JPH01215850A - Resin composition for fiber-reinforced plastic - Google Patents
Resin composition for fiber-reinforced plasticInfo
- Publication number
- JPH01215850A JPH01215850A JP4051788A JP4051788A JPH01215850A JP H01215850 A JPH01215850 A JP H01215850A JP 4051788 A JP4051788 A JP 4051788A JP 4051788 A JP4051788 A JP 4051788A JP H01215850 A JPH01215850 A JP H01215850A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- weight
- parts
- manufactured
- bisphenol
- 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 27
- 229920002430 Fibre-reinforced plastic Polymers 0.000 title claims description 9
- 239000011151 fibre-reinforced plastic Substances 0.000 title claims description 9
- 239000004593 Epoxy Substances 0.000 claims abstract description 21
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 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 claims description 26
- 239000003822 epoxy resin Substances 0.000 claims description 24
- 229920000647 polyepoxide Polymers 0.000 claims description 24
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 150000002460 imidazoles Chemical class 0.000 abstract description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 abstract 3
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 abstract 2
- 238000001723 curing Methods 0.000 description 11
- 239000012779 reinforcing material Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000011162 core material Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- -1 glycidyl ester Chemical class 0.000 description 3
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-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
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920003319 Araldite® Polymers 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229920013646 Hycar Polymers 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 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
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004188 dichlorophenyl group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 238000009730 filament winding Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は繊維強化プラスチック用樹脂組成物に関するも
のであり、より詳しくは作業性の優れた繊維強化プラス
チック用樹脂組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a resin composition for fiber-reinforced plastics, and more particularly to a resin composition for fiber-reinforced plastics with excellent workability.
（従来の技術）
炭素繊維やガラス繊維などの補強材にエポキシ樹脂や不
飽和ポリエステル樹脂を含浸させ、これを硬化させ様々
な形状、厚みの成形物を作る方法は周知のことであり、
この方法を用いてスポーツ用品の円筒状成形体やシャフ
トあるいは航空機の一次、二次構造体や各種の部分材料
に使われつつある。このとき、マトリックスとなる樹脂
を含浸した補強材はプリプレグと呼ばれ、その形状はロ
ープ状のもの、シート状に一方向に引きそろえたものな
どがある。望みの形状の成形体を得るには、ロープ状の
プリプレグを巻きつげるフィラメントワインディング法
やシート状のプリプレグを積層するレイアンプ法などが
知られている。(Prior art) It is well known that reinforcing materials such as carbon fibers and glass fibers are impregnated with epoxy resin or unsaturated polyester resin, and then cured to produce molded products of various shapes and thicknesses.
This method is being used for cylindrical molded bodies and shafts of sports equipment, primary and secondary structures of aircraft, and various partial materials. At this time, the reinforcing material impregnated with a resin serving as a matrix is called prepreg, and its shape may be a rope-like one or a sheet-like one stretched in one direction. In order to obtain a molded article with a desired shape, there are known methods such as filament winding, in which rope-like prepreg is wound, and lay-amp method, in which sheet-like prepreg is laminated.
シート状プリプレグを積層するためには、レイアップ時
に層間に空気が入りないように相互に密着する適当な粘
着性（タック性）と、レイアップしたプリプレグ層が曲
面や円筒などに正確に沿い形状を反映する柔軟性（ドレ
ープ性）を有することが重要である。こうした事情から
特公昭ｓｇ−月−３１特公昭ｊｔｇ−／７３３左、特公
昭５ｇ−グＯｑ７３．時開昭乙／−１Ｉ３乙／Ｓ号公報
等には、適当なタック性とドレープ性を兼ね備えたエポ
キシ樹脂組成物が提案されている。In order to laminate sheet-like prepreg, it is necessary to have appropriate adhesion (tackiness) that allows the layers to adhere to each other to prevent air from entering during layup, and the shape of the laid-up prepreg layers to accurately follow curved surfaces, cylinders, etc. It is important to have flexibility (drapeability) that reflects this. Due to these circumstances, special public show sg-month-31 special public show jtg-/733 left, special public show 5g-g Oq73. Epoxy resin compositions having appropriate tackiness and drapability are proposed in Jikai Sho-Otsu/-1I3 Otsu/S and other publications.
