JP2000086784A - Prepreg - Google Patents
PrepregInfo
- Publication number
- JP2000086784A JP2000086784A JP26174698A JP26174698A JP2000086784A JP 2000086784 A JP2000086784 A JP 2000086784A JP 26174698 A JP26174698 A JP 26174698A JP 26174698 A JP26174698 A JP 26174698A JP 2000086784 A JP2000086784 A JP 2000086784A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- prepreg
- resin
- parts
- resin flow
- 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.)
- Pending
Links
- 229920005989 resin Polymers 0.000 claims abstract description 154
- 239000011347 resin Substances 0.000 claims abstract description 154
- 239000003822 epoxy resin Substances 0.000 claims abstract description 52
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 52
- 239000011159 matrix material Substances 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 19
- -1 alkyl urea Chemical compound 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 44
- 239000004917 carbon fiber Substances 0.000 claims description 44
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 41
- 239000000835 fiber Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 9
- 229920006231 aramid fiber Polymers 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 230000002787 reinforcement Effects 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract description 68
- 230000000704 physical effect Effects 0.000 abstract description 23
- 239000011342 resin composition Substances 0.000 abstract description 18
- 238000000034 method Methods 0.000 description 56
- 239000000203 mixture Substances 0.000 description 34
- 239000012943 hotmelt Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011800 void material Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 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 5
- 239000002131 composite material Substances 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N methylguanidine Chemical compound CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- SNVRDQORMVVQBI-UPHRSURJSA-N (z)-but-2-enedihydrazide Chemical compound NNC(=O)\C=C/C(=O)NN SNVRDQORMVVQBI-UPHRSURJSA-N 0.000 description 1
- NQOFYFRKWDXGJP-UHFFFAOYSA-N 1,1,2-trimethylguanidine Chemical compound CN=C(N)N(C)C NQOFYFRKWDXGJP-UHFFFAOYSA-N 0.000 description 1
- COSWCAGTKRUTQV-UHFFFAOYSA-N 1,1,3-trimethylurea Chemical compound CNC(=O)N(C)C COSWCAGTKRUTQV-UHFFFAOYSA-N 0.000 description 1
- LINDOXZENKYESA-UHFFFAOYSA-N 1,2-dimethylguanidine Chemical compound CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 description 1
- POFFJVRXOKDESI-UHFFFAOYSA-N 1,3,5,7-tetraoxa-4-silaspiro[3.3]heptane-2,6-dione Chemical compound O1C(=O)O[Si]21OC(=O)O2 POFFJVRXOKDESI-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- HPDCRAOWFOIELP-UHFFFAOYSA-N 1-(diaminomethylidene)-2-(2,6-dimethylphenyl)guanidine Chemical compound CC1=CC=CC(C)=C1N=C(N)N=C(N)N HPDCRAOWFOIELP-UHFFFAOYSA-N 0.000 description 1
- VPSXHKGJZJCWLV-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(1-ethylpiperidin-4-yl)oxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OC1CCN(CC1)CC VPSXHKGJZJCWLV-UHFFFAOYSA-N 0.000 description 1
- CGWBIHLHAGNJCX-UHFFFAOYSA-N 2-butylguanidine Chemical compound CCCCNC(N)=N CGWBIHLHAGNJCX-UHFFFAOYSA-N 0.000 description 1
- KEWLVUBYGUZFKX-UHFFFAOYSA-N 2-ethylguanidine Chemical compound CCNC(N)=N KEWLVUBYGUZFKX-UHFFFAOYSA-N 0.000 description 1
- XSXYESVZDBAKKT-UHFFFAOYSA-N 2-hydroxybenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1O XSXYESVZDBAKKT-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- QRJZGVVKGFIGLI-UHFFFAOYSA-N 2-phenylguanidine Chemical compound NC(=N)NC1=CC=CC=C1 QRJZGVVKGFIGLI-UHFFFAOYSA-N 0.000 description 1
- BWMDMTSNSXYYSP-UHFFFAOYSA-N 2-propylguanidine Chemical compound CCCNC(N)=N BWMDMTSNSXYYSP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- LCLYWJDPJMDAQN-UHFFFAOYSA-N 3-(4-methoxyphenyl)-1,1-dimethylurea Chemical compound COC1=CC=C(NC(=O)N(C)C)C=C1 LCLYWJDPJMDAQN-UHFFFAOYSA-N 0.000 description 1
- NEVYNAFJLYYHPR-UHFFFAOYSA-N 3-[3-(dimethylcarbamoylamino)-2-methylphenyl]-1,1-dimethylurea Chemical compound CN(C)C(=O)NC1=CC=CC(NC(=O)N(C)C)=C1C NEVYNAFJLYYHPR-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- IKWQWOFXRCUIFT-UHFFFAOYSA-N benzene-1,2-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C(=O)NN IKWQWOFXRCUIFT-UHFFFAOYSA-N 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- XXOYNJXVWVNOOJ-UHFFFAOYSA-N fenuron Chemical compound CN(C)C(=O)NC1=CC=CC=C1 XXOYNJXVWVNOOJ-UHFFFAOYSA-N 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- BMLIZLVNXIYGCK-UHFFFAOYSA-N monuron Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C=C1 BMLIZLVNXIYGCK-UHFFFAOYSA-N 0.000 description 1
- ZWLFGLCGZUVIEA-UHFFFAOYSA-N nonanedihydrazide Chemical compound NNC(=O)CCCCCCCC(=O)NN ZWLFGLCGZUVIEA-UHFFFAOYSA-N 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- CUQCMXFWIMOWRP-UHFFFAOYSA-N phenyl biguanide Chemical compound NC(N)=NC(N)=NC1=CC=CC=C1 CUQCMXFWIMOWRP-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、炭素繊維などの繊
維強化材を使用した繊維強化成形物(FRP)製造用プ
リプレグに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a prepreg for producing a fiber reinforced molding (FRP) using a fiber reinforcing material such as carbon fiber.
【0002】更に詳しくは、複雑な形状の成形物を短時
間で成形可能な利点を有する加圧成形用プリプレグ、特
に内圧成形において、高い樹脂含有率にも関わらず、成
形時の樹脂フロー性(樹脂流出)を抑制したプリプレグ
に関するものである。More specifically, in a prepreg for pressure molding, which has an advantage that a molded article having a complicated shape can be molded in a short time, particularly in internal pressure molding, the resin flow property at the time of molding (in spite of a high resin content). (Prevents resin outflow).
【0003】[0003]
【従来の技術】炭素繊維などの繊維強化材とマトリック
ス樹脂とからなるプリプレグは、ゴルフシャフト、釣
竿、テニスラケットのフレーム等のスポーツレジャー用
途、自動車のドライブシャフト、ハンドル、車両ボディ
ー、航空機の構造部材等の運輸機関等に広く利用される
ようになっている。2. Description of the Related Art A prepreg comprising a fiber reinforced material such as carbon fiber and a matrix resin is used for sports and leisure applications such as a golf shaft, a fishing rod, a frame of a tennis racket, a drive shaft of an automobile, a steering wheel, a vehicle body, and a structural member of an aircraft. It is widely used by transportation organizations such as.
【0004】このような用途において、ゴルフシャフ
ト、釣竿等のパイプ状成形物の成形方法としては、マン
ドレルにプリプレグを所定配向にしてレイアップし、外
周に収縮性テープを巻き付け、加熱硬化したのち、テー
プを剥離すると共にマンドレルを引き抜き成形物を得る
方法(テープラッピング法)が、一般的である。In such applications, as a method of forming a pipe-shaped molded product such as a golf shaft and a fishing rod, a prepreg is laid up with a predetermined orientation on a mandrel, a shrinkable tape is wound around the outer periphery, and after heating and curing, A method (tape wrapping method) of removing a tape and pulling out a mandrel to obtain a molded product is common.
【0005】パイプ状成形物成形時の問題としては、主
に硬化時の樹脂の流れやはみ出しといった樹脂フローの
問題が挙げられる。樹脂フローは、成形の過程で繊維強
化材の乱れや樹脂のはみ出しによる製品重量のバラツ
キ、成形物における表面ボイド発生に繋がり、外観的、
繊維強化材の性能発現の上で、問題となってきた。[0005] As a problem at the time of molding a pipe-shaped molded product, there is mainly a problem of a resin flow such as a resin flow at the time of curing and a protrusion. The resin flow leads to irregularities in the product weight due to turbulence of the fiber reinforced material and extrusion of the resin in the molding process, leading to the generation of surface voids in the molded product,
This has been a problem in the performance of fiber reinforced materials.
【0006】このような樹脂流れを防止する方法はこれ
まで種々検討されてきており、大きく2つに分けられ
る。Various methods for preventing such a resin flow have been studied so far, and are roughly divided into two methods.
【0007】一つの方法は、プリプレグ自体の樹脂含有
比率(RC)を低くすることである(特開平1−279
932号、特開平9−220769号)。この方法は、
RC30%以下のプリプレグを用いてパイプ状成形物を
成形するものであり、繊維強化材の乱れもなく、良好な
成形物が得られる旨が前記公報に記載されている。しか
し,RCを低くして樹脂フローを抑えると、成形物の表
面部において樹脂の欠損部を生じやすい。One method is to reduce the resin content ratio (RC) of the prepreg itself (JP-A-1-279).
No. 932, JP-A-9-220969). This method
The above-mentioned publication describes that a pipe-shaped molded product is molded using a prepreg having an RC of 30% or less, and a good molded product is obtained without disturbance of a fiber reinforcing material. However, if the RC is lowered to suppress the resin flow, a resin defect is likely to occur on the surface of the molded product.
【0008】もう一つの方法として、ポリエステルウレ
タンをエポキシ樹脂に配合して樹脂フロー性を改善する
方法(特開平5−117423号公報)、有機系チキソ
トロピー付与材を配合して樹脂フロー性を改善する方法
(特開平7−76647号公報)、繊維状無機充填材を
配合して樹脂フロー性を改善する方法(特開平8−41
174号公報、特開平8−20706号公報)、フェノ
キシ樹脂を配合して樹脂フロー性を改善する方法(特開
平7−118414号公報)、分子内エポキシ化ポリブ
タジエンを配合して樹脂フロー性を改善する方法(特開
平4−153252号公報)、熱可塑性ポリエステル樹
脂を配合して樹脂フロー性を改善する方法(特開平7−
41645号公報)等が知られている。As another method, a method of improving the resin flow property by blending polyester urethane with an epoxy resin (Japanese Patent Laid-Open No. 5-117423), and a method of improving the resin flow property by blending an organic thixotropy-imparting material are disclosed. (Japanese Unexamined Patent Publication No. Hei 7-76647), a method of improving resin flowability by blending a fibrous inorganic filler (Japanese Unexamined Patent Publication No. Hei 8-41).
