JPH01148547A - Symmetric hybrid laminated material - Google Patents
Symmetric hybrid laminated materialInfo
- Publication number
- JPH01148547A JPH01148547A JP62305593A JP30559387A JPH01148547A JP H01148547 A JPH01148547 A JP H01148547A JP 62305593 A JP62305593 A JP 62305593A JP 30559387 A JP30559387 A JP 30559387A JP H01148547 A JPH01148547 A JP H01148547A
- Authority
- JP
- Japan
- Prior art keywords
- prepreg
- carbon fiber
- lamination
- inorganic
- fibers
- 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
- 239000002648 laminated material Substances 0.000 title claims abstract description 16
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 29
- 239000004917 carbon fiber Substances 0.000 claims abstract description 29
- 239000012784 inorganic fiber Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 238000010030 laminating Methods 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 abstract description 28
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 18
- 229920000647 polyepoxide Polymers 0.000 abstract description 11
- 238000003475 lamination Methods 0.000 abstract description 9
- 239000003822 epoxy resin Substances 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 description 19
- 238000001723 curing Methods 0.000 description 11
- 239000002131 composite material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- -1 acetylacetoxy Chemical group 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
- 230000000052 comparative effect Effects 0.000 description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 229920003257 polycarbosilane Polymers 0.000 description 4
- 230000005484 gravity Effects 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 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 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009787 hand lay-up Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、炭素繊維及び特定の無機繊維のそれぞれに熱
硬化性樹脂を含浸させたプリプレグを積層して製造され
る、反りのない対称ハイブリッド積層材に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention is a non-warping symmetrical hybrid manufactured by laminating prepregs in which carbon fibers and specific inorganic fibers are each impregnated with a thermosetting resin. Regarding laminated materials.
（従来技術及びその問題点）
炭素繊維強化プラスチツク複合体は、比強度、比弾性率
が高いために、スポーツ・レジャー用品などに使用され
ている。しかし、この材料は、圧縮強度あるいは曲げ強
度が低（、さらに伸びが小さく脆いという技術的問題点
を有している。(Prior art and its problems) Carbon fiber-reinforced plastic composites have high specific strength and specific modulus, and are therefore used in sports and leisure goods. However, this material has technical problems such as low compressive strength or bending strength (and low elongation and brittleness).
このため、炭素繊維層と他の繊維層とを組み合わせたい
わゆるハイブリッド積層材によって、上記問題点の解消
を図る試みがされている。炭素繊維と組み合わせる繊維
としては、従来、ガラス繊維及びアラミド繊維が好んで
使用されてきた。しかし、ガラス繊維は強度及び弾性率
が低く、そのうえ重いという問題を有しており、また、
アラミド繊維は、伸びは大きいが圧縮強度が小さく吸湿
しやすいという問題を有している。従って、これら繊維
と炭素繊維とを併用して得られるプラスチックス複合材
も実用上必ずしも満足のできる材料とは言いがたい。Therefore, attempts have been made to solve the above-mentioned problems by using a so-called hybrid laminate material that combines a carbon fiber layer and other fiber layers. Conventionally, glass fibers and aramid fibers have been preferably used as fibers to be combined with carbon fibers. However, glass fiber has the problem of low strength and elastic modulus, and is also heavy.
Aramid fibers have a problem of high elongation but low compressive strength and easy moisture absorption. Therefore, it is difficult to say that a plastics composite material obtained by using a combination of these fibers and carbon fibers is a material that is practically satisfactory.