しかしながら、従来の樹脂組成物においては、使用する
補強材の形状や機械的、物理的等の緒特性によりタンク
性とドレープ性等の作業性が大きく低下し、その結果作
業が煩雑であったり、あるいは特性的に満足すべき成形
物が得られないという難点を有していた。However, in conventional resin compositions, workability such as tankability and drapeability is greatly reduced due to the shape and mechanical and physical properties of the reinforcing material used, resulting in complicated work. Alternatively, it has been difficult to obtain a molded product with satisfactory characteristics.
すなわち、こうした成形の前の作業は、プリプレグを形
成する樹脂組成物のタンク性と補強材を含めたプリプレ
グのドレープ性に強（依存する。プリプレグのドレープ
性は、樹脂組成物の影響のみならず使用した補強材の特
性によっても変化する。こうした補強材の特性による影
響を小さ（するには、プリプレグのドレープ性が豊かに
なるような樹脂組成物がよいと考えられる。In other words, these operations prior to molding strongly depend on the tank properties of the resin composition forming the prepreg and the drape properties of the prepreg including reinforcing materials. The drape properties of the prepreg are not only influenced by the resin composition. It also changes depending on the characteristics of the reinforcing material used.In order to minimize the influence of the characteristics of the reinforcing material, it is thought that it is best to use a resin composition that gives the prepreg rich drape properties.
そこで、本発明者等は先に、特定物性の樹脂を組み合わ
せることによりドレープ性の良好なプリプレグが得られ
ることを見い出した（特願昭乙コー／グ３７９３ ）。Therefore, the present inventors have previously discovered that a prepreg with good drape properties can be obtained by combining resins with specific physical properties (Japanese Patent Application No. 3793).
（発明が解決しようとする問題点）
しかしながら、かかる樹脂組成物では、良好なドレープ
性を示すプリプレグが得られるものの、積層作業時に、
一方向プリプレグがｑｏ°方向に裂は易（、作業性に支
障をきたすことがあった。(Problems to be Solved by the Invention) However, although such resin compositions yield prepregs that exhibit good drape properties, during lamination work,
The unidirectional prepreg easily cracks in the qo direction (which may impede workability).
（問題点を解決するための手段）
そこで、本発明者等は更に鋭意検討した結果、先に提案
した樹脂組成物に更にニトリルゴムを特定量配合するこ
とにより良好なドレープ性を十分に維持したままでプリ
プレグにシート状の形状維持強度を付与することで作業
性を向上できることを見い出し本発明に到達した。(Means for Solving the Problems) Therefore, as a result of further intensive study, the present inventors were able to sufficiently maintain good drape properties by further blending a specific amount of nitrile rubber into the previously proposed resin composition. The present invention was achieved by discovering that workability can be improved by imparting sheet-like shape maintaining strength to prepreg as is.
すなわち、本発明の目的は良好なドレープ性を保持した
まま作業性の優れた繊維強化プラスチック用樹脂組成物
を提供することにある。That is, an object of the present invention is to provide a resin composition for fiber-reinforced plastics that has excellent workability while maintaining good drape properties.