174, JP-A-8-20706), a method of improving resin flowability by blending a phenoxy resin (JP-A-7-118414), and improving resin flowability by blending intramolecular epoxidized polybutadiene (Japanese Unexamined Patent Publication No. 4-153252), a method of improving the resin flowability by blending a thermoplastic polyester resin (Japanese Unexamined Patent Publication No.
No. 41645) is known.
【0009】これら従来のプリプレグを用い、テープラ
ッピング法にてパイプ状成形物を成形した場合、成形時
に過大な樹脂フローは無く、良好な成形品が得られる。When a pipe-like molded product is molded by tape wrapping using these conventional prepregs, there is no excessive resin flow during molding, and a good molded product can be obtained.
【0010】しかし、これらに示されたプリプレグは、
テープラッピング法のような長時間の成形法においては
有効であるものの、より高温、高圧、かつ短時間で成形
される内圧成形法に対しては、その急激な温度、圧力上
昇に伴う粘度低下に耐えられず、依然として樹脂フロー
が発生する問題を有している。However, the prepregs shown therein are
Although effective for long-time molding methods such as the tape wrapping method, the internal pressure molding method, which involves molding at higher temperatures, high pressures, and in a short time, suffers from a sharp decrease in viscosity due to the rapid temperature and pressure rise. It has a problem that it cannot withstand and still generates a resin flow.
【0011】内圧成形法とは、可膨張性マンドレルに成
形材料であるプリプレグをレイアップし、型内に配置後
マンドレルを膨張させ、成形材料を型の内面に押圧して
加熱硬化させる方法であり、複雑な形状の成形物を短時
間で成形できる利点を有する。The internal pressure molding method is a method in which a prepreg, which is a molding material, is laid up on an inflatable mandrel, the mandrel is expanded after being placed in a mold, and the molding material is pressed against the inner surface of the mold and cured by heating. This has the advantage that a molded article having a complicated shape can be molded in a short time.
【0012】内圧成形法の可膨張性マンドレルとして
は、中空体を使用し、流体を注入して膨張させる方法、
或いはマンドレル自体の熱膨張を利用し、マンドレルを
膨張させる方法等がある。[0012] A hollow body is used as an inflatable mandrel in the internal pressure molding method, and a fluid is injected to expand the mandrel;
Alternatively, there is a method of expanding the mandrel by utilizing the thermal expansion of the mandrel itself.
【0013】内圧成形法においては、成形時、レイアッ
プ層が型内面に高圧(約10kg/cm2 )で押圧され
る結果、押圧面では樹脂がフローし易く、特に性能向上
のためにプリプレグのRCを低く設定し、成形物の繊維
含有率(Vf)を高くするという最近の傾向では、表面
のマトリックス樹脂の欠損部が生じ易く、成形物にボイ
ドが生じ、成形物の物性低下の原因となるという問題点
が顕著に現れる。In the internal pressure molding method, at the time of molding, the lay-up layer is pressed against the inner surface of the mold at a high pressure (about 10 kg / cm 2 ). As a result, the resin easily flows on the pressed surface. With the recent trend of setting RC low and increasing the fiber content (Vf) of the molded product, a portion of the matrix resin on the surface is likely to be deficient, voids are generated in the molded product, and the physical properties of the molded product are deteriorated. The problem of becoming conspicuous appears.
【0014】一方、プリプレグのRCを高くすれば、押
圧面で樹脂フローが生じても、表面のマトリックス樹脂
の欠損部を発生することが無くなり、ボイドが生ずると
いう問題点が解消されると考えられるが、実際に、RC
が高いプリプレグを使用して成形した場合、樹脂フロー
が多くなり、その結果、成形物全体のVfは低くても、
成形物表面付近における高Vf化の傾向は変わらず、や
はりボイド発生の原因となる。On the other hand, if the RC of the prepreg is increased, it is considered that even if a resin flow occurs on the pressing surface, a defect of the matrix resin on the surface is not generated, and the problem that voids are generated is solved. But actually, RC
When molding is performed using a prepreg having a high resin flow, the resin flow increases, and as a result, even though the Vf of the entire molded product is low,
The tendency to increase Vf near the surface of the molded product does not change and still causes voids.
【0015】表面ボイドを生じた成形物は、表面の研磨
工程に、パテ埋め等の仕上げ処理を施すなどの工程を付
加されなければならず、コスト上昇の原因となる。A molded product having surface voids must be subjected to a step of performing a finishing treatment such as filling with putty or the like to the surface polishing step, which causes an increase in cost.
【0016】そこで、高温、高圧、短時間成形を特徴と
する内圧成形においても、成形物の仕上がり性が良好で
あるという要求に対し、高RCにも関わらず、樹脂フロ
ー抑制能が高く、しかも速硬化性とを兼ね備えたプリプ
レグを開発する必要性が生じた。Therefore, even in the internal pressure molding characterized by high temperature, high pressure and short time molding, the resin flow suppressing ability is high despite the high RC, in spite of the demand for good finish of the molded product. A need has arisen to develop prepregs that combine fast curing.
【0017】[0017]
【発明が解決しようとする課題】本発明が解決しようと
する課題は、成形物の仕上がり性が良好なプリプレグを
提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a prepreg having a good finished product.
【0018】特に、内圧成形に好適な、高RCにも関わ
らず高温、高圧下でも良好な樹脂フロー抑制能を有し、
且つ速硬化性を兼備したプリプレグを提供することにあ
る。In particular, it has good resin flow suppressing ability even under high temperature and high pressure despite high RC, suitable for internal pressure molding.
Another object of the present invention is to provide a prepreg having both quick-curing properties.
【0019】[0019]
【課題を解決するための手段】前記した課題を解決する
ための本発明のプリプレグは、繊維強化材にマトリック
ス樹脂を含浸してなるプリプレグにおいて、150℃で
のゲルタイムが0.1〜1.5分、温度150℃×圧力
10kg/cm2 の樹脂フロー指数が次式に示される関
係であり、且つ樹脂含有率が35重量%〜45重量%で
あることを特徴とする。According to the present invention, there is provided a prepreg comprising a fiber reinforced material impregnated with a matrix resin and having a gel time at 150 ° C. of 0.1 to 1.5. The resin flow index at a temperature of 150 ° C. × a pressure of 10 kg / cm 2 is represented by the following equation, and the resin content is 35% by weight to 45% by weight.
【0020】樹脂フロー指数=樹脂フロー(重量%)/
樹脂含有率(重量%) 0.03≦樹脂フロー指数≦0.51 本発明において、樹脂フロー指数とは、繊維強化材にマ
トリックス樹脂を含浸してなるプリプレグにおいて、樹
脂含有率と樹脂フローとの間に正の相関があるため、そ
の関係を樹脂フロー指数とし、樹脂フロー抑制能を表す
ものとして定義している。該樹脂フロー指数を調整する
ことによって、樹脂フロー抑制能を調整することができ
る。Resin flow index = resin flow (% by weight) /
Resin content (% by weight) 0.03 ≦ resin flow index ≦ 0.51 In the present invention, the resin flow index refers to the difference between the resin content and the resin flow in a prepreg obtained by impregnating a matrix resin into a fiber reinforced material. Since there is a positive correlation between them, the relationship is defined as a resin flow index, which is defined as a value that indicates the ability to suppress resin flow. By adjusting the resin flow index, the resin flow suppressing ability can be adjusted.
【0021】樹脂フロー指数が0.03未満であれば、
FRP成形時に樹脂のフローが不十分なためシャフト表
面にボイドが発生する。If the resin flow index is less than 0.03,
Voids are generated on the shaft surface due to insufficient resin flow during FRP molding.
【0022】樹脂フロー指数が0.51超であれば、樹
脂フローが大きく、このためFRP成形時に樹脂が流れ
てしまい、成形品表面にボイドが発生する。When the resin flow index is more than 0.51, the resin flow is large, so that the resin flows at the time of FRP molding, and voids are generated on the surface of the molded product.
【0023】このような物性を有する本発明のプリプレ
グを構成するためのマトリックス樹脂は下記の(A)、
(B)、(C)及び(D)成分を含有し、それぞれの配
合割合を下記量とすることが望ましい。: (A)エポキシ樹脂 100重量部 (B)アミン系潜在性硬化剤 2〜10重量部 (C)アルキル尿素型硬化促進剤 2〜5重量部 (D)揺変剤 5〜15重量部 前記物性を有する本発明のプリプレグを構成するための
繊維強化材は、炭素繊維、ボロン繊維、シリコーンカー
バイト繊維、ガラス繊維、チラノ繊維およびアラミド繊
維の1種又は2種以上の組み合わせから選択することが
できる。The matrix resin for constituting the prepreg of the present invention having such physical properties is as follows (A):
It is desirable to contain the components (B), (C) and (D), and to make the mixing ratios of the respective components below. : (A) 100 parts by weight of epoxy resin (B) 2 to 10 parts by weight of amine latent curing agent (C) 2 to 5 parts by weight of alkyl urea type curing accelerator (D) 5 to 15 parts by weight of thixotropic agent The fiber reinforcing material for constituting the prepreg of the present invention having the following can be selected from one or a combination of two or more of carbon fiber, boron fiber, silicone carbide fiber, glass fiber, tyrano fiber and aramid fiber. .
【0024】本発明のプリプレグは、その樹脂含有率
(RC)が35重量%〜45重量%であり、高RCプリ
プレグに属し、このプリプレグを加圧成形、特に内圧成
形に適用したときに、成形物表面にマトリックス樹脂の
欠損部を生じ難く、しかも速硬化性と樹脂フロー抑制効
果において優れている。The prepreg of the present invention has a resin content (RC) of 35% by weight to 45% by weight and belongs to a high RC prepreg. When this prepreg is applied to pressure molding, particularly to internal pressure molding, it is molded. It is unlikely to cause a defective portion of the matrix resin on the surface of the object, and is excellent in quick-curing property and resin flow suppressing effect.