特開昭６２−７７３７号公報には、Ｓｉ、Ｔｉ又はＺｒ
、Ｃ及びＯの各元素から構成される無機繊維及び炭素繊
維のそれぞれにプラスチックスが含浸されたプリプレグ
を積層し、この積層物を加圧加熱して得られる複合材、
いわゆる層間ハイブリッド複合材が開示されている。こ
の複合材は、上記無機繊維の優れた特長、即ち、マ）ｌ
ルンクス樹脂との良好な接着性及び繊維自体の可撓性が
生かされることによって、炭素繊維強化プラスチツク複
合材に比較して、引張強度、眉間剪断強度及びシャルピ
ー衝撃強度において優れている。JP-A-62-7737 discloses that Si, Ti or Zr
, a composite material obtained by laminating prepregs impregnated with plastics on inorganic fibers and carbon fibers each composed of the elements C and O, and pressurizing and heating this laminate,
So-called interlayer hybrid composites have been disclosed. This composite material has the excellent features of the above-mentioned inorganic fibers, namely,
By taking advantage of the good adhesion with Runx resin and the flexibility of the fiber itself, it is superior in tensile strength, glabellar shear strength, and Charpy impact strength compared to carbon fiber reinforced plastic composites.
上記の層間ハイブリッド積層材は、用いられる炭素繊維
と無機繊維とで弾性率あるいは熱膨張係数が異なるため
に反りが発生し、高い寸法精度が要求される構造材料と
して使用しがたいという問題点を有している。The above-mentioned interlayer hybrid laminate material has the problem that warping occurs due to the difference in elastic modulus or thermal expansion coefficient between the carbon fiber and inorganic fiber used, making it difficult to use as a structural material that requires high dimensional accuracy. have.
（発明の目的）
本発明の目的は、特開昭６２−７７３７号公報に記載さ
れた眉間ハイブリッド積層材の長所を維持しつつ、その
問題点である反りを光消した積層材を提供することにあ
る。(Object of the Invention) The object of the present invention is to provide a laminate material that eliminates the problem of warping while maintaining the advantages of the glabella hybrid laminate material described in JP-A No. 62-7737. It is in.
（問題点を解決するための技術的手段）本発明の上記目
的は、炭素繊維及び実質的にＳｉ、Ｔｉ又はＺｒ、Ｃ及
び０の各元素から構成される無機繊維のそれぞれに熱硬
化性樹脂を含浸させたプリプレグを積層して製造される
対称ノλイブリッド積層材において、積層構成が積層中
央面に対して面対称であることを特徴とする対称ノーイ
ブリッド積層材によって達成される。(Technical Means for Solving the Problems) The above object of the present invention is to apply a thermosetting resin to each of the carbon fibers and the inorganic fibers substantially composed of the elements Si, Ti or Zr, C and 0. This is achieved by a symmetrical no-brid laminated material manufactured by laminating prepregs impregnated with λ, in which the laminated structure is plane symmetrical with respect to the center plane of the lamination.
本発明における炭素繊維は、その前駆体としてポリアク
リロニトリル、石油ビ・ンチ及び石炭ピンチのいずれを
使用したものであってもよい。また、焼成温度に依存し
て呼称される炭素質繊維、黒鉛質繊維のいずれであって
もよい。The carbon fiber in the present invention may be made of polyacrylonitrile, petroleum vinyl, or coal pinch as a precursor thereof. Further, it may be either carbonaceous fiber or graphite fiber, which are called depending on the firing temperature.
本発明における無機繊維はアメリカ特許第４３４２７１
２号明細書及び同第４５１５７４２号明細書に記載の方
法に従って調製することができ、これら明細書の記載は
本明細書の一部として援用される。The inorganic fiber in the present invention is US Patent No. 434271.
It can be prepared according to the method described in Specification No. 2 and Specification No. 4515742, the descriptions of which are incorporated herein by reference.
調製法の一例を以下に示す。An example of the preparation method is shown below.
