JPH01104626A - Prepreg having high-toughness fine particles - Google Patents
Prepreg having high-toughness fine particlesInfo
- Publication number
- JPH01104626A JPH01104626A JP26203087A JP26203087A JPH01104626A JP H01104626 A JPH01104626 A JP H01104626A JP 26203087 A JP26203087 A JP 26203087A JP 26203087 A JP26203087 A JP 26203087A JP H01104626 A JPH01104626 A JP H01104626A
- Authority
- JP
- Japan
- Prior art keywords
- prepreg
- resin
- fine particles
- fiber
- resins
- 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.)
- Granted
Links
- 239000010419 fine particle Substances 0.000 title claims abstract description 47
- 229920005989 resin Polymers 0.000 claims abstract description 77
- 239000011347 resin Substances 0.000 claims abstract description 77
- 239000000835 fiber Substances 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 25
- 239000012783 reinforcing fiber Substances 0.000 claims description 17
- 239000002131 composite material Substances 0.000 abstract description 16
- 239000003822 epoxy resin Substances 0.000 abstract description 15
- 229920000647 polyepoxide Polymers 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 11
- 238000009826 distribution Methods 0.000 abstract description 8
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 7
- 239000004917 carbon fiber Substances 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010439 graphite Substances 0.000 abstract description 5
- 229910002804 graphite Inorganic materials 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 229910052796 boron Inorganic materials 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000010030 laminating Methods 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- 229920005992 thermoplastic resin Polymers 0.000 description 11
- 229920001187 thermosetting polymer Polymers 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011859 microparticle Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 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
- 239000004643 cyanate ester Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000002970 Calcium lactobionate Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 210000004709 eyebrow Anatomy 0.000 description 2
- 239000003733 fiber-reinforced composite Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000004963 Torlon Substances 0.000 description 1
- 229920003997 Torlon® Polymers 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000009975 flexible effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 1
- 239000012285 osmium tetroxide Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、先進複合材料として強度、弾性率、さらには
これらを比重で除した比強度、比弾性率の大なることを
要求される構造体に用いられるプリプレグに関する。さ
らに詳しくはプリプレグの粘着性と柔軟性を確保しつつ
、強化繊維の方向以外の強度、すなわち非繊維軸引張強
度や衝撃後圧縮強度に対して顕著に改良のなされた構造
体を与えるプリプレグに関する。Detailed Description of the Invention [Industrial Application Fields] The present invention is applicable to advanced composite materials that require high strength and elastic modulus, as well as specific strength and specific modulus obtained by dividing these by specific gravity. It relates to prepreg used for the body. More specifically, the present invention relates to a prepreg that provides a structure with markedly improved strength in directions other than the reinforcing fiber direction, that is, non-fiber axial tensile strength and post-impact compressive strength, while ensuring the adhesiveness and flexibility of the prepreg.
［従来の技術］
繊維強化複合材料は、強化繊維とマトリックス樹脂を必
須の構成要素とする不均一材料であり、このため繊維軸
方向の物性とそれ以外の方向の物性に大きな差が存在す
る。たとえば、落錘衝撃に対する抵抗性は層間剥離強度
によって支配されるため強化繊維の強度を向上させても
抜本的な改良には結びつかないことが知られている。こ
のため、繊維軸方向以外の物性を改良することを目的と
して、マトリックス樹脂の靭性を改良することの他に、
種々の方法による改良が提案されている。[Prior Art] A fiber-reinforced composite material is a non-uniform material containing reinforcing fibers and a matrix resin as essential components, and therefore there is a large difference in physical properties in the fiber axis direction and physical properties in other directions. For example, it is known that resistance to falling weight impact is controlled by delamination strength, so improving the strength of reinforcing fibers does not lead to drastic improvements. For this reason, in addition to improving the toughness of the matrix resin, with the aim of improving physical properties in directions other than the fiber axis direction,
Improvements have been proposed in various ways.
■Ｕ Ｓ Ｐ ３，４７２，７３０号明細書く１９６９
年）では、繊維強化シートの片面あるいは両面にエラス
トマー性物質により改質した熱硬化性樹脂からなる独立
外層フィルム（５ｅｐａｒａｔｅ Ｅｘｔｅｒｉｏｒ
Ｆｉｌｍ ）を配することにより耐層２間剥離力の改善
がなされることが開示されている。■USP No. 3,472,730 specification 1969
In 2013), an independent outer layer film (5 separate exterior layer film) consisting of a thermosetting resin modified with an elastomeric substance on one or both sides of a fiber-reinforced sheet was introduced.
It is disclosed that the peel strength between two layers can be improved by disposing a film.
■特開昭５１−５８４８４号公報（特公昭５８−３１２
９６号公報）では、繊維強化エポキシ樹脂プリプレグの
表面にポリエーテルスルホンフィルムを存在させること
で、成形性および曲げ強度の改善がなされることが開示
されている。■Unexamined Japanese Patent Publication No. 58-58484 (Japanese Patent Publication No. 58-312
No. 96) discloses that moldability and bending strength can be improved by providing a polyether sulfone film on the surface of a fiber-reinforced epoxy resin prepreg.
■特開昭５４−３８７９号公報、特開昭５６−１１５２
１６号公報、特開昭６０−４４３３４号公報では、繊維
強化シートの眉間に短繊維チップ、チョツプドストラン
ド、ミルドファイバーを配し、眉間強度の向上がなされ
ることが開示されている。■JP-A-54-3879, JP-A-56-1152
No. 16 and Japanese Unexamined Patent Publication No. 60-44334 disclose that short fiber chips, chopped strands, and milled fibers are arranged in the glabella of a fiber-reinforced sheet to improve the glabella strength.