【0025】本発明で速硬化性とは、150℃でのゲル
タイムが0.1〜1.5分であるものをいう。In the present invention, fast-curing means one having a gel time at 150 ° C. of 0.1 to 1.5 minutes.
【0026】本発明において樹脂フロー、ゲルタイムは
下記により測定される。 樹脂フローの測定 JIS K−7071−1988「炭素繊維およびエポ
キシ樹脂からなるプリプレグの試験方法」に記載の方法
に準拠したが、内圧成形用プリプレグに適用するため、
150℃ プレスセット後10kg/cm2 加圧×10
分間ホールドの条件で評価を行った。 ゲルタイムの測定 JSR型キュラストメーター(今中機械工業株式会社
製)を用いて、150℃でゲルタイムを測定した。In the present invention, the resin flow and the gel time are measured as follows. Measurement of Resin Flow According to the method described in JIS K-7071-1988 “Test method for prepreg composed of carbon fiber and epoxy resin”, but applied to prepreg for internal pressure molding,
0.99 ° C. press sets after 10 kg / cm 2 pressure × 10
The evaluation was performed under the condition of hold for one minute. Measurement of Gel Time The gel time was measured at 150 ° C. using a JSR type curast meter (manufactured by Imanaka Machine Industry Co., Ltd.).
【0027】本発明に用いることができる繊維強化材に
は、繊維強化樹脂複合材料に用いられる炭素繊維、ガラ
ス繊維、アラミド繊維、チラノ繊維等が挙げられるが、
特に高強度、高弾性率の複合材料を得る目的のためには
炭素繊維が適している。炭素繊維の内でも、取扱性及び
得られる複合材料の機械特性から、ポリアクリロニトリ
ル系の高強度炭素繊維が適している。The fiber reinforced material that can be used in the present invention includes carbon fiber, glass fiber, aramid fiber, and Tyranno fiber used for the fiber reinforced resin composite material.
In particular, carbon fibers are suitable for the purpose of obtaining a composite material having high strength and high elastic modulus. Among the carbon fibers, polyacrylonitrile-based high-strength carbon fibers are suitable from the viewpoint of handleability and mechanical properties of the obtained composite material.
【0028】繊維強化材の形態は、通常プリプレグに用
いられているもので、一方向配向繊維材、織物等が適用
できる。The form of the fiber reinforced material is usually used for a prepreg, and a unidirectionally oriented fiber material, a woven fabric or the like can be applied.
【0029】本発明に用いられるマトリックス樹脂はエ
ポキシ樹脂組成物であり、次の各成分の配合が好適に用
いられる。The matrix resin used in the present invention is an epoxy resin composition, and the following components are preferably used.
【0030】(A)成分 エポキシ樹脂は、特に限定されるものではなく、ビスフ
ェノールA型エポキシ樹脂、他のグリシジルエーテル型
エポキシ樹脂、例えば、ビスフェノールF型エポキシ樹
脂、ビスフェノールS型エポキシ樹脂、また、フェノー
ルノボラック型エポキシ樹脂、クレゾールノボラック型
エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ナフ
タレン型エポキシ樹脂、臭素化ビスフェノールA型エポ
キシ樹脂、グリシジルエステル型エポキシ樹脂、環式脂
肪族エポキシ樹脂、複素環式エポキシ樹脂等が挙げられ
る。また、所望に応じて、ウレタン変性エポキシ樹脂、
ゴム変性エポキシ樹脂、アルキド変性エポキシ樹脂等を
用いても良い。これらのうち取扱性、経済性、複合材料
物性等の必要特性に応じて、適宜混合して用いることが
できる。Component (A) The epoxy resin is not particularly limited, and bisphenol A type epoxy resin, other glycidyl ether type epoxy resin, for example, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and phenol Novolak epoxy resin, cresol novolak epoxy resin, glycidylamine epoxy resin, naphthalene epoxy resin, brominated bisphenol A epoxy resin, glycidyl ester epoxy resin, cycloaliphatic epoxy resin, heterocyclic epoxy resin, etc. No. Also, if desired, a urethane-modified epoxy resin,
A rubber-modified epoxy resin, an alkyd-modified epoxy resin, or the like may be used. Among them, they can be appropriately mixed and used according to necessary characteristics such as handleability, economy, and physical properties of the composite material.
【0031】(B)成分 エポキシ樹脂の硬化剤成分としては、プリプレグの貯蔵
安定性の面から50℃以上で硬化剤として働くものが好
ましく、アミン系潜在性硬化剤が挙げられる。例えば、
アミン系潜在性硬化剤として、ジシアンジアミド、メチ
ルグアニジン、エチルグアニジン、プロピルグアニジ
ン、ブチルグアニジン、ジメチルグアニジン、トリメチ
ルグアニジン、フェニルグアニジン、ジフェニルグアニ
ジン、トリイルグアニジン、2、3-グアニルウレア、
ベンゾイルジシアンジアミド、2、6-キシレニルビグ
アニド、フェニルビグアニド等のグアニジン系化合物が
挙げられる。Component (B) As the curing agent component of the epoxy resin, one that functions as a curing agent at 50 ° C. or higher from the viewpoint of storage stability of the prepreg is preferable, and an amine-based latent curing agent is mentioned. For example,
As an amine-based latent curing agent, dicyandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, triylguanidine, 2,3-guanylurea,
Guanidine-based compounds such as benzoyldicyandiamide, 2,6-xylenylbiguanide and phenylbiguanide are exemplified.
【0032】また、アミン系潜在性硬化剤の別の例に
は、アジピン酸ジヒドラジド、セバシン酸ジヒドラジ
ド、コハク酸ジヒドラジド、グルタン酸ジヒドラジド、
シュウ酸ジヒドラジド、フタル酸ジヒドラジド、イソフ
タル酸ジヒドラジド、テレフタル酸ジヒドラジド、p-
オキシ安息香酸ヒドラジド、サリチル酸ヒドラジド、マ
レイン酸ジヒドラジド、ダイマー酸ジヒドラジド、アゼ
ライン酸ジヒドラジド等の多価カルボン酸ポリヒドラジ
ド系化合物が挙げられる。Other examples of the amine-based latent curing agent include adipic dihydrazide, sebacic dihydrazide, succinic dihydrazide, glutanic dihydrazide,
Oxalic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, p-
Examples thereof include polyhydric carboxylic acid polyhydrazide compounds such as oxybenzoic acid hydrazide, salicylic acid hydrazide, maleic acid dihydrazide, dimer acid dihydrazide, and azelaic acid dihydrazide.
【0033】これらのアミン系潜在性硬化剤は、必要特
性に応じて一種もしくは二種以上を混合して用いること
が出来る。特に、貯蔵安定性、経済性、複合材料物性の
面でジシアンジアミド、アジピン酸ジヒドラジドが好ま
しい。These amine-based latent curing agents can be used alone or in combination of two or more depending on the required characteristics. In particular, dicyandiamide and adipic dihydrazide are preferable in terms of storage stability, economy, and physical properties of the composite material.
【0034】これらのアミン系潜在性硬化剤の配合量
は、硬化物の物性、貯蔵安定性等の必要特性に応じて適
宜調整されるが、(A)成分100重量部に対して2〜
10重量部が用いられる。2重量部より少ないと硬化が
不充分となり、10重量部より多いと硬化物物性が低下
しやすく好ましくない。The amount of these amine-based latent curing agents is appropriately adjusted depending on the required properties such as the physical properties and storage stability of the cured product.
10 parts by weight are used. When the amount is less than 2 parts by weight, curing is insufficient, and when the amount is more than 10 parts by weight, physical properties of a cured product are liable to be deteriorated.
【0035】(C)成分 硬化促進剤成分としては、アルキル尿素タイプの硬化促
進剤が挙げられる。例えば、3−(3,4−ジクロロフ
ェニル)−1,1−N−ジメチル尿素、3−フェニル−
1,1−ジメチル尿素、3−(4−クロロフェニル)−
1,1−ジメチル尿素、3−(4−メトキシフェニル)
−1,1−ジメチル尿素、1,1’−4(メチル−m−
フェニレン)ビス(3,3’ジメチルウレア)、トリメ
チル尿素等が挙げられる。特に常温での貯蔵安定性に優
れ、優れた速硬化性により樹脂フロー抑制に効果を及ぼ
す点で、1,1’−4(メチル−m−フェニレン)ビス
(3,3’ジメチルウレア)を用いることが好ましい。
硬化促進剤の添加量は、(A)成分100重量部に対し
て2〜5重量部が用いられる。2重量部未満の場合、速
硬化性が不十分であり、樹脂フロー抑制効果が得られな
い。逆に5重量部より多いと樹脂フロー抑制能が高過ぎ
て、成形物にボイドが生じる要因となるばかりか、プリ
プレグの貯蔵安定性が低下しやすく好ましくない。(C) Component The curing accelerator component includes an alkyl urea type curing accelerator. For example, 3- (3,4-dichlorophenyl) -1,1-N-dimethylurea, 3-phenyl-
1,1-dimethylurea, 3- (4-chlorophenyl)-
1,1-dimethylurea, 3- (4-methoxyphenyl)
-1,1-dimethylurea, 1,1′-4 (methyl-m-
(Phenylene) bis (3,3′dimethylurea), trimethylurea and the like. In particular, 1,1′-4 (methyl-m-phenylene) bis (3,3′dimethylurea) is used because it is excellent in storage stability at ordinary temperature and has an effect on resin flow suppression due to excellent fast curing property. Is preferred.
The addition amount of the curing accelerator is 2 to 5 parts by weight based on 100 parts by weight of the component (A). When the amount is less than 2 parts by weight, the quick-curing property is insufficient, and the resin flow suppressing effect cannot be obtained. Conversely, if the amount is more than 5 parts by weight, the resin flow suppressing ability is too high, which not only causes voids in the molded product, but also lowers the storage stability of the prepreg, which is not preferable.