そして、その目的は、下記のＡ、’Ｂ、Ｃ及びＤ成分を
必須成分とし、夫々、Ａ成分７００重量部に対し、Ｂ成
分、１ｏ−ｓｏ重量部、Ｃ成分１〜８重量部並びにＤ成
分を含有してなる繊維強化プラスチック用樹脂組成物
Ａ：エポキシ当量が２３θ以下で、かつ常温で液状のビ
スフェノールＡ型エポキシ樹脂Ｂ：エポキシ当量が／
３００〜５ｏｏｏの範囲で、かつ融点が１２０〜２００
℃のビスフェノールＡ型エポキシ樹脂
Ｃ：ニトリルゴム
Ｄ：硬化剤
により達成される。The purpose is to use the following components A, 'B, C and D as essential components, and for each 700 parts by weight of component A, component B, 1o-so parts by weight, 1 to 8 parts by weight of component C, and D Resin composition A for fiber-reinforced plastics containing the following components: Bisphenol A type epoxy resin B having an epoxy equivalent of 23θ or less and being liquid at room temperature: an epoxy equivalent of /
in the range of 300 to 5ooo, and the melting point is 120 to 200
C: bisphenol A type epoxy resin C: nitrile rubber D: curing agent.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明で用いるエポキシ当量２３Ｏ以下、常温で液状の
ビスフェノールＡ型エポキシ樹脂（Ａ成分）としてはエ
ポキシ当量がｓｓｏ以下、好ましくは／ｇＯ−２００の
常温で液状のものであれば特に限定されるものではな（
、具体的には
１′エピコート”ｇ／！；、ｇ２７２ｇλｇ（油化シェ
ル社製）、
゛°アラルダイト°′”ＧＹ２ｓｏ、ＧＹλ乙０（チバ
・ガイギー社製）、
” Ａ Ｅ Ｒ”３３グ、３３０，３．３／（無化成社
製）、
゛スミエポキン”ＥＬＡ−／／左、ＥＬＡ−／２？。The bisphenol A type epoxy resin (component A) that is liquid at room temperature and has an epoxy equivalent of 23O or less used in the present invention is particularly limited as long as it is liquid at room temperature and has an epoxy equivalent of sso or less, preferably /gO-200. Well then (
, Specifically, 1'Epicote"g/!;, g272gλg (manufactured by Yuka Shell Co., Ltd.), ゛°Araldite°'"GY2so, GYλotsu0 (manufactured by Ciba Geigy Co., Ltd.), "A E R" 33g, 330, 3.3/ (manufactured by Mukasei Co., Ltd.), "Sumiepokin" ELA-//Left, ELA-/2?.
ＥＬＡ−／２ｇ （住友化学社製）、 ”エピクロン”ｇｓｓ、ｇグｏ、ｇｓ。ELA-/2g (manufactured by Sumitomo Chemical), "Epicron" gss, ggo, gs.
（犬日本インキ化学社製）、
゛エポトート”ＹＤ−／ １５．ＹＤ−／２７゜ＹＤ
−／ ２ ｇ
（東部化成社製）、
１′エポミノク”Ｐ、／３０．Ｒ／、７９．Ｒ／グ０（
三井石化社製）、
等が挙げられる。(manufactured by Inu Nippon Ink Chemical Co., Ltd.), ゛Epotote'' YD-/15.YD-/27゜YD
-/2 g (manufactured by Tobu Kasei Co., Ltd.), 1'Epominoku"P, /30.R/, 79.R/g0 (
manufactured by Mitsui Sekika Co., Ltd.), etc.
ｔ タ、エポキシ当量が／ｊ００がらＪθ００の間で、
がり融点が／、２ｏがら２００℃の間にあるビスフェノ
ールＡ型エポキシ樹脂（Ｂ成分）としては、エポキシ当
量が１ｓｏｏがら左。００、好ましくは２０００〜３！
；００であり、かり融点が／＋２０〜ａｏｏ℃、好まし
くは７２０〜７６０℃のものであればよく、具体的には
゛エピコート”１００７，１００９，１０１０（油化シ
ェル社製〕、
Ａ０９７，６０９９
（チバ・ガイギー社製）、
”ＡＥＲ” ＡＡ７．ＡＡ９ （旭化成社製）、゛
スミエポ＃シ” ＥＳＡ−ｏ ／ ？、 ＥＳＡ−０／
ｑ（住友化学社製）、
゛エピクロン”りｏｓ。t, the epoxy equivalent is between /j00 and Jθ00,
As a bisphenol A type epoxy resin (component B) whose melting point is between 2°C and 200°C, the epoxy equivalent is 1°C. 00, preferably 2000-3!