式 Ｒ
＋Ｓｉ ＣＨｚ→−
■
（但し、式中のＲは水素原子、低級アルキル基又はフェ
ニル基を示す）で表される主鎖骨格を有する数平均分子
量的２００〜１００００のポリカルボシラン、及び
式Ｍ Ｘ ａ
（但し、式中のＭはＴｉ又はＺｒを示し、Ｘは炭素数１
〜２０個のアルコキシ基、フェノキシ基又はアセチルア
セトキシ基を示す）で表される有機金属化合物を、上記
ポリカルボシランのＡＳｉ−ＣＨ２弁の構造単位の全数
対上記有機金属化合物の４ト０井の構造単位の全数の比
率が２：１ないし２００：１の範囲内となる量比に添加
し、反応に対して不活性な雰囲気中において加熱反応し
て、前記ポリカルボシランの珪素原子の少なくとも一部
を、前記有機金属化合物の金属原子と酸素原子を介して
結合させて、数平均分子量的７００〜１０００００の有
機金属共重合体を生成させる第１工程、上記共重合体の
紡糸原液を調製し紡糸する第２工程、紡糸繊維を不融化
する第３工程、及び不融化した紡糸繊維を真空中あるい
は不活性ガス雰囲気中で８００〜１５００℃の温度範囲
で焼成する第４工程からなる製造方法によって、本発明
における無機繊維を得ることができる。A polycarbosilane with a number average molecular weight of 200 to 10,000 having a main chain skeleton represented by the formula R +Si CHz→- (wherein R in the formula represents a hydrogen atom, a lower alkyl group, or a phenyl group), and the formula M X a (However, M in the formula represents Ti or Zr, and X has 1 carbon number
~20 alkoxy groups, phenoxy groups or acetylacetoxy groups) is added to the total number of structural units of the ASi-CH2 valve of the above polycarbosilane to 4 to 0 wells of the above organometallic compound. At least one of the silicon atoms of the polycarbosilane is added to the polycarbosilane in an amount such that the ratio of the total number of structural units is within the range of 2:1 to 200:1, and is heated and reacted in an atmosphere inert to the reaction. a first step in which a spinning stock solution of the above-mentioned copolymer is prepared; By a manufacturing method consisting of a second step of spinning, a third step of making the spun fibers infusible, and a fourth step of firing the infusible spun fibers in a vacuum or in an inert gas atmosphere at a temperature range of 800 to 1500 ° C. , the inorganic fiber according to the present invention can be obtained.
無機繊維中の各構成元素の割合は、
Ｓｉ：３０〜６０重量％、
Ｔｉ又はＺｒ：０．５〜３５重量％、好ましくは１〜１
０重景％、
Ｃ：２５〜４０重量％、
０ ： ０．０１〜３０重量％
である。The proportions of each constituent element in the inorganic fiber are: Si: 30-60% by weight, Ti or Zr: 0.5-35% by weight, preferably 1-1
0 weight%, C: 25-40% by weight, 0: 0.01-30% by weight.
無機繊維と炭素繊維との合計に対する無機繊維の割合は
１〜８０体積％、特に３〜７０体積％であることが好ま
しい。上記割合が１体積％未満では積層材の曲げ特性の
改善効果が小さく、８０体積％より大きいと、相対的に
炭素繊維の割合が低下し、積層材に炭素繊維の高引張強
度及び軽量性を付与しがたくなる。The ratio of inorganic fibers to the total of inorganic fibers and carbon fibers is preferably 1 to 80% by volume, particularly 3 to 70% by volume. If the above proportion is less than 1% by volume, the effect of improving the bending properties of the laminated material is small, and if it is greater than 80% by volume, the proportion of carbon fiber decreases relatively, and the high tensile strength and lightweight properties of carbon fiber are added to the laminated material. It becomes difficult to grant.
積層材に対する炭素繊維と無機繊維との合計割合は、通
常３０〜８０体積％、好ましくは４５〜６５体積％であ
る。The total proportion of carbon fibers and inorganic fibers in the laminate is usually 30 to 80% by volume, preferably 45 to 65% by volume.
炭素繊維及び無機繊維は一方向に引き揃えた形態として
使用することが好ましいが、それぞれの繊維を織って形
成された織布（織物）の形態で使用することもできる。Although carbon fibers and inorganic fibers are preferably used in the form of unidirectionally aligned fibers, they can also be used in the form of a woven fabric (fabric) formed by weaving the respective fibers.