【0036】(D)成分 揺変剤成分としては、樹脂フロー抑制、繊維強化材への
含浸性またはプリプレグの作業性、成形性、経済性、貯
蔵安定性を考慮して、無機充填材を用いることが好まし
い。無機充填材としては、例えばホウ酸アルミニウム、
炭酸カルシウム、炭酸ケイ素、窒化ケイ素、チタン酸カ
リウム、塩基性硫酸マグネシウム、酸化亜鉛、グラファ
イト、硫酸カルシウム、ホウ酸マグネシウム、酸化マグ
ネシウム、ケイ酸マグネシウム、ケイ酸アルミニウム等
が挙げられる。これらの無機系充填材は、一種若しくは
二種以上が適宜用いられる。これらのうち特に、樹脂フ
ロー抑制効果の点から、みかけ密度100〜130g/
lのケイ酸マグネシウムとケイ酸アルミニウムの混合物
を用いることが好ましい。Component (D) As the thixotropic component, an inorganic filler is used in consideration of resin flow suppression, impregnation into fiber reinforcement or workability of prepreg, moldability, economy, and storage stability. Is preferred. As the inorganic filler, for example, aluminum borate,
Examples include calcium carbonate, silicon carbonate, silicon nitride, potassium titanate, basic magnesium sulfate, zinc oxide, graphite, calcium sulfate, magnesium borate, magnesium oxide, magnesium silicate, and aluminum silicate. One or two or more of these inorganic fillers are appropriately used. Among these, in particular, from the viewpoint of the resin flow suppressing effect, the apparent density is 100 to 130 g /
It is preferred to use a mixture of 1 magnesium silicate and aluminum silicate.
【0037】揺変剤の配合量は、(A)成分100重量
部に対し、5〜15重量部が用いられる。5重量部未満
では成形時に十分なフロー抑制効果が無く、15重量部
を超えると樹脂フロー抑制効果が高すぎるばかりか、プ
リプレグ化工程での繊維への含浸性が低下しやすく好ま
しくない。The mixing amount of the thixotropic agent is 5 to 15 parts by weight based on 100 parts by weight of the component (A). If the amount is less than 5 parts by weight, there is no sufficient flow suppressing effect at the time of molding, and if it exceeds 15 parts by weight, not only the resin flow suppressing effect is too high, but also the impregnating property to the fiber in the prepreg forming step tends to decrease, which is not preferable.
【0038】これらの繊維強化材、マトリックス樹脂を
用いてプリプレグを製造するには、一般のプリプレグ製
造方法が適用でき、繊維強化材に対し、例えばホットメ
ルト法により直接、あるいはフィルム法により含浸する
方法を用いれば良い。To manufacture a prepreg using these fiber reinforced materials and matrix resin, a general prepreg manufacturing method can be applied, and the fiber reinforced material is impregnated directly by, for example, a hot melt method or by a film method. May be used.
【0039】[0039]
【実施例】以下実施例により本発明について更に詳細に
説明する。The present invention will be described in more detail with reference to the following examples.
【0040】〔実施例1〕エポキシ樹脂100重量部
(フェノールノボラック型エポキシ樹脂:商品名:E
p.154、油化シェルエポキシ(株)製70重量部、
及びビスフェノールA型エポキシ樹脂:商品名:Ep.
1002、油化シェルエポキシ(株)製30重量部)に
対し、硬化剤としてジシアンジアミド(商品名:DIC
Y7、油化シェルエポキシ(株)製)を3重量部、硬化
促進剤として1,1’−4(メチル−m−フェニレン)
ビス(3,3’ジメチルウレア)(商品名オミキュア2
4、ACI(株))3重量部、揺変剤(商品名:DT−
5039、旭チバ(株)製)10重量部からなるエポキ
シ樹脂組成物をロールミルを使用して調製した。Example 1 100 parts by weight of an epoxy resin (phenol novolak type epoxy resin: trade name: E)
p. 154, 70 parts by weight manufactured by Yuka Shell Epoxy Co., Ltd.
And bisphenol A type epoxy resin: Trade name: Ep.
1002, 30 parts by weight of Yuka Shell Epoxy Co., Ltd.) as a curing agent, dicyandiamide (trade name: DIC)
3 parts by weight of Y7, Yuka Shell Epoxy Co., Ltd., and 1,1′-4 (methyl-m-phenylene) as a curing accelerator
Bis (3,3'dimethylurea) (trade name Omicure 2
4, ACI Corporation) 3 parts by weight, thixotropic agent (trade name: DT-
5039, manufactured by Asahi Chiba Co., Ltd.) was used to prepare an epoxy resin composition comprising 10 parts by weight using a roll mill.
【0041】この樹脂組成物と高強度炭素繊維(東邦レ
ーヨン(株)製,UT500ストランド引張強度490
kgf/mm2 、引張弾性率24.5ton/mm2 )
とから一方向プリプレグ(炭素繊維目付は115g/m
2 )をホットメルト法で製造し、本実施例1のプリプレ
グを得た。このプリプレグの樹脂含有率は40重量%、
150℃のゲルタイムは0.8分であった。This resin composition and high-strength carbon fiber (manufactured by Toho Rayon Co., Ltd., UT500 strand tensile strength 490)
kgf / mm 2 , tensile modulus 24.5 ton / mm 2 )
And one-way prepreg (carbon fiber weight is 115 g / m
2 ) was produced by a hot melt method to obtain a prepreg of Example 1. The resin content of this prepreg is 40% by weight,
The gel time at 150 ° C. was 0.8 minutes.
【0042】このプリプレグの樹脂フローは10.9重
量%でありフロー指数は0.27であった。また、得ら
れたプリプレグを用いてゴルフシャフトを成形温度15
0℃、成形時間10min、成形圧10kgf/cm2
条件の内圧成形法により成形してみると、シャフト成形
時の樹脂フローは3.4重量%であり、シャフト表面の
ボイドも0.10個/cm2 と非常に少なく、良好な成
形性を示した。The resin flow of this prepreg was 10.9% by weight, and the flow index was 0.27. A golf shaft was formed at a molding temperature of 15 using the obtained prepreg.
0 ° C., molding time 10 min, molding pressure 10 kgf / cm 2
When molded by the internal pressure molding method under the conditions, the resin flow at the time of molding the shaft was 3.4% by weight, and the number of voids on the shaft surface was very small at 0.10 / cm 2 , showing good moldability. Was.
【0043】用いたマトリックス樹脂の組成、プリプレ
グの性質、プリプレグを使用した場合の成形性について
下記の表1にまとめて示す。The composition of the matrix resin used, the properties of the prepreg, and the moldability when using the prepreg are summarized in Table 1 below.
【0044】〔実施例2〕前記実施例1に示す樹脂組成
物及び炭素繊維を使い、炭素繊維目付は115g/
m2 、樹脂含有率は42重量%のプリプレグを作製し
た。このプリプレグの150℃のゲルタイムは0.9分
であった。Example 2 The resin composition and carbon fiber shown in Example 1 were used, and the carbon fiber basis weight was 115 g /
A prepreg having m 2 and a resin content of 42% by weight was prepared. The gel time at 150 ° C. of this prepreg was 0.9 minutes.
【0045】このプリプレグの樹脂フローは、13.7
重量%であり、フロー指数は0.33であった。また、
得られたプリプレグを用いてゴルフシャフトを内圧成形
法により成形した結果、シャフト成形時の樹脂フローは
4.0重量%と適度なフローが認められ、シャフト表面
のボイドも0.15個/cm2 と非常に少なく、良好な
成形性を示した。The resin flow of this prepreg was 13.7.
% By weight and the flow index was 0.33. Also,
As a result of molding a golf shaft by an internal pressure molding method using the obtained prepreg, an appropriate resin flow at the time of molding the shaft was found to be 4.0% by weight, and voids on the shaft surface were also 0.15 / cm 2. , And showed good moldability.
【0046】用いたマトリックス樹脂の組成、プリプレ
グの性質、プリプレグを使用した成形品の物性について
下記の表1にまとめて示す。The composition of the matrix resin used, the properties of the prepreg, and the physical properties of the molded articles using the prepreg are summarized in Table 1 below.
【0047】〔実施例3〕前記実施例1に示す樹脂組成
物及び炭素繊維を使い、炭素繊維目付は115g/
m2 、樹脂含有率は38重量%の本実施例3のプリプレ
グを作製した。このプリプレグの、150℃のゲルタイ
ムは0.6分であった。Example 3 The resin composition and carbon fiber shown in Example 1 were used, and the basis weight of carbon fiber was 115 g /
A prepreg of Example 3 having m 2 and a resin content of 38% by weight was produced. The gel time at 150 ° C. of this prepreg was 0.6 minutes.
【0048】このプリプレグの樹脂フローは、8.5重
量%であり、フロー指数は0.22であった。また、得
られたプリプレグを用いてゴルフシャフトを内圧成形法
により成形した結果、シャフト成形時の樹脂フローは
3.0重量%と適度なフローが認められ、シャフト表面
のボイドも0.13個/cm2 と非常に少なく、良好な
成形性を示した。The resin flow of this prepreg was 8.5% by weight, and the flow index was 0.22. In addition, as a result of molding the golf shaft by the internal pressure molding method using the obtained prepreg, the resin flow at the time of molding the shaft was 3.0% by weight, which was an appropriate flow, and the voids on the shaft surface were 0.13 / void. cm 2 , indicating a good moldability.
【0049】用いたマトリックス樹脂の組成、プリプレ
グの性質、プリプレグを使用した成形品の物性について
下記の表1にまとめて示す。The composition of the matrix resin used, the properties of the prepreg, and the physical properties of the molded article using the prepreg are summarized in Table 1 below.
【0050】〔実施例4〕エポキシ樹脂100重量部に
対し、硬化剤成分を3重量部、硬化促進剤成分を3重量
部、揺変剤成分5重量部からなるエポキシ樹脂組成物を
ロールミルを使用して調製した。Example 4 An epoxy resin composition comprising 3 parts by weight of a curing agent component, 3 parts by weight of a curing accelerator component and 5 parts by weight of a thixotropic agent component was used on a roll mill with respect to 100 parts by weight of an epoxy resin. Prepared.
【0051】この樹脂組成物と高強度炭素繊維(東邦レ
ーヨン(株)製,UT500ストランド引張強度490
kgf/mm2 、引張弾性率24.5ton/mm2 )
とから一方向プリプレグ(炭素繊維目付は115g/m
2 )をホットメルト法で製造し、樹脂含有率は40重量
%の本実施例4のプリプレグを得た。このプリプレグの
150℃のゲルタイムは1.0分であった。This resin composition and high-strength carbon fiber (manufactured by Toho Rayon Co., Ltd., UT500 strand tensile strength 490)
kgf / mm 2 , tensile modulus 24.5 ton / mm 2 )
And one-way prepreg (carbon fiber weight is 115 g / m
2 ) was produced by a hot melt method to obtain a prepreg of Example 4 having a resin content of 40% by weight. The gel time at 150 ° C. of this prepreg was 1.0 minute.
