded product will deteriorate,
If the amount is less than 0.1 part by weight, the unwinding property of the prepreg during winding and the drape property against the molding die will be poor, and the object of the present invention will not be achieved. Conventionally, the manufacturing method for roving prepreg is to immerse a fiber bundle in a resin solution in which a thermosetting resin is dissolved in a solvent.
This is then carried out by drying. In contrast, the method of the present invention applies a specific trace amount of silicone resin, silicone oil, or vaseline to the surface of this thermosetting resin-impregnated roving prepreg without using a solvent, thereby imparting non-adhesive properties to the prepreg. . In the present invention, it is important to apply the silicone resin, silicone oil, or vaseline without a solvent.If applied without a solvent in this way, the silicone resin etc. can be present only on the surface of the prepreg. Amounts of % by weight can provide low tack and thus good unwinding properties. In the present invention, the method of applying 0.1 to 1.5% by weight of silicone resin, silicone oil, or vaseline to the surface of the roving prepreg without a solvent is as follows:
A roller transfer method, a spray method, a lip method, etc. may be employed, but the roller transfer method is preferable in order to uniformly control the amount of application. When silicone resin, silicone oil, and petrolatum are solid, they are heated and applied in a liquid state. Silicone resins and silicone oils include those modified with acrylic resins, polyester resins, urethane resins, etc., and those having a methoxy group or hydroxyl group in the molecule are particularly preferred. Silicone resins are solid at room temperature, and examples include KR216, KR213, KR206 (manufactured by Shin-Etsu Chemical Co., Ltd.), SH-6018 (manufactured by Toray Silicone Co., Ltd.), and the like. In addition, silicone oil is liquid or grease-like at room temperature, such as TSR-165 (manufactured by Toshiba Silicone Corporation) KF69, KS64, KS69, KR213,
KS63W (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. [Effects of the Invention] As shown in the table below, the roving prepreg of the present invention has low peel strength itself, and therefore has good unwinding properties, and the mechanical properties of molded products obtained from it are reduced. It is a very useful item.
【表】
〔実施例及び比較列〕
実施例 １
（樹脂溶液の調製）
フエノール・ノボラツク型エポキシ樹脂（チバ
ガイギー社製アラルダイトEPN−1138）70重量
部、ビスフエノールＡ型エポキシ樹脂30重量部
（シエル化学社製エピコート1002・20重量部、エ
ピコート828・10重量部の混合系）を混合して樹
脂混合物（100ポイズ・80℃）とした。これに硬
化剤ジシアンジアミド３重量部、硬化促進剤３−
（３，４ジクロフエニル）−１，１−Ｎジメチル尿
素５重量部を加えアセトン及びエチレングリコー
ルモノメチルエーテルの１対１の混合溶剤に溶か
し40重量％溶液とした。
（含浸・塗布）
この樹脂溶液に12000フイラメントからなる高
強度炭素繊維束を通して樹脂溶液を含浸後、100
℃、５分間、熱風乾燥炉を通し、ロービングプリ
プレグを得た。ロービングプリプレグの樹脂含有
量は36重量％であつた。
このロービングプリプレグにシリコーン樹脂と
してKR216（信越化学工業社製、水酸基含有シリ
コーン樹脂）をローラー転写法（無溶剤）にて塗
布した。塗布量は0.7重量％とした。このものの
ピール強度は下表の通りであつた。
比較のために同一のシリコーン樹脂をアセトン
に溶解し、ロービングプリプレグに対し、0.7重
量％と10重量％と量を変えそれぞれ塗布し乾燥し
た。
（成形）
このシリコーン樹脂等を塗布したロービングプ
リプレグを一方向に引き揃え、100℃でプレスし
てシート状プリプレグとした後、積層して130℃
×７Kg／cm2×90分の成形条件で成形し、成形物の
機械的強度を測定した。その結果を下表に示す。
比較のために、タルク粉を３％付与したもの及
び何も付与しないものについて、同時に示す。[Table] [Examples and comparison column] Example 1 (Preparation of resin solution) 70 parts by weight of phenol novolac type epoxy resin (Araldite EPN-1138 manufactured by Ciba Geigy), 30 parts by weight of bisphenol A type epoxy resin (Ciel Chemical) A resin mixture (100 poise, 80°C) was prepared by mixing 20 parts by weight of Epicote 1002 and 10 parts by weight of Epicote 828. To this, 3 parts by weight of curing agent dicyandiamide and 3 parts by weight of curing accelerator.
5 parts by weight of (3,4 dichlorophenyl)-1,1-N dimethylurea was added and dissolved in a 1:1 mixed solvent of acetone and ethylene glycol monomethyl ether to form a 40% by weight solution. (Impregnation/coating) After impregnating the resin solution through a high-strength carbon fiber bundle consisting of 12,000 filaments,
A roving prepreg was obtained by passing through a hot air drying oven at ℃ for 5 minutes. The resin content of the roving prepreg was 36% by weight. KR216 (manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl group-containing silicone resin) as a silicone resin was applied to this roving prepreg by a roller transfer method (solventless). The coating amount was 0.7% by weight. The peel strength of this product was as shown in the table below. For comparison, the same silicone resin was dissolved in acetone and applied to the roving prepreg in different amounts, 0.7% by weight and 10% by weight, and dried. (Molding) The roving prepreg coated with silicone resin etc. is pulled in one direction, pressed at 100℃ to form a sheet prepreg, and then laminated at 130℃.