;00 and have a melting point of /+20~aoo°C, preferably 720~760°C, specifically, "Epicote" 1007, 1009, 1010 (manufactured by Yuka Shell Co., Ltd.), A097, 6099 ( (manufactured by Ciba Geigy), "AER" AA7.AA9 (manufactured by Asahi Kasei), "Sumi Epo#shi" ESA-o/?, ESA-0/
q (manufactured by Sumitomo Chemical Co., Ltd.), "Epicron" os.
（犬日本インキ化学社製）、
エ ボ ト − ト ” ＹＤ−０／ ？、
ＹＤ−０／ ９（東部化成社製）、
“エポミノク” Ｒ，？０７．Ｒ３ｏ？（三井石化社製
）、
等が挙げられる。(manufactured by Inu Nippon Ink Kagaku Co., Ltd.), "Evoto" YD-0/?,
YD-0/9 (manufactured by Tobu Kasei Co., Ltd.), “Epominoku” R,? 07. R3o? (manufactured by Mitsui Sekika Co., Ltd.), etc.
そして、Ｃ成分であるニトリルゴムとしては特に限定さ
れるものではないが、通常平均分子量が７０，０θＯ以
上のものが用いられ、具体的にはブタジェンとアクリロ
ニトリルの共重合体であり、またこれらにアクリル酸を
加えた共電体でもよ（、通常平均分子量５Ｏ２０θＯ程
度のものが用いられる。アクリロニトリル含量は通常／
夕〜り０ｗｔ％である。The nitrile rubber that is the C component is not particularly limited, but one with an average molecular weight of 70.0θO or more is usually used, specifically a copolymer of butadiene and acrylonitrile; A co-electric material containing acrylic acid may also be used (usually one with an average molecular weight of about 5O20θO is used.The acrylonitrile content is usually /
It is 0wt% from evening to evening.
同、Ｃ成分のニトリルゴムは、ニトリルゴム単味として
本発明のエポキシ樹脂組成物に配合してもよいが好まし
くは予じめＡ成分のエポキシ樹脂と混合、反応させて得
られるエポキシ樹脂変性ニトリルゴムの形態として配合
するのがよい。Although the nitrile rubber of component C may be blended into the epoxy resin composition of the present invention as a single nitrile rubber, it is preferably an epoxy resin-modified nitrile obtained by mixing and reacting with the epoxy resin of component A in advance. It is best to blend it in the form of a rubber.
本発明においては、これらの各成分な必須成分とするも
のであり、その配合比率としてはＡ成分７００重量部に
対し、Ｂ成分２０−３０重量部、Ｃ成分１〜８重量部、
好ましくはＢ成分ｘ ｓ −ｇ ｓ重量部、Ｃ成分３〜
７重量部とする＝ ７−
のがよい。In the present invention, each of these components is considered to be an essential component, and their blending ratio is 700 parts by weight of component A, 20-30 parts by weight of component B, 1-8 parts by weight of component C,
Preferably B component x s - g s parts by weight, C component 3~
It is preferable that 7 parts by weight = 7-.
そして、これら樹脂混合物はｔｉｏ℃における粘度（７
２７０℃）が２０００〜グｏ、ｏｏｏ、好ましくはグ０
００〜３０，０００の範囲にあり、２００θを下回ると
得られたプリプレグシートは樹脂自体が軟い分だけ作業
性が良くなる傾向にあるものの、若干表面がベタつくの
で好ましくな（、また粘度（ｌグ０℃）かりｏ、ｏｏｏ
ポイズをこえると得られたプリプレグシートが硬くなり
すぎ、所望の成形形状を反映させることが難しく、成形
作業に耐えない。The viscosity of these resin mixtures at tio°C (7
270℃) is 2000~guo, ooo, preferably g0
00 to 30,000, and prepreg sheets obtained below 200θ tend to have better workability as the resin itself is softer, but the surface is slightly sticky, which is undesirable (and the viscosity (l) (0°C) Kari o, ooo
If the poise is exceeded, the resulting prepreg sheet becomes too hard, making it difficult to reflect the desired molded shape and unable to withstand molding operations.