【0052】このプリプレグの樹脂フローは16.1重
量%であり、フロー指数は0.40であった。また、得
られたプリプレグを用いてゴルフシャフトを内圧成形法
により成形してみると、シャフト成形時の樹脂フローは
4.4重量%と若干多めであったが、シャフト表面のボ
イドは0.19個/cm2 と少なく、良好な成形性を示
した。The resin flow of this prepreg was 16.1% by weight, and the flow index was 0.40. When a golf shaft was molded by an internal pressure molding method using the obtained prepreg, the resin flow at the time of molding the shaft was slightly larger at 4.4% by weight, but the void on the shaft surface was 0.19%. Pieces / cm 2 , indicating good moldability.
【0053】用いたマトリックス樹脂の組成、プリプレ
グの性質、プリプレグを使用した成形品の物性について
下記の表1にまとめて示す。The composition of the used matrix resin, the properties of the prepreg, and the physical properties of the molded article using the prepreg are shown in Table 1 below.
【0054】〔実施例5〕エポキシ樹脂100重量部に
対し、硬化剤成分を3重量部、硬化促進剤成分を3重量
部、揺変剤成分8重量部からなるエポキシ樹脂組成物を
ロールミルを使用して調製した。Example 5 An epoxy resin composition comprising 3 parts by weight of a curing agent component, 3 parts by weight of a curing accelerator component, and 8 parts by weight of a thixotropic agent component was used on a roll mill with respect to 100 parts by weight of an epoxy resin. Prepared.
【0055】この樹脂組成物と高強度炭素繊維(東邦レ
ーヨン(株)製,UT500ストランド引張強度490
kgf/mm2 、引張弾性率24.5ton/mm2 )
とから一方向プリプレグ(炭素繊維目付は115g/m
2 )をホットメルト法で製造し、樹脂含有率は40重量
%の本実施例5のプリプレグを得た。このプリプレグの
150℃のゲルタイムは0.9分であった。This resin composition and high-strength carbon fiber (trade name: UT500 strand tensile strength 490, manufactured by Toho Rayon Co., Ltd.)
kgf / mm 2 , tensile modulus 24.5 ton / mm 2 )
And one-way prepreg (carbon fiber weight is 115 g / m
2 ) was produced by a hot melt method to obtain a prepreg of Example 5 having a resin content of 40% by weight. The gel time at 150 ° C. of this prepreg was 0.9 minutes.
【0056】このプリプレグの樹脂フローは13.2重
量%であり、フロー指数は0.33であった。また、得
られたプリプレグを用いてゴルフシャフトを内圧成形法
により成形してみると、シャフト成形時の樹脂フローは
2.0重量%と適度なフローが認められ、シャフト表面
のボイドも0.15個/cm2 と非常に少なく、良好な
成形性を示した。The resin flow of this prepreg was 13.2% by weight, and the flow index was 0.33. Further, when a golf shaft is molded by an internal pressure molding method using the obtained prepreg, a resin flow at the time of molding the shaft is 2.0% by weight, which is an appropriate flow, and a void on the shaft surface is 0.15%. Pcs / cm 2, which was very small, indicating good moldability.
【0057】用いたマトリックス樹脂の組成、プリプレ
グの性質、プリプレグを使用した成形品の物性について
下記の表1にまとめて示す。The composition of the used matrix resin, the properties of the prepreg, and the physical properties of the molded article using the prepreg are shown in Table 1 below.
【0058】〔実施例6〕エポキシ樹脂100重量部に
対し、硬化剤成分を3重量部、硬化促進剤成分を3重量
部、揺変剤成分12重量部からなるエポキシ樹脂組成物
をロールミルを使用して調製した。Example 6 An epoxy resin composition comprising 3 parts by weight of a curing agent component, 3 parts by weight of a curing accelerator component and 12 parts by weight of a thixotropic agent component was used on a roll mill with respect to 100 parts by weight of an epoxy resin. Prepared.
【0059】この樹脂組成物と高強度炭素繊維(東邦レ
ーヨン(株)製,UT500ストランド引張強度490
kgf/mm2 、引張弾性率24.5ton/mm2 )
とから一方向プリプレグ(炭素繊維目付は115g/m
2 )をホットメルト法で製造し、樹脂含有率は40重量
%の本実施例6のプリプレグを得た。このプリプレグの
150℃のゲルタイムは0.7分であった。This resin composition and high-strength carbon fiber (manufactured by Toho Rayon Co., Ltd., UT500 strand tensile strength 490)
kgf / mm 2 , tensile modulus 24.5 ton / mm 2 )
And one-way prepreg (carbon fiber weight is 115 g / m
2 ) was produced by a hot melt method to obtain a prepreg of Example 6 having a resin content of 40% by weight. The gel time at 150 ° C. of this prepreg was 0.7 minutes.
【0060】このプリプレグの樹脂フローは9.6重量
%であり、フロー指数は0.24であった。また、得ら
れたプリプレグを用いてゴルフシャフトを内圧成形法に
より成形してみると、シャフト成形時の樹脂フローは
3.2重量%と適度なフローが認められ、シャフト表面
のボイドも0.12個/cm2 と非常に少なく、良好な
成形性を示した。The resin flow of this prepreg was 9.6% by weight, and the flow index was 0.24. Also, when a golf shaft was molded by an internal pressure molding method using the obtained prepreg, a resin flow at the time of molding the shaft was 3.2% by weight, and an appropriate flow was recognized. Pcs / cm 2, which was very small, indicating good moldability.
【0061】用いたマトリックス樹脂の組成、プリプレ
グの性質、プリプレグを使用した成形品の物性について
下記の表1にまとめて示す。The composition of the matrix resin used, the properties of the prepreg, and the physical properties of the molded article using the prepreg are summarized in Table 1 below.
【0062】〔実施例7〕エポキシ樹脂100重量部に
対し、硬化剤成分を3重量部、硬化促進剤成分を3重量
部、揺変剤成分15重量部からなるエポキシ樹脂組成物
をロールミルを使用して調製した。Example 7 An epoxy resin composition comprising 3 parts by weight of a curing agent component, 3 parts by weight of a curing accelerator component and 15 parts by weight of a thixotropic agent component was used on a roll mill with respect to 100 parts by weight of an epoxy resin. Prepared.
【0063】この樹脂組成物と高強度炭素繊維(東邦レ
ーヨン(株)製,UT500ストランド引張強度490
kgf/mm2 、引張弾性率24.5ton/mm2 )
とから一方向プリプレグ(炭素繊維目付は115g/m
2 )をホットメルト法で製造し、樹脂含有率は40重量
%の本実施例7のプリプレグを得た。このプリプレグの
150℃のゲルタイムは0.6分であった。This resin composition and high-strength carbon fiber (manufactured by Toho Rayon Co., Ltd., UT500 strand tensile strength 490)
kgf / mm 2 , tensile modulus 24.5 ton / mm 2 )
And one-way prepreg (carbon fiber weight is 115 g / m
2 ) was produced by a hot melt method to obtain a prepreg of Example 7 having a resin content of 40% by weight. The gel time at 150 ° C. of this prepreg was 0.6 minutes.
【0064】このプリプレグの樹脂フローは7.9重量
%であり、フロー指数は0.20であった。また、得ら
れたプリプレグを用いてゴルフシャフトを内圧成形法に
より成形してみると、シャフト成形時の樹脂フローは
2.8重量%と若干少なめであったが、シャフト表面の
ボイドは0.16個/cm2 と少なく、良好な成形性を
示した。The resin flow of this prepreg was 7.9% by weight, and the flow index was 0.20. When a golf shaft was molded by an internal pressure molding method using the obtained prepreg, the resin flow at the time of molding the shaft was slightly lower at 2.8% by weight, but the void on the shaft surface was 0.16% by weight. Pieces / cm 2 , indicating good moldability.
【0065】用いたマトリックス樹脂の組成、プリプレ
グの性質、プリプレグを使用した成形品の物性について
下記の表1にまとめて示す。The composition of the used matrix resin, the properties of the prepreg, and the physical properties of the molded article using the prepreg are shown in Table 1 below.
【0066】〔実施例8〕エポキシ樹脂100重量部に
対し、硬化剤成分を2重量部、硬化促進剤成分を2重量
部、揺変剤成分5重量部からなるエポキシ樹脂組成物を
ロールミルを使用して調製した。Example 8 An epoxy resin composition comprising 2 parts by weight of a curing agent component, 2 parts by weight of a curing accelerator component, and 5 parts by weight of a thixotropic agent component was used on a roll mill with respect to 100 parts by weight of an epoxy resin. Prepared.
【0067】この樹脂組成物と高強度炭素繊維(東邦レ
ーヨン(株)製,UT500ストランド引張強度490
kgf/mm2 、引張弾性率24.5ton/mm2 )
とから一方向プリプレグ(炭素繊維目付は115g/m
2 )をホットメルト法で製造し、樹脂含有率は40重量
%の本実施例8のプリプレグを得た。このプリプレグの
150℃のゲルタイムは1.3分であった。This resin composition and high-strength carbon fiber (manufactured by Toho Rayon Co., Ltd., UT500 strand tensile strength 490)
kgf / mm 2 , tensile modulus 24.5 ton / mm 2 )
And one-way prepreg (carbon fiber weight is 115 g / m
2 ) was produced by a hot melt method to obtain a prepreg of Example 8 having a resin content of 40% by weight. The gel time at 150 ° C. of this prepreg was 1.3 minutes.
【0068】このプリプレグの樹脂フローは17.0重
量%であり、フロー指数は0.43であった。また、得
られたプリプレグを用いてゴルフシャフトを内圧成形法
により成形してみると、シャフト成形時の樹脂フローは
4.6重量%と若干多めであったが、シャフト表面のボ
イドは0.21個/cm2 と少なく、良好な成形性を示
した。The resin flow of this prepreg was 17.0% by weight, and the flow index was 0.43. When a golf shaft was molded by an internal pressure molding method using the obtained prepreg, the resin flow at the time of molding the shaft was slightly higher at 4.6% by weight, but the void on the shaft surface was 0.21%. Pieces / cm 2 , indicating good moldability.