■特開昭６０−６３２２９号公報では、繊維強化プリプ
レグの層間にエラストマーで改質したエポキシ樹脂フィ
ルムを配して眉間強度の改善がなされることが開示され
ている。(1) JP-A-60-63229 discloses that glabella strength can be improved by disposing an epoxy resin film modified with an elastomer between the layers of fiber-reinforced prepreg.
■Ｕ Ｓ Ｐ ４，５３９，２５３号明細書 （１９８
５年）（対応特開昭 ６０−２３１７３８号公報）では
、繊維強化プリプレグの眉間に軽″量繊維を基材とする
、不織布、織布、マット、キャリアーにエラストマーで
改質したエポキシ樹脂を含浸させたフィルムを配して層
間強度の改善がなされることが開示されている。■USP No. 4,539,253 specification (198
5) (corresponding to Japanese Patent Application Laid-open No. 60-231738), non-woven fabrics, woven fabrics, mats, and carriers based on lightweight fibers are impregnated with epoxy resin modified with elastomer between the eyebrows of fiber-reinforced prepregs. It is disclosed that the interlaminar strength can be improved by disposing a film having a laminate structure.
■Ｕ Ｓ Ｐ ４，６０４，３１９号明細書（１９８６
年）（対応特開昭号公報 ６０−２３１７３８ ）では
、繊維強化プリプレグの眉間に熱可塑性樹脂フィルムを
配して眉間強度の改善がなされることが開示されている
。■USP No. 4,604,319 (1986
2006) (corresponding Japanese Patent Application Laid-open No. 60-231738) discloses that glabella strength can be improved by disposing a thermoplastic resin film in the glabella of a fiber-reinforced prepreg.
しかし、これらの手法は、その効果が不十分であるばか
りでなく、それぞれに欠点を有している。However, these methods are not only insufficiently effective, but also have their own drawbacks.
エラストマー改質熱硬化性樹脂を含む独立外層フィルム
を用いた場合には、エラストマーの含量が多くなると耐
熱性が低下し、エラストマーの含量が少ないと眉間強度
の改善効果は非常に少ない。When using an independent outer layer film containing an elastomer-modified thermosetting resin, the heat resistance decreases as the elastomer content increases, and the glabella strength improvement effect is very small when the elastomer content is low.
また、熱可塑性樹脂フィルムを用いた場合には耐熱性の
良好な熱可塑性樹脂フィルムを用いることにより耐熱性
と眉間強度の改善効果の両立がなされるが熱硬化性樹脂
の利点であるタック性（粘着性）やドレープ性が失われ
る。また、耐溶剤性が良くないという熱可塑性樹脂の一
般的欠点が複合材料に反映してしまう。In addition, when a thermoplastic resin film is used, it is possible to achieve both heat resistance and glabella strength improvement effects by using a thermoplastic resin film with good heat resistance. (adhesion) and drape properties are lost. Moreover, the general drawback of thermoplastic resins, such as poor solvent resistance, is reflected in the composite material.
また、短繊維チョップ、チョツプドストランドミルドフ
ァイバーを用いることは、眉間を厚くするため、コンポ
ジット全体としての強度低下を招く。Furthermore, the use of chopped short fibers or chopped strand milled fibers increases the thickness of the glabella, resulting in a decrease in the strength of the composite as a whole.
［発明が解決しようとする問題点コ
そこで、本発明者らは上記欠点のない、優れた耐衝撃性
を与えるプリプレグについて鋭意研究を行った結果、構
成要素［Ｃ］に歪エネルギー開放係数（Ｇ １ｃ）の大
きな樹脂からなる微粒子を使用し、かつ微粒子の分布状
態を制御する事により予想をはるかに上回る優れた耐衝
撃性を与えるプリプレグを得る事ができ、本発明に致っ
たのである。[Problems to be Solved by the Invention] Therefore, the present inventors conducted intensive research on prepregs that do not have the above-mentioned drawbacks and provide excellent impact resistance. By using fine particles made of large resin 1c) and controlling the distribution state of the fine particles, it was possible to obtain a prepreg with excellent impact resistance that far exceeded expectations, which led to the present invention.
［問題点を解決するための手段］
本願発明は前記特許請求の範囲の欄に記載のとうりの、
次の構成要素［Ａ］ 、［Ｂ］ 、ＥＣ］を必須とし、
構成要素［Ｃ］の９０％以上の量がプリプレグの表面か
らプリプレグの厚さの３０％の深さの範囲内に局在化す
るプリプレグ
［Ａ］：長繊維からなる強化繊維
［Ｂ］ ：マトリックス樹脂
［Ｃコ ：Ｇｌｃが１５００Ｊ／ｍ２以上の樹脂を素材
とする微粒子
（長繊維からなる強化繊維の説明）
本発明の構成要素［Ａ］は長繊維からなる強化繊維であ
る。本発明に用いる強化繊維は、一般に高性能強化繊維
として用いられる耐熱性および引張強度の良好な繊維で
ある。たとえば、その強化繊維には、炭素繊維、黒鉛繊
維、アラミド繊維、炭化ケイ素繊維、アルミナ繊維、ボ
ロン繊維があげらる。このうち比強度、比弾性率が良好
で軽量化に大きな寄与が認められる炭素繊維や黒鉛繊維
が本発明には最も良好である。炭素繊維や黒鉛繊維は用
途に応じてあらゆる種類の炭素繊維や黒鉛繊維を用いる
ことが可能であるが、引張強度４５０に８ｆ／ｍｍ２、
引張伸度１．６ ＄以上の高強度高伸度炭素繊維が最も
適している。また、本発明には長繊維状の強化繊維を用
いるが、その長さは５ｃｍ以上であることが好ましい。[Means for solving the problem] The present invention has the following features as described in the scope of claims.