ここで、本発明においては、Ａ成分及びＢ成分は主とし
て樹脂混合物の粘度を調整するものであり、Ｃ成分は主
として良好な作業性を付与するものであって、Ｃ成分を
配合しないとプリプレグシートの製造時あるいは成形作
業時に適正な粘度で良好な可撓性が付与されないので非
常に不都合となる。Here, in the present invention, the A component and the B component are mainly used to adjust the viscosity of the resin mixture, and the C component is mainly used to impart good workability. This is very inconvenient because it does not provide good flexibility with an appropriate viscosity during manufacturing or molding operations.
同、該樹脂混合物の物性範囲を越えない限り、必要に応
じて他の成分例えば脂環式エポキシ樹脂、Ｏ−クレゾー
ルノボラック型エポキシ樹脂、ポリグリシジルアミン、
会スフエノールＦ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、／、 ／、 、２．．２−テトラ
ビス（ｑ−−グリシドキシフェニル）エタン、グリシジ
ルエステル型エポキシ樹脂、ｌ官能性のエポキシ化合物
等を更に混合してもよい。Similarly, other components such as alicyclic epoxy resin, O-cresol novolac type epoxy resin, polyglycidyl amine,
Bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, /, /, ,2. ．． 2-tetrabis(q-glycidoxyphenyl)ethane, glycidyl ester type epoxy resin, l-functional epoxy compound, etc. may be further mixed.
またＤ成分である硬化剤は、−船釣には何でもよくジシ
アンジアミド、酸無水物、芳香族ジアミン、ジメルカプ
タン、フェノール樹脂などがあるが、更にプリプレグに
保存安定性と低温硬化性を付与するためには、ジシアン
ジアミドと硬化促進剤の組み合わせがすぐれている。ま
た、ジシアンジアミド単独でも硬化温度などの成形条件
が変わるだけで、成形の前の作業性には何ら変わるとこ
ろはない。硬化促進剤としてはイミダゾール誘導体、例
えばλ−エチルークーメチルイミダゾール、コー（２−
シアノエチル）−イミダゾールなどあるいは、尿素誘導
体例えばＮ−（３，１７−ジクロロフェニル）−Ｎ’、
Ｎ’−ジメチルウレア、Ｎ−（ｌＩ−クロロフェニル
）−Ｎ／、 Ｎ／−ジメチルウレア、Ｎ−（３−クロロ
フェニル） Ｎ／ 、 Ｎ／−ジメチルウレアなどが
挙げられる。こうしたジシアンジアミドと硬化促進剤と
いった硬化剤の組み合わせにおいては、ジシアンジアミ
ドは上記の樹脂混合換金てな１００重量部としたとき０
．に〜１０重量部、また硬化促進剤は０． 、Ｓ−〜１
０重量部を添加するのが好ましい。In addition, the curing agent, which is component D, can be used for boat fishing, such as dicyandiamide, acid anhydride, aromatic diamine, dimercaptan, phenolic resin, etc., but it also provides storage stability and low-temperature curing properties to the prepreg. has an excellent combination of dicyandiamide and curing accelerator. Further, even if dicyandiamide is used alone, the only difference is the molding conditions such as the curing temperature, but there is no change in workability before molding. As curing accelerators, imidazole derivatives such as λ-ethyl-coumethylimidazole, co(2-
or urea derivatives such as N-(3,17-dichlorophenyl)-N',
Examples include N'-dimethylurea, N-(lI-chlorophenyl)-N/, N/-dimethylurea, N-(3-chlorophenyl)N/, N/-dimethylurea, and the like. In such a combination of dicyandiamide and a curing agent such as a curing accelerator, dicyandiamide is 0 when 100 parts by weight of the above resin mixture is used.
．． ~10 parts by weight, and 0.0 parts by weight of curing accelerator. , S-~1
Preferably, 0 parts by weight are added.
同、本発明で使用する粘度はレオメ） ＩＪックス社製
゛′ダイナミック・メカニカル・スペクトルメーター″
により測定されたものである。The viscosity used in the present invention is Rheome) "Dynamic Mechanical Spectrum Meter" manufactured by IJx Co., Ltd.