【0069】用いたマトリックス樹脂の組成、プリプレ
グの性質、プリプレグを使用した成形品の物性について
下記の表1にまとめて示す。The composition of the matrix resin used, the properties of the prepreg, and the physical properties of the molded article using the prepreg are summarized in Table 1 below.
【0070】〔実施例9〕エポキシ樹脂100重量部に
対し、硬化剤成分を2重量部、硬化促進剤成分を2重量
部、揺変剤成分5重量部からなるエポキシ樹脂組成物を
ロールミルを使用して調製した。Example 9 An epoxy resin composition comprising 2 parts by weight of a curing agent component, 2 parts by weight of a curing accelerator component, and 5 parts by weight of a thixotropic agent component was used in a roll mill with respect to 100 parts by weight of an epoxy resin. Prepared.
【0071】この樹脂組成物と高強度炭素繊維(東邦レ
ーヨン(株)製,UT500ストランド引張強度490
kgf/mm2 、引張弾性率24.5ton/mm2 )
とから一方向プリプレグ(炭素繊維目付は115g/m
2 )をホットメルト法で製造し、樹脂含有率は42重量
%の本実施例9のプリプレグを得た。このプリプレグの
150℃のゲルタイムは1.4分であった。This resin composition and high-strength carbon fiber (UT500 strand tensile strength 490, manufactured by Toho Rayon Co., Ltd.)
kgf / mm 2 , tensile modulus 24.5 ton / mm 2 )
And one-way prepreg (carbon fiber weight is 115 g / m
2 ) was produced by a hot melt method to obtain a prepreg of Example 9 having a resin content of 42% by weight. The gel time at 150 ° C. of this prepreg was 1.4 minutes.
【0072】このプリプレグの樹脂フローは19.3重
量%であり、フロー指数は0.46であった。また、得
られたプリプレグを用いてゴルフシャフトを内圧成形法
により成形してみると、シャフト成形時の樹脂フローは
4.8重量%と若干多めであったが、シャフト表面のボ
イドは0.23個/cm2 と少なく、良好な成形性を示
した。The resin flow of this prepreg was 19.3% by weight, and the flow index was 0.46. Also, when a golf shaft was molded by an internal pressure molding method using the obtained prepreg, the resin flow at the time of molding the shaft was slightly higher at 4.8% by weight, but the void on the shaft surface was 0.23% by weight. Pieces / cm 2 , indicating good moldability.
【0073】用いたマトリックス樹脂の組成、プリプレ
グの性質、プリプレグを使用した成形品の物性について
下記の表1にまとめて示す。The composition of the matrix resin used, the properties of the prepreg, and the physical properties of the molded articles using the prepreg are shown in Table 1 below.
【0074】〔実施例10〕エポキシ樹脂100重量部
に対し、硬化剤成分を10重量部、硬化促進剤成分を5
重量部、揺変剤成分15重量部からなるエポキシ樹脂組
成物をロールミルを使用して調製した。Example 10 10 parts by weight of a curing agent component and 5 parts by weight of a curing accelerator component were added to 100 parts by weight of an epoxy resin.
An epoxy resin composition comprising 15 parts by weight of a thixotropic agent component was prepared using a roll mill.
【0075】この樹脂組成物と高強度炭素繊維(東邦レ
ーヨン(株)製,UT500ストランド引張強度490
kgf/mm2 、引張弾性率24.5ton/mm2 )
とから一方向プリプレグ(炭素繊維目付は115g/m
2 )をホットメルト法で製造し、樹脂含有率は40重量
%の本実施例10のプリプレグを得た。このプリプレグ
の150℃のゲルタイムは0.5分であった。This resin composition and high-strength carbon fiber (manufactured by Toho Rayon Co., Ltd., UT500 strand tensile strength 490)
kgf / mm 2 , tensile modulus 24.5 ton / mm 2 )
And one-way prepreg (carbon fiber weight is 115 g / m
2 ) was produced by a hot melt method to obtain a prepreg of Example 10 having a resin content of 40% by weight. The gel time at 150 ° C. of this prepreg was 0.5 minutes.
【0076】このプリプレグの樹脂フローは7.1重量
%であり、フロー指数は0.18であった。また、得ら
れたプリプレグを用いてゴルフシャフトを内圧成形法に
より成形してみると、シャフト成形時の樹脂フローは
2.8重量%と若干少なめであったが、シャフト表面の
ボイドは0.16個/cm2 と少なく、良好な成形性を
示した。The resin flow of this prepreg was 7.1% by weight, and the flow index was 0.18. When a golf shaft was molded by an internal pressure molding method using the obtained prepreg, the resin flow at the time of molding the shaft was slightly lower at 2.8% by weight, but the void on the shaft surface was 0.16% by weight. Pieces / cm 2 , indicating good moldability.
【0077】用いたマトリックス樹脂の組成、プリプレ
グの性質、プリプレグを使用した成形品の物性について
下記の表1にまとめて示す。The composition of the matrix resin used, the properties of the prepreg, and the physical properties of the molded article using the prepreg are shown in Table 1 below.
【0078】〔実施例11〕エポキシ樹脂100重量部
に対し、硬化剤成分を10重量部、硬化促進剤成分を5
重量部、揺変剤成分15重量部からなるエポキシ樹脂組
成物をロールミルを使用して調製した。Example 11 10 parts by weight of a curing agent component and 5 parts by weight of a curing accelerator component were added to 100 parts by weight of an epoxy resin.
An epoxy resin composition comprising 15 parts by weight of a thixotropic agent component was prepared using a roll mill.
【0079】この樹脂組成物と高強度炭素繊維(東邦レ
ーヨン(株)製,UT500ストランド引張強度490
kgf/mm2 、引張弾性率24.5ton/mm2 )
とから一方向プリプレグ(炭素繊維目付は115g/m
2 )をホットメルト法で製造し、樹脂含有率は38重量
%の本実施例11のプリプレグを得た。このプリプレグ
の150℃のゲルタイムは0.4分であった。This resin composition and high-strength carbon fiber (manufactured by Toho Rayon Co., Ltd., UT500 strand tensile strength 490)
kgf / mm 2 , tensile modulus 24.5 ton / mm 2 )
And one-way prepreg (carbon fiber weight is 115 g / m
2 ) was produced by a hot melt method to obtain a prepreg of Example 11 having a resin content of 38% by weight. The gel time at 150 ° C. of this prepreg was 0.4 minutes.
【0080】このプリプレグの樹脂フローは4.9重量
%であり、フロー指数は0.13であった。また、得ら
れたプリプレグを用いてゴルフシャフトを内圧成形法に
より成形してみると、シャフト成形時の樹脂フローは
2.4重量%と若干少なめであったが、シャフト表面の
ボイドは0.21個/cm2 と少なく、良好な成形性を
示した。The resin flow of this prepreg was 4.9% by weight, and the flow index was 0.13. When a golf shaft was molded by the internal pressure molding method using the obtained prepreg, the resin flow at the time of molding the shaft was slightly lower at 2.4% by weight, but the void on the shaft surface was 0.21%. Pieces / cm 2 , indicating good moldability.
【0081】用いたマトリックス樹脂の組成、プリプレ
グの性質、プリプレグを使用した成形品の物性について
下記の表1にまとめて示す。The composition of the matrix resin used, the properties of the prepreg, and the physical properties of the molded article using the prepreg are shown in Table 1 below.
【0082】〔比較例1〕エポキシ樹脂100重量部に
対し、硬化剤成分を3重量部、硬化促進剤成分を3重量
部、揺変剤成分10重量部からなるエポキシ樹脂組成物
をロールミルを使用して調製した。Comparative Example 1 An epoxy resin composition comprising 3 parts by weight of a curing agent component, 3 parts by weight of a curing accelerator component, and 10 parts by weight of a thixotropic agent component was used on a roll mill with respect to 100 parts by weight of an epoxy resin. Prepared.
【0083】この樹脂組成物と高強度炭素繊維(東邦レ
ーヨン(株)製,UT500ストランド引張強度490
kgf/mm2 、引張弾性率24.5ton/mm2 )
とから一方向プリプレグ(炭素繊維目付は115g/m
2 )をホットメルト法で製造し、樹脂含有率は32重量
%の比較例1のプリプレグを得た。このプリプレグの1
50℃のゲルタイムは0.4分であった。The resin composition and high-strength carbon fiber (trade name: UT500 strand tensile strength 490, manufactured by Toho Rayon Co., Ltd.)
kgf / mm 2 , tensile modulus 24.5 ton / mm 2 )
And one-way prepreg (carbon fiber weight is 115 g / m
2 ) was produced by a hot melt method to obtain a prepreg of Comparative Example 1 having a resin content of 32% by weight. 1 of this prepreg
The gel time at 50 ° C. was 0.4 minutes.
【0084】このプリプレグの樹脂フローは0.7重量
%であり、フロー指数は0.02と低かった。また、得
られたプリプレグを用いてゴルフシャフトを内圧成形法
により成形してみると、シャフト成形時の樹脂フローは
1.6重量%と少なく、樹脂フロー抑制能が高いため、
シャフト表面のボイドは0.30個/cm2 と多く、良
好な成形物は得られなかった。The resin flow of this prepreg was 0.7% by weight, and the flow index was as low as 0.02. Also, when a golf shaft is molded by an internal pressure molding method using the obtained prepreg, the resin flow at the time of molding the shaft is as small as 1.6% by weight, and the resin flow suppressing ability is high.
The voids on the shaft surface were as large as 0.30 / cm 2, and no good molded product was obtained.
【0085】用いたマトリックス樹脂の組成、プリプレ
グの性質、プリプレグを使用した成形品の物性について
下記の表2にまとめて示す。The composition of the matrix resin used, the properties of the prepreg, and the physical properties of the molded article using the prepreg are shown in Table 2 below.
【0086】〔比較例2〕エポキシ樹脂100重量部に
対し、硬化剤成分を3重量部、硬化促進剤成分を3重量
部、揺変剤成分10重量部からなるエポキシ樹脂組成物
をロールミルを使用して調製した。Comparative Example 2 An epoxy resin composition comprising 3 parts by weight of a curing agent component, 3 parts by weight of a curing accelerator component, and 10 parts by weight of a thixotropic agent component was used in a roll mill with respect to 100 parts by weight of an epoxy resin. Prepared.