The following components [A], [B], EC] are required,
Prepreg in which 90% or more of the component [C] is localized within a depth range of 30% of the thickness of the prepreg from the surface of the prepreg [A]: Reinforced fibers consisting of long fibers [B]: Matrix Resin [Cco: Fine particles made of resin with Glc of 1500 J/m2 or more (Description of reinforcing fibers made of long fibers) Component [A] of the present invention is reinforcing fibers made of long fibers. The reinforcing fibers used in the present invention are generally used as high-performance reinforcing fibers and have good heat resistance and tensile strength. For example, the reinforcing fibers include carbon fiber, graphite fiber, aramid fiber, silicon carbide fiber, alumina fiber, and boron fiber. Among these, carbon fibers and graphite fibers are most suitable for the present invention because they have good specific strength and specific modulus and are recognized to greatly contribute to weight reduction. All kinds of carbon fibers and graphite fibers can be used depending on the purpose, but tensile strength of 450 and 8f/mm2,
High strength and high elongation carbon fibers with a tensile elongation of 1.6 $ or more are most suitable. Further, although long reinforcing fibers are used in the present invention, the length thereof is preferably 5 cm or more.
それより短い場合、強化繊維の強度を複合材料として十
分に発現させることが困難となる。また、炭素繊維や黒
鉛繊維は他の強化繊維を混合して用いてもかまわない。If it is shorter than that, it becomes difficult to fully develop the strength of the reinforcing fibers as a composite material. Further, carbon fibers and graphite fibers may be used in combination with other reinforcing fibers.
また、強化繊維はその形状や配列を限定されず、たとえ
ば、単一方向、ランダム方向、シート状、マット状、織
物状、組み紐状であっても使用可能である。また、特に
、比強度、非弾性率が高いことを要求される用途には強
化繊維が単一方向に引き揃えられた配列が最も適してい
るが、取り扱いの容易なりロス（織物）状の配列も本発
明には適している。Further, the reinforcing fibers are not limited in their shape or arrangement, and may be used in, for example, a unidirectional direction, a random direction, a sheet shape, a mat shape, a woven fabric shape, or a braided cord shape. In addition, in particular, for applications that require high specific strength and inelastic modulus, an arrangement in which the reinforcing fibers are aligned in a single direction is most suitable; are also suitable for the present invention.
（マトリックス樹脂の説明） 本発明の構成要素［Ｂ］はマトリックス樹脂である。(Explanation of matrix resin) Component [B] of the present invention is a matrix resin.
本発明に用いるマトリックス樹脂には熱硬化性樹脂およ
び熱硬化性樹脂と熱可塑性樹脂を混合した樹脂が挙げら
れる。Matrix resins used in the present invention include thermosetting resins and resins in which thermosetting resins and thermoplastic resins are mixed.
本発明に用いる熱硬化性樹脂は、熱または光や電子線な
どの外部からのエネルギーにより硬化して、少なくとも
部分的に三次元硬化物を形成する樹脂であれば特に限定
されない。好ましい熱硬化性樹脂としては、エポキシ樹
脂があげられ、一般に硬化剤や硬化触媒と組合せて用い
られる。本発明に適したエポキシ樹脂としては特に、ア
ミン類、フェノール類、炭素炭素二重結合を有する化合
物を前駆体とするエポキシ樹脂が好ましい。The thermosetting resin used in the present invention is not particularly limited as long as it is a resin that can be cured by heat or external energy such as light or an electron beam to at least partially form a three-dimensional cured product. Preferred thermosetting resins include epoxy resins, which are generally used in combination with curing agents and curing catalysts. Particularly preferred epoxy resins suitable for the present invention are epoxy resins whose precursors are amines, phenols, and compounds having carbon-carbon double bonds.
また、これらのエポキシ樹脂は単独で用いてもよいし、
適宜配合して用いてもよい。Moreover, these epoxy resins may be used alone,
They may be used in an appropriate combination.
エポキシ樹脂はエポキシ硬化剤と組合せて、好ましく用
いられる。エポキシ硬化剤はエポキシ基と反応しうる活
性基を有する化合物であればこれを用いることができる
。好ましくは、アミノ基、酸無水物基、アジド基を有す
る化合物が適している。Epoxy resins are preferably used in combination with epoxy curing agents. Any compound having an active group capable of reacting with an epoxy group can be used as the epoxy curing agent. Preferably, compounds having an amino group, an acid anhydride group, or an azide group are suitable.
本発明においては、マトリックス樹脂としてさらに、マ
レイミド樹脂、アセチレン末端を有する樹脂、ナジック
酸末端を有する樹脂、シアン酸エステル末端を有する樹
脂、ビニル末端を有する樹脂、アリル末端を有する樹脂
が好ましく用いられる。これらは、適宜、エポキシ樹脂
や、他の樹脂と混合しても良い。また、反応性希釈剤を
用いたり、熱可塑性樹脂やエラストマーなどの改質剤を
混合して用いてもかまわない。In the present invention, as the matrix resin, maleimide resins, resins having acetylene ends, resins having nadic acid ends, resins having cyanate ester ends, resins having vinyl ends, and resins having allyl ends are preferably used. These may be mixed with epoxy resin or other resins as appropriate. Further, a reactive diluent may be used, or a modifier such as a thermoplastic resin or an elastomer may be mixed and used.