また、両繊維は公知の表面処理、サイジング処理が施さ
れていてもよい。Further, both fibers may be subjected to known surface treatment and sizing treatment.
本発明における熱硬化性樹脂については特に制限はなく
、エポキシ樹脂、不飽和ポリエステル樹脂、ビニルエス
テル樹脂、フェノール樹脂、ヒスマレイミド樹脂、ポリ
イミド樹脂などが挙げられる。これらの樹脂の中でもエ
ポキシ樹脂が好んで使用される。上記エポキシ樹脂は、
ポリエポキシド、硬化剤、硬化触媒などからなる樹脂組
成物である。The thermosetting resin in the present invention is not particularly limited, and examples include epoxy resins, unsaturated polyester resins, vinyl ester resins, phenol resins, hismaleimide resins, and polyimide resins. Among these resins, epoxy resins are preferably used. The above epoxy resin is
It is a resin composition consisting of polyepoxide, a curing agent, a curing catalyst, etc.
ポリエポキシドとしては、例えば、ビスフェノールＡ、
Ｆ及びＳのグリシジル化合物、タレゾールノボラック又
はフェノールノボラックのグリシジル化合物及び脂環族
ポリエポキシドなどが挙げられる。Examples of polyepoxide include bisphenol A,
Examples include glycidyl compounds of F and S, glycidyl compounds of talesol novolak or phenol novolak, and alicyclic polyepoxides.
ポリエポキシドの別の例としては、多価フェノール、多
価アルコール又は芳香族アミンのグリシジル化合物が挙
げられる。Other examples of polyepoxides include glycidyl compounds of polyhydric phenols, polyhydric alcohols or aromatic amines.
これらのポリエポキシドの内、ビスフェノールＡのグリ
シジルエーテル、タレゾールノボラック又はフェノール
ノボラックのグリシジル化合物、ジアミノジフェニルメ
タンのグリシジル化合物、アミノフェノールのグリシジ
ル化合物が一般に使用される。また、本発明の積層材を
航空機の一次構造材料のような高機能を要求される部材
として使用する場合は、上記ポリエポキシドの中でも、
ジアミノジフェニルメタンなどの多官能アミンのグリシ
ジル化合物を使用することが好ましい。Among these polyepoxides, the glycidyl ether of bisphenol A, the glycidyl compound of talesol novolak or phenol novolak, the glycidyl compound of diaminodiphenylmethane, and the glycidyl compound of aminophenol are generally used. In addition, when the laminate material of the present invention is used as a member requiring high functionality such as a primary structural material of an aircraft, among the above polyepoxides,
Preference is given to using glycidyl compounds of polyfunctional amines such as diaminodiphenylmethane.
本発明の積層材は、炭素繊維及び無機繊維のそれぞれに
熱硬化性樹脂を含浸したプリプレグを積層し、ついで熱
硬化性樹脂を硬化させることによって製造される。The laminate of the present invention is manufactured by laminating prepregs in which carbon fibers and inorganic fibers are each impregnated with a thermosetting resin, and then curing the thermosetting resin.
プリプレグの調製法としては、多数本の前記繊維かなる
フィラメント糸を一方向に引き揃えて熱硬化性樹脂に挟
み込んでプリプレグとする方法、熱硬化性樹脂を含浸し
たフィラメント糸束をドラムに巻き掛けてプリプレグと
する方法、多数本のフィラメント糸を引き揃えた後に熱
硬化性樹脂のフィルム状物を溶融含浸させてプリプレグ
とする方法、織布又は不織布を熱硬化性樹脂溜まりに導
き、含浸、乾燥してプリプレグとする方法、熱硬化性樹
脂製のシート状物を織布又は不織布に溶融含浸させてプ
リプレグとする方法などの、それ自体公知の方法を適宜
採用することができる。Methods for preparing prepreg include a method in which a large number of filament threads made of the above-mentioned fibers are aligned in one direction and sandwiched between thermosetting resins to make a prepreg, and a bundle of filament threads impregnated with thermosetting resin is wound around a drum. A method of preparing prepreg by pulling a large number of filament threads together and then melting and impregnating them with a thermosetting resin film. A method of introducing a woven or nonwoven fabric into a thermosetting resin reservoir, impregnating it, and drying it. Methods known per se can be appropriately employed, such as a method of preparing a prepreg by melting and impregnating a sheet-like material made of a thermosetting resin into a woven or nonwoven fabric.