【0087】この樹脂組成物と高強度炭素繊維(東邦レ
ーヨン(株)製,UT500ストランド引張強度490
kgf/mm2 、引張弾性率24.5ton/mm2 )
とから一方向プリプレグ(炭素繊維目付は115g/m
2 )をホットメルト法で製造し、樹脂含有率は49重量
%の比較例2のプリプレグを得た。このプリプレグの1
50℃のゲルタイムは1.2分であった。This resin composition and high-strength carbon fiber (manufactured by Toho Rayon Co., Ltd., UT500 strand tensile strength 490)
kgf / mm 2 , tensile modulus 24.5 ton / mm 2 )
And one-way prepreg (carbon fiber weight is 115 g / m
2 ) was produced by a hot melt method to obtain a prepreg of Comparative Example 2 having a resin content of 49% by weight. 1 of this prepreg
The gel time at 50 ° C. was 1.2 minutes.
【0088】このプリプレグの樹脂フローは26.0重
量%であり、フロー指数は0.53と高かった。また、
得られたプリプレグを用いてゴルフシャフトを内圧成形
法により成形してみると、シャフト成形時の樹脂フロー
は5.2重量%と多く、樹脂フロー抑制能が低いため、
シャフト表面のボイドも0.32個/cm2 と多く、良
好な成形物は得られなかった。The resin flow of this prepreg was 26.0% by weight, and the flow index was as high as 0.53. Also,
When a golf shaft is molded by the internal pressure molding method using the obtained prepreg, the resin flow at the time of molding the shaft is as large as 5.2% by weight, and the resin flow suppressing ability is low.
The number of voids on the shaft surface was as large as 0.32 / cm 2, and no good molded product was obtained.
【0089】用いたマトリックス樹脂の組成、プリプレ
グの性質、プリプレグを使用した成形品の物性について
下記の表2にまとめて示す。The composition of the used matrix resin, the properties of the prepreg, and the physical properties of the molded article using the prepreg are shown in Table 2 below.
【0090】〔比較例3〕エポキシ樹脂100重量部に
対し、硬化剤成分を10重量部、硬化促進剤成分を8重
量部、揺変剤成分18重量部からなるエポキシ樹脂組成
物をロールミルを使用して調製した。Comparative Example 3 An epoxy resin composition comprising 10 parts by weight of a curing agent component, 8 parts by weight of a curing accelerator component and 18 parts by weight of a thixotropic agent component was used on a roll mill with respect to 100 parts by weight of an epoxy resin. Prepared.
【0091】この樹脂組成物と高強度炭素繊維(東邦レ
ーヨン(株)製,UT500ストランド引張強度490
kgf/mm2 、引張弾性率24.5ton/mm2 )
とから一方向プリプレグ(炭素繊維目付は115g/m
2 )をホットメルト法で製造し、樹脂含有率は40重量
%の比較例3のプリプレグを得た。このプリプレグの1
50℃のゲルタイムは0.08分であった。This resin composition and a high-strength carbon fiber (manufactured by Toho Rayon Co., Ltd., UT500 strand tensile strength 490)
kgf / mm 2 , tensile modulus 24.5 ton / mm 2 )
And one-way prepreg (carbon fiber weight is 115 g / m
2 ) was produced by a hot melt method to obtain a prepreg of Comparative Example 3 having a resin content of 40% by weight. 1 of this prepreg
The gel time at 50 ° C. was 0.08 minutes.
【0092】このプリプレグの樹脂フローは0.6重量
%であり、フロー指数も0.02と低かった。また、得
られたプリプレグを用いてゴルフシャフトを内圧成形法
により成形してみると、シャフト成形時の樹脂フローは
1.0重量%と少なかった。樹脂フロー抑制能が高く且
つより短時間で硬化するため、シャフト表面のボイドは
0.38個/cm2 と多く、良好な成形物は得られなか
った。The prepreg had a resin flow of 0.6% by weight and a low flow index of 0.02. When a golf shaft was molded by the internal pressure molding method using the obtained prepreg, the resin flow at the time of molding the shaft was as small as 1.0% by weight. Since the resin flow suppressing ability was high and the resin was cured in a shorter time, voids on the shaft surface were as large as 0.38 / cm 2, and a good molded product was not obtained.
【0093】用いたマトリックス樹脂の組成、プリプレ
グの性質、プリプレグを使用した成形品の物性について
下記の表2にまとめて示す。The composition of the matrix resin used, the properties of the prepreg, and the physical properties of the molded article using the prepreg are shown in Table 2 below.
【0094】〔比較例4〕エポキシ樹脂100重量部に
対し、硬化剤成分を2重量部、硬化促進剤成分を1重量
部、揺変剤成分3重量部からなるエポキシ樹脂組成物を
ロールミルを使用して調製した。Comparative Example 4 An epoxy resin composition comprising 2 parts by weight of a curing agent component, 1 part by weight of a curing accelerator component, and 3 parts by weight of a thixotropic agent component was used on a roll mill with respect to 100 parts by weight of an epoxy resin. Prepared.
【0095】この樹脂組成物と高強度炭素繊維(東邦レ
ーヨン(株)製,UT500ストランド引張強度490
kgf/mm2 、引張弾性率24.5ton/mm2 )
とから一方向プリプレグ(炭素繊維目付は115g/m
2 )をホットメルト法で製造し、樹脂含有率は40重量
%の比較例4のプリプレグを得た。このプリプレグの1
50℃のゲルタイムは1.8分であった。The resin composition and a high-strength carbon fiber (UT500 strand tensile strength 490, manufactured by Toho Rayon Co., Ltd.)
kgf / mm 2 , tensile modulus 24.5 ton / mm 2 )
And one-way prepreg (carbon fiber weight is 115 g / m
2 ) was produced by a hot melt method to obtain a prepreg of Comparative Example 4 having a resin content of 40% by weight. 1 of this prepreg
The gel time at 50 ° C. was 1.8 minutes.
【0096】このプリプレグの樹脂フローは28.0重
量%であり、フロー指数も0.70と高かった。また、
得られたプリプレグを用いてゴルフシャフトを内圧成形
法により成形してみると、シャフト成形時の樹脂フロー
は7.0重量%と多かった。樹脂フロー抑制能が低く且
つ硬化に長時間を有するため、シャフト表面のボイドは
0.40個/cm2 と多く良好な成形物は得られなかっ
た。The resin flow of this prepreg was 28.0% by weight, and the flow index was as high as 0.70. Also,
When a golf shaft was molded by the internal pressure molding method using the obtained prepreg, the resin flow at the time of molding the shaft was as high as 7.0% by weight. Since the resin flow suppressing ability was low and the curing had a long time, the number of voids on the shaft surface was as large as 0.40 / cm 2, and a good molded product could not be obtained.
【0097】用いたマトリックス樹脂の組成、プリプレ
グの性質、プリプレグを使用した成形品の物性について
下記の表2にまとめて示す。The composition of the matrix resin used, the properties of the prepreg, and the physical properties of the molded articles using the prepreg are summarized in Table 2 below.
【0098】〔比較例5〕エポキシ樹脂100重量部に
対し、硬化剤成分を10重量部、硬化促進剤成分を8重
量部、揺変剤成分5重量部からなるエポキシ樹脂組成物
をロールミルを使用して調製した。Comparative Example 5 An epoxy resin composition comprising 10 parts by weight of a curing agent component, 8 parts by weight of a curing accelerator component and 5 parts by weight of a thixotropic agent component was used on a roll mill with respect to 100 parts by weight of an epoxy resin. Prepared.
【0099】この樹脂組成物と高強度炭素繊維(東邦レ
ーヨン(株)製,UT500ストランド引張強度490
kgf/mm2 、引張弾性率24.5ton/mm2 )
とから一方向プリプレグ(炭素繊維目付は115g/m
2 )をホットメルト法で製造し、樹脂含有率は32重量
%の本比較例5のプリプレグを得た。このプリプレグの
150℃のゲルタイムは0.05分であった。This resin composition and high-strength carbon fiber (trade name: UT500 strand tensile strength 490, manufactured by Toho Rayon Co., Ltd.)
kgf / mm 2 , tensile modulus 24.5 ton / mm 2 )
And one-way prepreg (carbon fiber weight is 115 g / m
2 ) was produced by a hot melt method to obtain a prepreg of Comparative Example 5 having a resin content of 32% by weight. The gel time at 150 ° C. of this prepreg was 0.05 minutes.
【0100】このプリプレグの樹脂フローは1.2重量
%であり、フロー指数は0.04であった。また、得ら
れたプリプレグを用いてゴルフシャフトを内圧成形法に
より成形してみると、シャフト成形時の樹脂フローは
1.8重量%であったが、プリプレグがより短時間で硬
化するため、シャフト表面のボイドは0.28個/cm
2 と多く、良好な成形物は得られなかった。The resin flow of this prepreg was 1.2 weight
% And the flow index was 0.04. Also obtained
Golf shaft using internal prepreg
More molding, the resin flow during shaft molding is
1.8% by weight, but the prepreg hardened in a shorter time.
0.28 voids / cm on the shaft surface
TwoAnd a good molded product was not obtained.
【0101】用いたマトリックス樹脂の組成、プリプレ
グの性質、プリプレグを使用した成形品の物性について
下記の表2にまとめて示す。The composition of the used matrix resin, the properties of the prepreg, and the physical properties of the molded article using the prepreg are shown in Table 2 below.
【0102】〔比較例6〕エポキシ樹脂100重量部に
対し、硬化剤成分を2重量部、硬化促進剤成分を1重量
部、揺変剤成分15重量部からなるエポキシ樹脂組成物
をロールミルを使用して調製した。Comparative Example 6 An epoxy resin composition comprising 2 parts by weight of a curing agent component, 1 part by weight of a curing accelerator component, and 15 parts by weight of a thixotropic agent component was used on a roll mill with respect to 100 parts by weight of an epoxy resin. Prepared.
【0103】この樹脂組成物と高強度炭素繊維(東邦レ
ーヨン(株)製,UT500ストランド引張強度490
kgf/mm2 、引張弾性率24.5ton/mm2 )
とから一方向プリプレグ(炭素繊維目付は115g/m
2 )をホットメルト法で製造し、樹脂含有率は49重量
%の比較例6のプリプレグを得た。このプリプレグの1
50℃のゲルタイムは2.1分であった。This resin composition and a high-strength carbon fiber (manufactured by Toho Rayon Co., Ltd., UT500 strand tensile strength 490)
kgf / mm 2 , tensile modulus 24.5 ton / mm 2 )
And one-way prepreg (carbon fiber weight is 115 g / m
2 ) was produced by a hot melt method to obtain a prepreg of Comparative Example 6 having a resin content of 49% by weight. 1 of this prepreg
The gel time at 50 ° C. was 2.1 minutes.