マレイミド樹脂は、末端にマレイミド基を平均２個以上
含む化合物である。シアン酸エステル末端を有する樹脂
は、ビスフェノールＡに代表される多価フェノールのシ
アン酸エステル化合物が好適である。シアン酸エステル
樹脂は、特にビスマレイミド樹脂と組合わせることによ
りプリプレグに適した樹脂とすることができ、三菱ガス
化学（株）製ＢＴレジンが市販されており本発明に適し
ている。これらは一般にエポキシ樹脂より、耐熱性と耐
水性が良好である半面、靭性や耐衝撃性が劣るため用途
に応じて選択して用いられる。本発明においてエポキシ
樹脂の代わりにこれ−らの他の熱硬化性樹脂を用いても
、本発明の効果は同様である。また、ビニル末端を有す
る樹脂およびアリル末端を有する樹脂は、市販の汎用樹
脂が用いられるが耐熱性が前者の樹脂群より劣るので、
主として希釈剤として用いられる。A maleimide resin is a compound containing an average of two or more maleimide groups at its terminal ends. As the resin having a cyanate ester terminal, a cyanate ester compound of a polyhydric phenol represented by bisphenol A is suitable. Cyanate ester resin can be made into a resin suitable for prepregs, especially when combined with bismaleimide resin, and BT resin manufactured by Mitsubishi Gas Chemical Co., Ltd. is commercially available and suitable for the present invention. These generally have better heat resistance and water resistance than epoxy resins, but are inferior in toughness and impact resistance, so they are selected and used depending on the application. Even if these other thermosetting resins are used in place of the epoxy resin in the present invention, the effects of the present invention are the same. In addition, commercially available general-purpose resins are used as resins with vinyl ends and resins with allyl ends, but their heat resistance is inferior to the former resin group.
Mainly used as a diluent.
本発明に、マトリックス樹脂として、上記の熱硬化性樹
脂に熱可塑性樹脂を混合して用いることも好適である。In the present invention, it is also suitable to use a mixture of the above thermosetting resin and a thermoplastic resin as the matrix resin.
本発明に好適な熱可塑性樹脂は、主鎖に炭素炭素結合、
アミド結合、イミド結合、エステル結合、エーテル結合
、カーボネート結合、ウレタン結合、尿素結合、チオエ
ーテル結合、スルホン結合、イミダゾール結合、カルボ
ニル結合から選ばれる結合を有する熱可塑性樹脂である
。The thermoplastic resin suitable for the present invention has a carbon-carbon bond in the main chain,
It is a thermoplastic resin having bonds selected from amide bonds, imide bonds, ester bonds, ether bonds, carbonate bonds, urethane bonds, urea bonds, thioether bonds, sulfone bonds, imidazole bonds, and carbonyl bonds.
これらの熱可塑性樹脂は、市販のポリマーを用いても良
く、また、市販のポリマーより分子量の低い、いわゆる
オリゴマーを用いても良い。オリゴマーとしては、熱硬
化性樹脂と反応しうる官能基を末端または分子鎖中に有
するオリゴマーがさらに好ましい。As these thermoplastic resins, commercially available polymers may be used, or so-called oligomers having a lower molecular weight than commercially available polymers may be used. As the oligomer, an oligomer having a functional group capable of reacting with the thermosetting resin at the terminal or in the molecular chain is more preferable.
熱硬化性樹脂と熱可塑性樹脂の混合物は、それらを単独
で用いた場合より良好な結果を与える。Mixtures of thermosets and thermoplastics give better results than when they are used alone.
これは、熱硬化性樹脂が一般に脆い欠点を有しながらオ
ートクレーブによる低圧成型が可能であるのに対して、
熱可塑性樹脂が一般に強靭である利点を有しながらオー
トクレーブによる低圧成型が困難であるという二律背゛
反した特性を示すため、これらを混合して用いることで
物性と成形性のバランスをとることができるためである
。This is because while thermosetting resins generally have the disadvantage of being brittle, they can be molded at low pressure in an autoclave.
Thermoplastic resins generally have the advantage of being tough, but they exhibit contradictory characteristics such as being difficult to mold at low pressure in an autoclave, so it is necessary to balance physical properties and moldability by using a mixture of these resins. This is because it can be done.
また、エポキシ樹脂に微粉末状シリカなどの無機質微粒
子やエラストマーなどを少量混合することも可能である
。It is also possible to mix a small amount of inorganic fine particles such as finely powdered silica or an elastomer with the epoxy resin.