It was measured by
本発明の樹脂組成物は繊維強化プラスチックに用いられ
るが、補強繊維としてはガラス繊維、炭素繊維、アラミ
ド繊維、アルミナ繊維、ボロン繊維等が用いられ、特に
炭素繊維を用いるのがよい。また、かかる繊維強化プラ
スチックは溶液法、熱溶融法等の常法により製造される
。The resin composition of the present invention is used for fiber-reinforced plastics, and the reinforcing fibers used include glass fibers, carbon fibers, aramid fibers, alumina fibers, boron fibers, and carbon fibers are particularly preferred. Further, such fiber-reinforced plastics are manufactured by conventional methods such as a solution method and a hot melt method.
（実施例） 次に実施例により本発明を更に詳細に説明する。(Example) Next, the present invention will be explained in more detail with reference to Examples.
実施例／
ニトリルゴム（ＢＦＧ製” Ｈｙｃａｒ ／ ＩＩ７
ｓ ”、アクリロニトリル含量２７％）３重量部とエポ
キシ当量７ｇ’ｌ〜／９グで常温で液状ビスフェノール
Ａ型エポキシ樹脂（油化シェルエポキシ社製、エピコー
トｇ２ｇ）９に重量部を予め混合し、反応させて得られ
るニトリルゴム変性エポキシ樹脂７２重量部とエポキシ
当量λｌ／、００〜３３００で常温で固形のビスフェノ
ールＡ型エポキシ樹脂（油化シェルエポキシ社製、゛エ
ピコート１００９’”）２３重量部、これに硬化剤とし
てジシアンジアミド（油化シェルエポキシ社製、” Ｄ
ＩＣＹ ？ ” ） ２．７重量部、硬化促進剤トして
Ｎ−（３，ＩＩ−ジクロロフェニル）−Ｎ、 Ｎ’−ジ
メチルウレア（採土ケ谷化学社製、” ＤＣＭＵ ？
？ ”） ３． ｇ重量部を加えてなる樹脂組成物を作
製した。この樹脂組成物のｑｏ℃での粘度はλθ、００
０ポイズであった。Example / Nitrile rubber (manufactured by BFG “Hycar / II7
s'', acrylonitrile content 27%) and an epoxy equivalent of 7 g'l~/9 g in a liquid bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat g 2 g) 9 in advance. 72 parts by weight of a nitrile rubber-modified epoxy resin obtained by the reaction and 23 parts by weight of a bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., "Epicoat 1009'") which is solid at room temperature with an epoxy equivalent λl/, 00 to 3300, Dicyandiamide (manufactured by Yuka Shell Epoxy Co., Ltd., "D"
ICY? ) 2.7 parts by weight as a curing accelerator and N-(3,II-dichlorophenyl)-N,N'-dimethylurea (manufactured by Odugaya Chemical Co., Ltd., "DCMU?")
? ”) 3. A resin composition was prepared by adding 3.g parts by weight.The viscosity of this resin composition at qo℃ was λθ, 00
It was 0 poise.
この樹脂組成物を炭素繊維に含浸して得られ一’１１−
る一方向性プリプレグを用いてテーパー形状のマンドレ
ルに巻きつけ積層したところ、芯材の曲面の形状をよく
反映した積層が可能であり、その作業性も極めて良かっ
た。When a unidirectional prepreg obtained by impregnating carbon fiber with this resin composition was wound around a tapered mandrel and laminated, it was possible to form a lamination that closely reflected the shape of the curved surface of the core material. Yes, and its workability was extremely good.