【0104】このプリプレグの樹脂フローは22.7重
量%であり、フロー指数は0.46であった。また、得
られたプリプレグを用いてゴルフシャフトを内圧成形法
により成形してみると、シャフト成形時の樹脂フローは
5.0重量%と多かった。プリプレグの硬化により長時
間かかるため、十分なフロー抑制能が得られず、シャフ
ト表面のボイドも0.30個/cm2 と多めで良好な成
形物は得られなかった。The resin flow of this prepreg was 22.7% by weight, and the flow index was 0.46. Also, when a golf shaft was molded by the internal pressure molding method using the obtained prepreg, the resin flow at the time of molding the shaft was as high as 5.0% by weight. Since it took a long time to cure the prepreg, sufficient flow suppressing ability was not obtained, and the voids on the shaft surface were as large as 0.30 / cm 2, and a good molded product was not obtained.
【0105】用いたマトリックス樹脂の組成、プリプレ
グの性質、プリプレグを使用した成形品の物性について
下記の表2にまとめて示す。The composition of the matrix resin used, the properties of the prepreg, and the physical properties of the molded articles using the prepreg are shown in Table 2 below.
【0106】下記の表1、表2の判定欄における◎、
○、△、×はそれぞれ成形後のシャフト表面に発生する
ボイドの個数より判定し、その定義は次の通りである。 ◎:シャフト表面ボイド0.15個/cm2 以下で非常
に良好なもの。 ○:シャフト表面ボイド0.16〜0.25個/cm2
で良好なもの。 △:シャフト表面ボイド0.26〜0.35個/cm2
で成形状態に支障があるもの。 ×:シャフト表面ボイド0.36個/cm2 以上で成形
状態が悪いもの。In the judgment columns of Tables 1 and 2 below, ◎,
○, △, and × are each determined from the number of voids generated on the shaft surface after molding, and the definitions are as follows. A: Very good with a shaft surface void of 0.15 / cm 2 or less. :: shaft surface voids 0.16 to 0.25 / cm 2
And good ones. Δ: shaft surface voids 0.26 to 0.35 / cm 2
With trouble in molding condition. ×: Shaft surface voids of 0.36 / cm 2 or more and poor molded state.
【0107】[0107]
【表1】 [Table 1]
【0108】[0108]
【表2】 [Table 2]
【0109】[0109]
【発明の効果】本発明のプリプレグは、樹脂含有率が3
5重量%〜45重量%と高いにも関わらず、高温、高圧
下でも良好な樹脂フロー抑制能を有し、且つ150℃で
のゲルタイムが0.1〜1.5分と速硬化性を兼備する
ことにより、成形後の成形物の表面の仕上がり状態も良
好である。特に、本発明のプリプレグは、内圧成形用材
料として好適である。The prepreg of the present invention has a resin content of 3
Despite its high content of 5% to 45% by weight, it has good resin flow suppression ability even under high temperature and high pressure, and has a gel time at 150 ° C. of 0.1 to 1.5 minutes and has fast curing properties. By doing so, the finished state of the surface of the molded article after molding is good. In particular, the prepreg of the present invention is suitable as a material for internal pressure molding.
フロントページの続き (72)発明者 安藤 正人 静岡県駿東郡長泉町上土狩234番地 東邦 レーヨン株式会社研究所内 Fターム(参考) 4F072 AA06 AB06 AB08 AB09 AB10 AB11 AD23 AE02 AE04 AE15 AF28 AG03 Continued on the front page (72) Inventor Masato Ando 234, Kamitsukari, Nagaizumi-cho, Sunto-gun, Shizuoka Prefecture Toho Rayon Co., Ltd. F-term (reference) 4F072 AA06 AB06 AB08 AB09 AB10 AB11 AD23 AE02 AE04 AE15 AF28 AG03
Claims (4)
てなるプリプレグにおいて、150℃でのゲルタイムが
0.1〜1.5分、温度150℃×圧力10kg/cm
2 の樹脂フロー指数が次式に示される関係であり、且つ
樹脂含有率が35重量%〜45重量%であることを特徴
とするプリプレグ。 樹脂フロー指数=樹脂フロー(重量%)/樹脂含有率
(重量%) 0.03≦樹脂フロー指数≦0.511. A prepreg comprising a fiber reinforced material impregnated with a matrix resin, having a gel time at 150 ° C. of 0.1 to 1.5 minutes, a temperature of 150 ° C. and a pressure of 10 kg / cm.
2. A prepreg, wherein the resin flow index of 2 has a relationship represented by the following formula, and the resin content is 35% by weight to 45% by weight. Resin flow index = resin flow (% by weight) / resin content (% by weight) 0.03 ≦ resin flow index ≦ 0.51
(B)、(C)及び(D)成分を含有し、それぞれの配
合割合が下記量であることを特徴とする請求項1記載の
プリプレグ。 (A)エポキシ樹脂 100重量部 (B)アミン系潜在性硬化剤 2〜10重量部 (C)アルキル尿素型硬化促進剤 2〜5重量部 (D)揺変剤 5〜15重量部2. The matrix resin according to the following (A),
2. The prepreg according to claim 1, comprising components (B), (C) and (D), and the mixing ratio of each is as follows. (A) 100 parts by weight of epoxy resin (B) 2 to 10 parts by weight of amine-based latent curing agent (C) 2 to 5 parts by weight of alkyl urea type curing accelerator (D) 5 to 15 parts by weight of thixotropic agent
リコーンカーバイト繊維、ガラス繊維、チラノ繊維およ
びアラミド繊維の1種又は2種以上の組み合わせからな
ることを特徴する請求項1記載のプリプレグ。3. The prepreg according to claim 1, wherein the fiber reinforcement comprises one or a combination of two or more of carbon fiber, boron fiber, silicone carbide fiber, glass fiber, Tyranno fiber and aramid fiber.
とする請求項1記載のプリプレグ。4. The prepreg according to claim 1, wherein the fiber reinforcement is carbon fiber.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26174698A JP2000086784A (en) | 1998-09-16 | 1998-09-16 | Prepreg |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26174698A JP2000086784A (en) | 1998-09-16 | 1998-09-16 | Prepreg |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2000086784A true JP2000086784A (en) | 2000-03-28 |
Family
ID=17366143
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP26174698A Pending JP2000086784A (en) | 1998-09-16 | 1998-09-16 | Prepreg |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2000086784A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7608655B2 (en) * | 2004-08-12 | 2009-10-27 | Illinois Tool Works Inc. | Sprayable skin composition and method of applying |
US7959838B2 (en) | 2002-11-28 | 2011-06-14 | Mitsubishi Rayon Co., Ltd. | Epoxy resin for prepreg, prepreg, fiber-reinforced composite material and methods for production thereof |
WO2012081407A1 (en) | 2010-12-13 | 2012-06-21 | 東レ株式会社 | Carbon fiber prepreg, method for producing same and carbon fiber reinforced composite material |
-
1998
- 1998-09-16 JP JP26174698A patent/JP2000086784A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7959838B2 (en) | 2002-11-28 | 2011-06-14 | Mitsubishi Rayon Co., Ltd. | Epoxy resin for prepreg, prepreg, fiber-reinforced composite material and methods for production thereof |
US8470435B2 (en) | 2002-11-28 | 2013-06-25 | Mitsubishi Rayon Co., Ltd. | Epdxy resin for prepreg, prepreg, fiber-reinforced composite material, and methods for production thereof |
US8486518B2 (en) | 2002-11-28 | 2013-07-16 | Mitsubishi Rayon Co., Ltd. | Epoxy resin for prepreg, prepreg, and fiber-reinforced composite material and methods for production thereof |
US7608655B2 (en) * | 2004-08-12 | 2009-10-27 | Illinois Tool Works Inc. | Sprayable skin composition and method of applying |
WO2012081407A1 (en) | 2010-12-13 | 2012-06-21 | 東レ株式会社 | Carbon fiber prepreg, method for producing same and carbon fiber reinforced composite material |
US9074064B2 (en) | 2010-12-13 | 2015-07-07 | Toray Industries, Inc. | Carbon fiber prepreg, method for producing same and carbon fiber reinforced composite material |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3985224B2 (en) | Matrix resin composition | |
JP3661194B2 (en) | Woven prepreg and honeycomb sandwich panel | |
JPH1143546A (en) | Cloth prepreg and honeycomb structure | |
JP2000086784A (en) | Prepreg | |
JPH0820708A (en) | Epoxy resin composition and prepreg prepared therefrom | |
JPH0820706A (en) | Epoxy resin composition and prepreg prepared therefrom | |
JPH05239317A (en) | Epoxy resin composition, prepreg and production of prepreg | |
JP2604778B2 (en) | Matrix resin composition | |
JP2001302823A (en) | Resin composition for fiber-reinforced composite material, prepreg and fiber-reinforced composite material | |
JP2000281747A (en) | Epoxy resin composition for composite material | |
JP2000273224A (en) | Prepreg and its molding product | |
JPH0841174A (en) | Epoxy resin composition and prepreg | |
JP2004292594A (en) | Epoxy resin composition, prepreg, and fiber-reinforced composite material | |
JPH024607B2 (en) | ||
JPH0820654A (en) | Epoxy resin composition and prepreg using the same | |
JPH04153252A (en) | Matrix resin composition | |
JPH01185351A (en) | Epoxy resin composition for carbon fiber reinforced material | |
JP3986663B2 (en) | Unidirectional fiber reinforced prepreg | |
JPH0812861A (en) | Epoxy resin composition and prepreg | |
JP4266696B2 (en) | Manufacturing method of fiber reinforced composite material | |
JPH07137163A (en) | Manufacture of tubular composite moldings | |
JPH0776616A (en) | Epoxy resin composition for prepreg and prepreg | |
JPH0812860A (en) | Epoxy resin composition and prepreg using the same | |
KR102461792B1 (en) | Tow prepreg having high impact strength for the filament winding | |
TWI805651B (en) | Prepregs and Fiber Reinforced Composites |