（微粒子の説明）
従来、繊維強化複合材料の耐衝撃性を向上させるために
は、マトリックス樹脂の歪エネルギー開放率（Ｇ Ｉｃ
値）を高くすることが必要であると考えられてきた。し
かしながら、これを実現するためにはマトリックス樹脂
の具備すべき弾性率、破断伸度、耐熱性、耐水性、接着
性、粘着性、室温での樹脂の柔軟性、溶融流動性などの
緒特性をかなり損うため、両者を同時に満足することに
は限界があった。ところが、本発明によれば、意外にも
、一定レベル以上の（ｇｃを有する樹脂を微粒子状態で
層間に局在化させるだけで複合材料としての耐衝撃性を
著しく向上させ得ることを見出したのである。微粒子で
あれば、マトリックス樹脂中に分散した状態で存在する
ため、マトリックス樹脂のもつタック性、ドレープ性が
プリプレグ特性として反映され、取り扱い性に優れたプ
リプレグとなる。すなわち、本発明によるプリプレグは
複合材料としたときの耐衝撃性と従来のマトリックス樹
脂に要求される特性とを同時に満足するのである。(Explanation of fine particles) Conventionally, in order to improve the impact resistance of fiber-reinforced composite materials, the strain energy release rate (G Ic
It has been thought that it is necessary to increase the However, in order to achieve this, the matrix resin must have certain characteristics such as elastic modulus, elongation at break, heat resistance, water resistance, adhesiveness, tackiness, resin flexibility at room temperature, and melt flowability. There was a limit to satisfying both at the same time, as it would cause considerable damage. However, according to the present invention, it has surprisingly been found that the impact resistance of a composite material can be significantly improved simply by localizing a resin having a gc above a certain level between layers in the form of fine particles. If the particles are fine particles, they exist in a dispersed state in the matrix resin, so the tackiness and drape properties of the matrix resin are reflected in the prepreg properties, resulting in a prepreg with excellent handling properties.In other words, the prepreg according to the present invention When made into a composite material, it simultaneously satisfies the impact resistance and properties required of conventional matrix resins.
しかも微粒子にはマトリックス樹脂として具備すべき粘
着性やドレープ性が要求されないため、微粒子として選
択できる素材は広範に及ぶ。Furthermore, since the fine particles do not require the adhesiveness and drape properties that a matrix resin should have, there is a wide range of materials that can be selected for the fine particles.
このため従来、性能が優れているにもかかわららずマト
リックス樹脂として使用することが困難であった樹脂で
も微粒子化して用いることによりマトリックス樹脂を構
成する成分として使用し、マトリックス樹脂の性能を改
良することができるのである。For this reason, even resins that have conventionally been difficult to use as matrix resins despite their excellent performance can be made into fine particles and used as constituent components of matrix resins, improving the performance of matrix resins. It is possible.
蓋臣五Ω素且
微粒子は［Ｂｃ値が１５００Ｊ／ｍ２以上の樹脂を素材
とするものであれば、どんなものであってもよい。Ｇｌ
ｃ値が３０００Ｊ／ｍ２以上であればさらに好ましい。The vassal five-ohm fine particles may be of any kind as long as they are made of a resin having a Bc value of 1500 J/m2 or more. Gl
It is more preferable that the c value is 3000 J/m2 or more.
Ｇｌｃ値が１５００Ｊ／ｍ２未満の場合は複合材料とし
たときの耐衝撃性が十分に上がらないため好ましくない
。If the Glc value is less than 1500 J/m2, it is not preferable because the impact resistance when made into a composite material will not be sufficiently increased.
Ｇｓｃ値の評価は微粒子素材を成形した樹脂板を用い、
ＡＳＴＭ Ｅ３９９ （タイプＡ４）に定められたコ
ンパクトテンション法またはダブルトーション法により
行う。The Gsc value was evaluated using a resin plate made of fine particle material.
The compact tension method or double torsion method specified in ASTM E399 (Type A4) is used.
１包玉辺血施
微粒子の分布については、プリプレグの表面層すなわち
、成形して複合材料になった場合のプリプレグシートと
プリプレグシートとの間に偏って存在することが耐衝撃
性の優れた複合材料を与えるために重要である。Regarding the distribution of fine particles, it is important to note that they are unevenly present in the surface layer of the prepreg, that is, between the prepreg sheets when molded into a composite material. It is important to give the material.
通常の微粒子の添加ではマトリックス樹脂に対する微粒
子の含有率の分だけの改質効果のみが期待されるにすぎ
ないが、プリプレグの表面層に偏って存在する場合は前
述の加成性に基づく予想をはるかに越え、特に耐衝撃性
の向上に関しては、全く予期し得ないほどの著しい効果
が見出されたのである。これを満たす条件は、微粒子の
９０％以上が、プリプレグの表面からプリプレグの厚さ
の３０％の深さの範囲内に局在化するということである
。この条件をはずれて、プリプレグ内部深くに微粒子が
入った場合、複合材料の耐衝撃性は条件にあフたものと
比べて劣る。With the addition of normal fine particles, only the modification effect corresponding to the content of fine particles in the matrix resin is expected, but if they are concentrated in the surface layer of the prepreg, the prediction based on the additivity described above cannot be expected. A completely unexpected and remarkable effect has been discovered, especially in terms of improved impact resistance. The condition that satisfies this is that 90% or more of the fine particles are localized within a depth range of 30% of the thickness of the prepreg from the surface of the prepreg. If this condition is exceeded and fine particles enter deep inside the prepreg, the impact resistance of the composite material will be inferior to that of a composite material that has been filled under these conditions.
微粒子の９０％以上が、プリプレグの表面からプリプレ
グの厚さの１０％の深さの範囲内に局在化する場合は、
より顕著な効果が現れるのでさらに好ましいといえる。If 90% or more of the fine particles are localized within a depth range of 10% of the thickness of the prepreg from the surface of the prepreg,
It can be said that it is even more preferable because a more remarkable effect appears.
なお、本発明によるプリプレグは、プリプレグの両面に
おいて微粒子が偏フて分布したものが、プリプレグの表
裏にかかわりなく、自由に積層することが可能であるた
め、最適である。しかし、プリプレグの片面のみに微粒
子が同様の分布をしたプリプレグでも、プリプレグとお
しを積層する時に微粒子が必ずプリプレグ間にくるよう
に注意を払って使用すれば同様の効果が得られるため、
プリプレグの片面のみに微粒子が偏った分布も本発明に
は含まれる。In addition, the prepreg according to the present invention is optimal because fine particles are unevenly distributed on both sides of the prepreg because it can be laminated freely regardless of the front and back sides of the prepreg. However, even if the prepreg has a similar distribution of fine particles on only one side of the prepreg, the same effect can be obtained if care is taken to ensure that the fine particles are between the prepregs when laminating the prepreg and the layer.