本発明においては、上記プリプレグを積層するに際じて
、炭素繊維プリプレグと無機繊維プリプレグとを、積層
中央面に対して面対称に積層することが必要である。プ
リプレグを積層中央面に対して非対称に構成すると、炭
素繊維と無機繊維とでは弾性率あるいは熱膨張係数が異
なるため、積層中央面に関して上側部分と下側部分とで
硬化による収縮応力が相違し、反りが発生する。炭素繊
維プリプレグと無機繊維プリプレグとを、積層中央面に
対して面対称に積層することによって、上記の収縮応力
の相違をなくすことができる。In the present invention, when laminating the above-mentioned prepregs, it is necessary to laminate the carbon fiber prepreg and the inorganic fiber prepreg in plane symmetry with respect to the center plane of the lamination. If the prepreg is configured asymmetrically with respect to the center plane of the stack, the elastic modulus or coefficient of thermal expansion will be different between carbon fibers and inorganic fibers, so the shrinkage stress due to curing will be different between the upper and lower parts with respect to the center plane of the stack. Warpage occurs. By laminating the carbon fiber prepreg and the inorganic fiber prepreg in plane symmetry with respect to the center plane of the lamination, the difference in shrinkage stress described above can be eliminated.
プリプレグを積層する方法については特に制限はなく、
ハンドレイアップ法、自動レイアップなどの公知の方法
をすべて採用することができる。There are no particular restrictions on the method of laminating prepreg.
All known methods such as hand layup method and automatic layup method can be employed.
プリプレグの積層形態、構成、順序、繰り返し厚みに関
しては、前記した積層中央面に対して面対称構成にする
こと以外は特別の制限はない。なお、積層角度について
は反りの面から対称積層にすることが必要である。There are no particular restrictions on the stacking form, configuration, order, and repeating thickness of the prepregs, other than that they should be symmetrical with respect to the center plane of the stack. In addition, regarding the lamination angle, it is necessary to make the lamination symmetrical in terms of warpage.
プリプレグの積層物から積層材を形成する方法はなんら
制限されるものではなく、減圧バック／オートクレーブ
硬化法、ホットプレス成形法、シートワインディング法
、シートラッピング法、テープワインディング法、テー
プラッピング法などの公知の方法を適宜採用することが
できる。The method of forming a laminate from a prepreg laminate is not limited in any way, and may include known methods such as vacuum bag/autoclave curing method, hot press molding method, sheet winding method, sheet wrapping method, tape winding method, tape wrapping method, etc. The following methods can be adopted as appropriate.
硬化温度、硬化圧力、硬化時間などの硬化条件は、使用
される熱硬化性樹脂によって決定される。Curing conditions such as curing temperature, curing pressure, and curing time are determined by the thermosetting resin used.
例えば、熱硬化性樹脂としてエポキシ樹脂を使用する場
合の一般的硬化温度は１００〜２５０°Ｃ１好ましくは
１２０〜２００°Ｃである。また、プレキュア−あるい
はポストキュアーも適宜行うことができる。For example, when an epoxy resin is used as the thermosetting resin, the general curing temperature is 100 to 250°C, preferably 120 to 200°C. Moreover, pre-cure or post-cure can be performed as appropriate.