It was molded under molding conditions of ×7 Kg/cm 2 ×90 minutes, and the mechanical strength of the molded product was measured. The results are shown in the table below. For comparison, a sample to which 3% talcum powder was added and a sample to which no talcum powder was added are shown at the same time.
【表】
第２表の結果によれば、本発明にかかるロービ
ングプリプレグは、それ自体のピール強度が小
で、したがつて、解舒性が良好であることがわか
る。更にそれから得られる成形物の曲げ強度、曲
げ弾性率、ILSS等の機械的特性に悪影響を及ぼ
さないこともわかる。
実施例 ２
実施例１の方法に準じ、塗布剤としてシリコー
ン油としてKR213、（信越化学工業社製、メトキ
シ基含有シリコーン油）を用いロービングプリプ
レグを製造した。
このもの及び成形物の性能は下記の通りであつ
た。[Table] According to the results in Table 2, it can be seen that the roving prepreg according to the present invention has a low peel strength and therefore has good unwinding properties. Furthermore, it can be seen that there is no adverse effect on the mechanical properties such as bending strength, bending modulus, ILSS, etc. of the molded product obtained from it. Example 2 According to the method of Example 1, a roving prepreg was produced using KR213 (manufactured by Shin-Etsu Chemical Co., Ltd., methoxy group-containing silicone oil) as a silicone oil as a coating agent. The properties of this product and the molded product were as follows.
【表】【table】
【表】
実施例 ３
シリコーン油としてメトキシ油、水酸基を含ま
ないKS64、KS69（信越化学工業社製）を用い実
施例１と同様にしてロービングプリプレグを製造
した。このもの及び成形物の性質は下記の通りで
あつた。[Table] Example 3 A roving prepreg was produced in the same manner as in Example 1 using methoxy oil and hydroxyl-free KS64 and KS69 (manufactured by Shin-Etsu Chemical Co., Ltd.) as silicone oils. The properties of this product and the molded product were as follows.
【表】【table】
Claims (1)
プリプレグにおいて、実質上その表面のみに該ロ
ービングプリプレグに対し0.1〜1.5重量％のシリ
コーン樹脂、シリコーン油及びワセリンの一種又
は二種以上が無溶剤法にて付与されて存在してい
る低粘着性ロービングプリプレグ。 ２ 熱硬化性樹脂がエポキシ樹脂である特許請求
の範囲１のロービングプリプレグ。 ３ 熱硬化性樹脂がエポキシ樹脂であり、かつシ
リコーン樹脂又はシリコーン油が末端にメトキシ
基、水酸基を有するものである特許請求の範囲１
のロービングプリプレグ。 ４ 繊維束に熱硬化性樹脂を含浸したロービング
プリプレグの製造に当り、ロービングプリプレグ
に樹脂を含浸させた後その表面に該ロービングプ
リプレグに対し0.1〜1.5重量％のシリコーン樹
脂、シリコーン油及びワセリンの一種又は二種以
上を無溶剤法にて付与することを特徴とする実質
上その表面のみにシリコーン樹脂等が存在してい
る低粘着性ロービングプリプレグの製造法。[Claims] 1. In a roving prepreg in which a fiber bundle is impregnated with a thermosetting resin, 0.1 to 1.5% by weight of one or both of silicone resin, silicone oil, and petrolatum is added to the roving prepreg substantially only on the surface thereof. A low-tack roving prepreg that has been applied using a solvent-free method. 2. The roving prepreg according to claim 1, wherein the thermosetting resin is an epoxy resin. 3 Claim 1 in which the thermosetting resin is an epoxy resin, and the silicone resin or silicone oil has a methoxy group or a hydroxyl group at the end.
roving prepreg. 4. When manufacturing a roving prepreg in which fiber bundles are impregnated with a thermosetting resin, the roving prepreg is impregnated with the resin, and then 0.1 to 1.5% by weight of silicone resin, silicone oil, and a type of vaseline to the roving prepreg are applied to the surface of the roving prepreg. Or, a method for producing a low-tack roving prepreg in which a silicone resin or the like is present substantially only on the surface thereof, characterized in that two or more types are applied by a solvent-free method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13927086A JPS62297336A (en) | 1986-06-17 | 1986-06-17 | Roving prepreg |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13927086A JPS62297336A (en) | 1986-06-17 | 1986-06-17 | Roving prepreg |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62297336A JPS62297336A (en) | 1987-12-24 |
| JPH04499B2 true JPH04499B2 (en) | 1992-01-07 |
Family
ID=15241371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13927086A Granted JPS62297336A (en) | 1986-06-17 | 1986-06-17 | Roving prepreg |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62297336A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5721428A (en) * | 1980-07-14 | 1982-02-04 | Toho Rayon Co Ltd | Strand prepreg |
-
1986
- 1986-06-17 JP JP13927086A patent/JPS62297336A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5721428A (en) * | 1980-07-14 | 1982-02-04 | Toho Rayon Co Ltd | Strand prepreg |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62297336A (en) | 1987-12-24 |
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