The present invention also includes a biased distribution of fine particles on only one side of the prepreg.
Ｗ′
プリプレグ中の微粒子の分布状態の評価は、次のように
して行う。The distribution state of fine particles in the W′ prepreg is evaluated as follows.
まず、プリプレグを二枚の平滑な支持板の間にはさんで
密着させ、長時間かけて徐々に温度を上げて硬化させる
。この時に重要なのは可能なかぎり低温でゲル化させる
ことである。ゲル化しないうちに温度を上げるとプリプ
レグ中の樹脂が流動し、微粒子が移動するため、プリプ
レグ中における正確な分布状態の評価ができない。First, the prepreg is sandwiched between two smooth support plates and brought into close contact with each other, and the temperature is gradually raised over a long period of time to harden the prepreg. What is important at this time is to gel at the lowest possible temperature. If the temperature is raised before gelation occurs, the resin in the prepreg will flow and the fine particles will move, making it impossible to accurately evaluate the distribution state in the prepreg.
ゲル化した後、さらに時間をかけて徐々に温度をかけて
プリプレグを硬化させる。この、硬化したプリプレグを
用いてその断面を２００倍以上に拡大して、２００ｍｍ
Ｘ ２００ｍｍ以上の写真を撮る。After gelation, the prepreg is cured by gradually increasing the temperature over an additional period of time. Using this hardened prepreg, the cross section was enlarged more than 200 times to 200 mm.
Take a photo of 200mm or larger.
この断面写真を用い、まず平均的なプリプレグの厚みを
求める。層の平均厚みは写真上で、任意に選んだ少なく
とも５箇所で測り、その平均をとる。次に、両方の支持
板に接していた面からプリプレグの厚みの３０％の位置
にプリプレグの面方向と平行に線をひく。支持板に接し
ていた面と３０％の平行線の間に存在する微粒子の面積
をプリプレグの両面について定量し、これと、プリプレ
グの全幅に渡って存在する微粒子の面積を定量し、その
比をとることによりプリプレグの表面からプリプレグの
厚さの３０％以内に存在する微粒子の量が算出される。Using this cross-sectional photograph, first determine the average thickness of the prepreg. The average thickness of the layer is measured at at least 5 arbitrarily selected points on the photograph, and the average thickness is taken. Next, a line is drawn parallel to the surface direction of the prepreg at a position 30% of the thickness of the prepreg from the surface that was in contact with both support plates. Quantify the area of fine particles existing between the surface that was in contact with the support plate and the 30% parallel line on both sides of the prepreg, quantify this and the area of fine particles that exist across the entire width of the prepreg, and calculate the ratio. By doing so, the amount of fine particles present within 30% of the thickness of the prepreg from the surface of the prepreg is calculated.
微粒子の面積の定量は断面写真から所定の領域に存在す
る微粒子部分を全て切り取り、その重量を秤ることによ
り行う。微粒子の部分的な分布のばらつきの影響を排除
するため、この評価は得られた写真の幅全域に渡って行
い、かつ、任意に選んだ５箇所以上の写真について同様
の評価を行い、その平均をとる必要がある。The area of the microparticles is determined by cutting out all the microparticles present in a predetermined area from a cross-sectional photograph and weighing them. In order to eliminate the influence of variations in the local distribution of fine particles, this evaluation was performed over the entire width of the obtained photograph, and the same evaluation was performed on five or more randomly selected photographs, and the average It is necessary to take
微粒子とマトリックス樹脂との見分けがつきにくい時は
、一方を選択的に染色して観察する。顕微鏡は光学顕微
鏡でも観察可能であるが、染色剤によっては走査型電子
顕微鏡のほうが観察に適している場合もある。If it is difficult to distinguish between the fine particles and the matrix resin, selectively stain one of them for observation. Although it is possible to observe using an optical microscope, depending on the stain, a scanning electron microscope may be more suitable for observation.
救臣五Ω形上
微粒子は、いかなる形状であってもよい。もちろん球状
であってもよいが、樹脂塊を粉砕した微粉体や、スプレ
ードライ法、再沈殿法で得られる微粒子のごとく形状さ
まざまの状態で一向に差し支えない。その他、繊維を短
く切断したミルドファイバー状でも、また針状、ウィス
カー状でも差し支えない。The five-ohm type fine particles may have any shape. Of course, it may be spherical, but it may be in various shapes, such as fine powder obtained by crushing a resin lump, or fine particles obtained by a spray drying method or a reprecipitation method. In addition, it may be in the form of milled fibers obtained by cutting the fibers into short lengths, or may be in the form of needles or whiskers.
政症五Ω大皇皇
微粒子の大きさは粒径で表現されるが、この場合の粒径
とは遠心沈降速度法などで求められる体積平均粒径を意
味する。The size of the five-ohm Daehuo microparticles is expressed by the particle size, and the particle size in this case means the volume average particle size determined by the centrifugal sedimentation velocity method.
微粒子の大きさは、複合材料となった時、強化繊維の配
列を著しく乱すほど大きくなければよい。The size of the fine particles does not need to be so large as to significantly disturb the arrangement of reinforcing fibers when a composite material is formed.