本発明の対称ハイブリッド積層材は、板、パイプなどの
単純形状の製品の他に、曲面あるいは凹凸を有する種々
の大きさの三次元形状の製品を再現性よ（容易に与える
ことができる。The symmetrical hybrid laminate material of the present invention can be reproducibly produced (easily produced) in addition to products with simple shapes such as plates and pipes, as well as products with three-dimensional shapes of various sizes having curved surfaces or irregularities.
（実施例）
以下に実施例及び比較例を示す。各側における対称ハイ
ブリッド積層材の引張強度及び圧縮強度は、以下の試験
片について、オリエンチック■製のテンシロンＵＴＭ５
Ｔを用い、温度２３℃、相対湿度５０％の条件下に繊維
の長さ方向に各１０回測定した。(Example) Examples and comparative examples are shown below. The tensile and compressive strengths of the symmetrical hybrid laminates on each side were determined for the following specimens by Tensilon UTM5 manufactured by Orientic ■.
Using T, measurements were made 10 times each in the longitudinal direction of the fiber under conditions of a temperature of 23° C. and a relative humidity of 50%.
■張試験 １２．７ ２００ １．５ ２ ｍｍ
／ｍ／前圧縮試験１０ ６０ ２ ０．５ｍｍ
／分積層材の反りは２５０ｍｍＸ ２５０ｍｍＸ ２ｍ
ｍの成形品を平盤の上に配置し、最大反り高さ及び最小
接地部分の長さを計測し、以下の式によって求めた値（
％）である。■Tension test 12.7 200 1.5 2 mm
/m/Pre-compression test 10 60 2 0.5mm
/min Warp of laminated material is 250mm x 250mm x 2m
m molded product was placed on a flat plate, the maximum warp height and the minimum length of the ground contact part were measured, and the value obtained by the following formula (
%).
積層材の繊維体積含有率（Ｖ ｆ ）はＡＳＴＭＤ３１
７１に従って測定した。その単位は体積％である。The fiber volume content (V f ) of the laminate is in accordance with ASTM D31.
Measured according to 71. Its unit is volume %.
以下において部はすべて重量部である。In the following, all parts are by weight.
実施例１
ビスフェノールＡ型エポキシ樹脂（チバガイギー社製、
ＸＢ２８７９Ａ）１００部及びジシアンジアミド硬化剤
（チバガイギー社製、Ｘ Ｂ ２８．７９Ｂ）２０部を
均一に混合した後に、混合物を重量比で１＝１のメチル
セロソルブとアセトンとの混合溶媒に溶解して、上記混
合物の２８重量％溶液を調製した。Example 1 Bisphenol A epoxy resin (manufactured by Ciba Geigy,
After uniformly mixing 100 parts of XB2879A) and 20 parts of a dicyandiamide curing agent (manufactured by Ciba Geigy, XB28.79B), the mixture was dissolved in a mixed solvent of methyl cellosolve and acetone in a weight ratio of 1=1, A 28% by weight solution of the above mixture was prepared.
炭素繊維（東邦レーヨン■製、ベスファイ）ＨＴＡ６０
００：引張弾性率２４ｔ／胴２、比重１゜７７）に上記
溶液を含浸した後に、ドラムワイングーを用いて一方向
に巻き取り、熱風循環オーブン中１００°Ｃで１４分間
加熱することによって、半硬化状態の一方向引揃え炭素
繊維プリプレグを調製した。このプリプレグの樹脂含有
量は３８重量％、厚みは０．２ ｍｍであった。Carbon fiber (manufactured by Toho Rayon, Besphi) HTA60
00: Tensile elastic modulus 24t/shell 2, specific gravity 1°77) After impregnating with the above solution, winding it in one direction using a drum wine goo and heating it at 100 ° C for 14 minutes in a hot air circulation oven. A semi-cured unidirectionally aligned carbon fiber prepreg was prepared. This prepreg had a resin content of 38% by weight and a thickness of 0.2 mm.