粒径が１５０μｍをこえる場合は強化繊維の配列を乱し
たり、積層して得られる複合材料の眉間を必要以上に厚
くするため複合材料としたときの物性を低下させる欠点
がある。When the particle size exceeds 150 μm, the arrangement of the reinforcing fibers is disturbed, and the glabella of the composite material obtained by lamination becomes thicker than necessary, which has the disadvantage of deteriorating the physical properties of the composite material.
政校五辺１
微粒子の量としてはマトリックス樹脂１００重量部に対
して１重量部〜１００重量部の範囲が適している。１重
量部未満では微粒子の効果がほとんど現れず、また１０
０重量部をこえるとマトリックス樹脂との混合が困難に
なるうえ、プリプレグのタック性、ドレープ性が大幅に
低下してしまう。A suitable amount of the fine particles is 1 part by weight to 100 parts by weight based on 100 parts by weight of the matrix resin. If the amount is less than 1 part by weight, the effect of the fine particles will hardly appear;
If it exceeds 0 parts by weight, it will be difficult to mix with the matrix resin, and the tackiness and drapeability of the prepreg will be significantly reduced.
特にマトリックス樹脂の剛性を複合材料の圧縮強度の発
現に活かしたまま、破断伸度の高い柔軟な特性を有する
微粒子で複合材料の層間を高靭化するような目的で使用
する場合は、むしろ１重量部〜３０重量部の少ない範囲
のほうが好適である。In particular, if the rigidity of the matrix resin is utilized to develop the compressive strength of the composite material while using fine particles with flexible properties such as high elongation at break to increase the toughness between the layers of the composite material, it is preferable to A smaller range of 30 parts by weight is more suitable.
以下、実施例により本発明をより詳細に説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
［実施例］
以下の構成よりなる一方向ブリブレグを製造した。プリ
プレグの製造は、まずあらかじめ下記のＡとＢからなる
樹脂の重量分率２１％のプリプレグを作成し、この両面
にＣとＢのブレンド樹脂を離型紙上に薄く塗布した樹脂
フィルムを貼りつけることにより行なった。なお下記の
Ｃの重量部は上記の二段階の工程を経て最終的に得られ
たプリプレグ樹脂中に含まれる微粒子の量である。[Example] A unidirectional brev leg having the following configuration was manufactured. To manufacture prepreg, first, prepare a prepreg with a weight fraction of 21% of the following resins A and B, and then paste a resin film on both sides of this prepreg with a thin layer of release paper coated with a blended resin of C and B. This was done by Note that the part by weight C below is the amount of fine particles contained in the prepreg resin finally obtained through the above two-step process.
Ａ０強化繊維−炭素繊維Ｔ８００ （東しく株）製）Ｂ
、マトリックス樹脂−以下の組成を有する樹脂組成物
１）フェノールノボラック型エポキシ樹脂（油化シェル
エポキシ（株）製、エビコー一−−−−−−−−−６０
重量部
２）ビスフェノールＡ型エポキシ樹脂
（油化シェルエポキシ（株）製、エピコー）８２８）−
−−一−−−４０重量部
３）４．４’ジアミノジフエニルスルホン（住友化学工
業（株）製、スミキュアＳ）−一−−−−−−３３．９
重量部
４）ポリエーテルスルホン５２００Ｇ
（三井東圧■製）
−−−−−−−−−−１０重量部
Ｃ０微粒子−ボリアミドイミド（アモコ社製トーロン４
０００Ｔ）を凍結粉砕して得た平均粒径１５μの微粒子
−ｍ−１５重量部
得られたプリプレグ中の樹脂の重量分率は３０％であっ
た。単位面積あたりの樹脂量は６９ｇ／ｍ２、単位面積
あたりの炭素＊維量は１４９ｇ／ｍ２であ
った。A0 reinforcing fiber - carbon fiber T800 (manufactured by Toshiku Co., Ltd.) B
, Matrix resin - Resin composition having the following composition 1) Phenol novolac type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Ebiko 1 - 60
Weight part 2) Bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicor) 828) -
--1---40 parts by weight 3) 4.4' Diaminodiphenyl sulfone (Sumicure S, manufactured by Sumitomo Chemical Co., Ltd.) -1---33.9
Part by weight 4) Polyether sulfone 5200G (manufactured by Mitsui Toatsu ■) ---10 parts by weight C0 fine particles - Boryamideimide (Torlon 4 manufactured by Amoco)
The weight fraction of the resin in the prepreg obtained was 30% by weight of fine particles (m-15 parts by weight) with an average particle diameter of 15 μm obtained by freeze-pulverizing 000T). The amount of resin per unit area was 69 g/m2, and the amount of carbon*fiber per unit area was 149 g/m2.
ポリアミドイミドをプレス成形し樹脂板としたのち、Ａ
ＳＴＭ Ｅ３９９に基づき、コンパクトテンション法
によるＧｔｃ値を測定したところ。２３５０Ｊ／ｍ２で
あった。After press-molding polyamide-imide to make a resin plate, A
The Gtc value was measured using the compact tension method based on STM E399. It was 2350J/m2.
このプリプレグを２枚の平滑なテフロン板の間にはさみ
、７日間かけて徐々に１５０℃まで上げて硬化させ、そ
の断面を観察した。プリプレグ表面からプリプレグの厚
みの３０％までの範囲に存在する微粒子の量を評価した
ところその値は９６％であり、微粒子は十分に眉間領域
に局在化していた。断面観察は、微粒子を四酸化オスミ
ウムで選択的に染色し、走査型電子顕微鏡で行った。This prepreg was sandwiched between two smooth Teflon plates, and the temperature was gradually raised to 150° C. for 7 days to cure it, and its cross section was observed. When the amount of fine particles present in the range from the surface of the prepreg to 30% of the thickness of the prepreg was evaluated, the value was 96%, and the fine particles were sufficiently localized in the area between the eyebrows. Cross-sectional observation was performed by selectively staining the microparticles with osmium tetroxide and using a scanning electron microscope.