Ｓｉ、Ｔｉ、Ｃ及び０からなる無機繊維（宇部興産■製
、チラノ繊維：引張弾性率２１ ｔ ７ｍｍ２、比重２
．３５ ）を用いて上記と同様にして、半硬化状態の一
方向引揃えチラノ繊維プリプレグを調製した。このプリ
プレグの樹脂含有量は３０重景％、厚みは０．２胴であ
った。Inorganic fiber consisting of Si, Ti, C and 0 (manufactured by Ube Industries, Tyranno fiber: tensile modulus 21t 7mm2, specific gravity 2
．． A unidirectionally aligned tyranno fiber prepreg in a semi-cured state was prepared using 35) in the same manner as above. The resin content of this prepreg was 30%, and the thickness was 0.2 mm.
上記２種類のプリプレグを用いて、第１表に示す構成で
一方向に重ね合わせ、１３０°ｃ、ｉｉｂ／ ｃｒＡで
９０分間プレス成形することによって、２５０ｍｍＸ２
５０ｍｍの大きさの一方向層間ハイブリッド積層材を製
造した。この積層材から各種試験片をダイアモンド鋸を
用いて切り出し試験に供した。結果を第２表に示す。Using the above two types of prepregs, stack them in one direction with the configuration shown in Table 1 and press-form them at 130°C and IIB/CRA for 90 minutes to form a 250mm x 2
A unidirectional interlayer hybrid laminate with a size of 50 mm was produced. Various test pieces were cut out from this laminated material using a diamond saw and subjected to tests. The results are shown in Table 2.
実施例２
積層構成を第１表に記載のように変えた以外は実施例１
と同様の方法を繰り返した。結果を第２表に示す。Example 2 Example 1 except that the laminated structure was changed as shown in Table 1.
The same method was repeated. The results are shown in Table 2.
実施例３
チラノ繊維プリプレグの厚みを０．１５ｍｍに変えた以
外は実施例２と同様の方法を繰り返した。結果を第２表
に示す。Example 3 The same method as Example 2 was repeated except that the thickness of the tyranno fiber prepreg was changed to 0.15 mm. The results are shown in Table 2.
実施例４
チラノ繊維プリプレグの厚みを０．１ ｍｍに変えた以
外は実施例２と同様の方法を繰り返した。結果を第２表
に示す。Example 4 The same method as Example 2 was repeated except that the thickness of the tyranno fiber prepreg was changed to 0.1 mm. The results are shown in Table 2.
実施例５
炭素繊維として、引張弾性率４２ ｔ ／ｌｒｍ２、比
重１．８３の炭素繊維（東邦レーヨン■製、ベスファイ
）ＨＭ４０）を使用した以外は実施例１と同様の方法を
繰り返した。結果を第２表に示す。Example 5 The same method as in Example 1 was repeated, except that carbon fiber (manufactured by Toho Rayon ■, Besphi) HM40) having a tensile modulus of elasticity of 42 t/lrm2 and a specific gravity of 1.83 was used as the carbon fiber. The results are shown in Table 2.
実施例６
炭素繊維として、実施例５で使用した炭素繊維を使用し
た以外は実施例２と同様の方法を繰り返した。結果を第
２表に示す。Example 6 The same method as in Example 2 was repeated except that the carbon fiber used in Example 5 was used as the carbon fiber. The results are shown in Table 2.
比較例１〜３
積層構成を第１表に記載のように変えた以外は実施例１
と同様の方法を繰り返した。結果を第２表に示す。Comparative Examples 1 to 3 Example 1 except that the laminated structure was changed as shown in Table 1.
The same method was repeated. The results are shown in Table 2.
比較例４〜６
積層構成を第１表に記載のように変えた以外は実施例５
と同様の方法を繰り返した。結果を第２表に示す。Comparative Examples 4 to 6 Example 5 except that the laminated structure was changed as shown in Table 1
The same method was repeated. The results are shown in Table 2.
第１表
１割合 構 成
−Ｃ札積受Ｏ−
実施例１ ３１ ＴＣＴＣＣ，ＣＣＴＣＴ
〃２ １３ ＴＣＣＣＣＣＣＣＣＴ〃３
１０ ＴＣＣＣＣＣＣＣＣＴ〃４
６ ＴＣＣＣＣＣＣＣＣＴ／／ ５
３１ ＴＣＴＣＣＣＣＴＣＴ〃６ １３
ＴＣＣＣＣＣＣＣＣＴ比較例１ ３１
ＴＴＴＴＣＣＣＣＣＣ／／ ２ １３
ＴＴＣＣＣＣＣＣＣＣＮ ３ ６
ＴＣＣＣＣＣＣＣＣ（：／／ ４ ３１
ＴＴＴＴＣＣＣＣＣＣ／／ ５ １３
ＴＴＣＣＣＣＣＣＣＣ〃６ ６ Ｔ
ＣＣＣＣＣＣＣＣＣ第１表の構成の欄において、Ｔはチ
ラノ繊維層を示し、Ｃは炭素繊維層を示す。Table 1 1 Ratio Composition - C tag loading O - Example 1 31 TCTCC, CCTCT
〃2 13 TCCCCCCCCCT〃3
10 TCCCCCCCCCT〃4
6 TCCCCCCCCCT // 5
31 TCTCCCCT〃6 13
TCCCCCCCCCT Comparative Example 1 31
TTTTCCCCCC// 2 13
TTCCCCCCCCN 3 6
TCCCCCCCC (:// 4 31
TTTTCCCCCC// 5 13
TTCCCCCCC〃6 6 T
CCCCCCCCCC In the structure column of Table 1, T indicates a tyranno fiber layer, and C indicates a carbon fiber layer.
第２表 Ｖｆ 引張強度 圧縮強度 反 り 生盪／’ Ｍ ｋＺ！Ｌ −Ｘ−Table 2 Vf Tensile strength Compressive strength Warpage Raw soup／’ M kZ! L -X-
Claims (1)
各元素から構成される無機繊維のそれぞれに熱硬化性樹
脂を含浸させたプリプレグを積層して製造される対称ハ
イブリッド積層材において、積層構成が積層中央面に対
して面対称であることを特徴とする対称ハイブリッド積
層材。In a symmetrical hybrid laminate manufactured by laminating prepregs in which carbon fibers and inorganic fibers substantially composed of Si, Ti, or each element of Zr, C, and O are impregnated with a thermosetting resin, A symmetrical hybrid laminate material characterized by a structure having plane symmetry with respect to the center plane of the laminate.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62305593A JPH01148547A (en) | 1987-12-04 | 1987-12-04 | Symmetric hybrid laminated material |
| KR1019880016114A KR930009294B1 (en) | 1987-12-04 | 1988-12-03 | Interply-hybridized laminated material |
| EP88311494A EP0319346A3 (en) | 1987-12-04 | 1988-12-05 | Interply-hybridized laminated material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62305593A JPH01148547A (en) | 1987-12-04 | 1987-12-04 | Symmetric hybrid laminated material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01148547A true JPH01148547A (en) | 1989-06-09 |
Family
ID=17947009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62305593A Pending JPH01148547A (en) | 1987-12-04 | 1987-12-04 | Symmetric hybrid laminated material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01148547A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5658852A (en) * | 1979-10-18 | 1981-05-22 | Mitsubishi Heavy Ind Ltd | Tabular molding blank for structure |
| JPS6146891A (en) * | 1984-08-14 | 1986-03-07 | バブコツク日立株式会社 | Clinker cooling shifter |
-
1987
- 1987-12-04 JP JP62305593A patent/JPH01148547A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5658852A (en) * | 1979-10-18 | 1981-05-22 | Mitsubishi Heavy Ind Ltd | Tabular molding blank for structure |
| JPS6146891A (en) * | 1984-08-14 | 1986-03-07 | バブコツク日立株式会社 | Clinker cooling shifter |
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