つぎに、このプリプレグを３２枚疑似等方的に積層し、
通常のオートクレーブによる成形を１８０℃で２時間、
６ ｋｇｆ／ｃｍ２の圧力下で行った。成形後、断面を
光学顕微鏡で観察すると、微粒子は積層板の層間部分に
集中的に存在していることが確認できた。Next, 32 sheets of this prepreg were laminated in a quasi-isotropic manner,
Molding in a normal autoclave at 180℃ for 2 hours,
The test was carried out under a pressure of 6 kgf/cm2. After molding, the cross section was observed under an optical microscope, and it was confirmed that the fine particles were concentrated in the interlayer portions of the laminate.
疑似等方硬化板を縦１５０ｍｍ、横１００ｍｍに切削・
して、中心に１５００インチ・ボンド／インチの落錘衝
撃を与えたのち、超音波探傷機により損傷面積を測定し
たところ２．２平方インチであった。ついで、ＡＳＴＭ
Ｄ−６９５に従い衝撃後の圧縮強度を測定すると３
０ 、２ ｋｇ／ｍｍ２であった。Cutting a quasi-isotropically hardened plate to 150 mm in length and 100 mm in width.
After applying a falling weight impact of 1500 inch bond/inch to the center, the damaged area was measured with an ultrasonic flaw detector and was found to be 2.2 square inches. Next, ASTM
When the compressive strength after impact is measured according to D-695, it is 3
It was 0.2 kg/mm2.
［比較例コ
微粒子として、ポリアミドイミドの粉砕品の代りに、フ
ェノール樹脂微粒子であるベルパールＲ−ＳＯＯ＜平均
粒径２０μ、鐘紡■製）を用いた他は実施例と同様の手
順を繰り返した。[Comparative Example] The same procedure as in Example was repeated, except that phenol resin fine particles, Bell Pearl R-SOO (average particle size 20 μm, manufactured by Kanebo), were used as fine particles in place of the pulverized polyamide-imide product.
ベルバールＲ−８００をプレス成形し樹脂板としたのち
、ＡＳＴＭ Ｅ３９９に基づき、コンパクトテンショ
ン法によるＧＩＣ値を測定したところ９２０Ｊ／ｍ２と
いう低い値であった。After Belvar R-800 was press-molded into a resin plate, the GIC value was measured by the compact tension method based on ASTM E399, and the GIC value was as low as 920 J/m2.
プリプレグ表面からプリプレグの厚みの３０％までの範
囲に存在する微粒子の量を評価したところその値は９５
％であり、微粒子は十分に眉間領域に局在化していた。When the amount of fine particles present in the range from the prepreg surface to 30% of the prepreg thickness was evaluated, the value was 95.
%, and the microparticles were well localized in the glabellar area.
成形品に１５００インチ・ボンド／インチの落鍾衝撃を
与えたのち、超音波探傷機により損傷面積を測定したと
ころ４．１平方インチであった。ついで、ＡＳＴＭ
Ｄ−６９５に従い衝撃後の圧縮強度を測定したところ２
３゜３ ｋｇ／ｍｍ２であり実施例と比較して大幅に劣
っていた。After the molded product was subjected to a 1500 inch bond/inch falling impact, the damaged area was measured using an ultrasonic flaw detector and was found to be 4.1 square inches. Next, ASTM
Compressive strength after impact was measured according to D-695 2
It was 3°3 kg/mm2, which was significantly inferior to that of the example.
［発明の効果］
本発明によるプリプレグは、プリプレグとしてのタック
性、ドレープ性を確保しつつ、コンポジットとしたとき
に高い耐衝撃性および非繊維軸引張強度を得ることがで
きる。[Effects of the Invention] The prepreg according to the present invention can obtain high impact resistance and non-fiber axis tensile strength when made into a composite while ensuring the tackiness and drapability as a prepreg.
Claims (1)
、構成要素［Ｃ］の９０％以上の量がプリプレグの表面
からプリプレグの厚さの３０％の深さの範囲内に局在化
するプリプレグ ［Ａ］：長繊維からなる強化繊維 ［Ｂ］：マトリックス樹脂 ［Ｃ］：Ｇ＿１＿Ｃが１５００Ｊ／ｍ＾２以上の樹脂を
素材とする微粒子(1) The following components [A], [B], and [C] are essential, and 90% or more of component [C] is within the range from the surface of the prepreg to a depth of 30% of the thickness of the prepreg. Prepreg localized within [A]: Reinforcing fiber made of long fibers [B]: Matrix resin [C]: Fine particles made of resin with G_1_C of 1500 J/m^2 or more
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26203087A JPH01104626A (en) | 1987-10-16 | 1987-10-16 | Prepreg having high-toughness fine particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26203087A JPH01104626A (en) | 1987-10-16 | 1987-10-16 | Prepreg having high-toughness fine particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01104626A true JPH01104626A (en) | 1989-04-21 |
| JPH045689B2 JPH045689B2 (en) | 1992-02-03 |
Family
ID=17370052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26203087A Granted JPH01104626A (en) | 1987-10-16 | 1987-10-16 | Prepreg having high-toughness fine particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01104626A (en) |
-
1987
- 1987-10-16 JP JP26203087A patent/JPH01104626A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH045689B2 (en) | 1992-02-03 |
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