実施例コ ・
実施例／で用いた二） ＩＪルゴム変性エポキシ樹脂ｇ
ｏ重量部とエポキシ当量が２グ００〜３３００の常温固
形のビスフェノールＡ型エポキシ樹脂（゛エピコート／
００９ ”、油化シェル社製）２０重量部に硬化剤の
ジシアンシア者ド（”ＤＩＣＹ７”、油化シェルエポキ
シ社製）３．０重量部と硬化促進剤のＮ−（３，ｌＩ−
ジクロロフェニル）−Ｎ、Ｎ’−ジメチルウレア（”Ｄ
ＣＭＵ９９″、採土ケ谷化学社製）３８ｇ重量部を加え
て樹脂組成物を作製した。この樹脂組成物のｌＩｏ℃で
の粘度はｔ、ｏｏｏポイズであった。Example 2) IJ rubber modified epoxy resin used in Example 2)
Bisphenol A type epoxy resin solid at room temperature with o parts by weight and epoxy equivalent of 2g00 to 3300 (Epicoat/
009'', manufactured by Yuka Shell Epoxy Co., Ltd.), 3.0 parts by weight of a hardening agent, Dicyanthide ("DICY7", manufactured by Yuka Shell Epoxy Co., Ltd.), and a curing accelerator, N-(3,lI-).
dichlorophenyl)-N,N'-dimethylurea ("D
A resin composition was prepared by adding 38 g parts by weight of CMU99'' (manufactured by Odugaya Kagaku Co., Ltd.).The viscosity of this resin composition at lIo°C was t, ooo poise.
この樹脂組成物を用いて、実施例／と同様に一方向性プ
リプレグを作り、これを用いて巻回、積層を行ったとこ
ろ、芯材の曲面の形状をよ（反映した積層成形物が得ら
れ、またその作業性も極めて良好であった。Using this resin composition, a unidirectional prepreg was made in the same manner as in Example 1, and when it was wound and laminated, a laminate molded product that reflected the shape of the curved surface of the core material was obtained. The workability was also very good.
比較例／
エポキシ当量／ｇ’ｌ〜／ｑ４’の常温で液状のビスフ
ェノールＡ型エポキシ樹脂（油化シェルエポキシ社製、
゛エピコートｇ２ｇ”）７０重量部とエポキシ当量λ１
Ｉｏｏ〜３３００の常温で固形のビスフェノールＡ型エ
ポキシ樹脂（油化シェルエポキシＫｌ、”エピコート１
０Ｏｑ”）３０重量部、これに硬化剤としてジシアンジ
アミド（油化シェルエポキシ社製、” ＤＩＣＹ？”
）２．７重量部、硬化促進剤としてＮ−（３，ＩＩ−ジ
クロロフェニル）−Ｎ、Ｎ’−ジメチルウレア（採土ケ
谷化学社製、”ＤＣＭＵ ９ ｑ”）３．ｇ重量部を加
えた樹脂組成物を作製した。この樹脂組成物のｌＩＯ℃
での粘度は２０，０００ポイズであった。この樹脂組成
物を用いて得られる一方向性プリプレグで、実施例と同
様に巻きつげおよび積層をしようとしたところ、プリプ
レグのドレープが不足で芯材の曲面の形状追随性が悪か
った。Comparative Example / Bisphenol A-type epoxy resin that is liquid at room temperature with an epoxy equivalent of /g'l~/q4' (manufactured by Yuka Shell Epoxy Co., Ltd.,
70 parts by weight of “Epicote g2g”) and epoxy equivalent λ1
Bisphenol A type epoxy resin (oiled shell epoxy Kl, "Epicote 1") which is solid at room temperature with Ioo~3300
0Oq") 30 parts by weight, and dicyandiamide (manufactured by Yuka Shell Epoxy Co., Ltd., "DICY?") as a hardening agent.
) 2.7 parts by weight, N-(3,II-dichlorophenyl)-N,N'-dimethylurea (manufactured by Odugaya Chemical Co., Ltd., "DCMU 9 q") as a curing accelerator;3. A resin composition was prepared by adding g parts by weight. lIO℃ of this resin composition
The viscosity was 20,000 poise. When attempting to wrap and laminate the unidirectional prepreg obtained using this resin composition in the same manner as in the examples, the drape of the prepreg was insufficient and the ability to follow the shape of the curved surface of the core material was poor.
比較例コ
エポキシ当量７ｇグル／９グの常温で液状のビスフェノ
ールＡ型エポキシ樹脂（油化シェルエポキシ社製、“°
エピコー） ｇ 、！ｇ ” ） ？ Ａ重量部とエポ
キシ当量２り００〜３３００の常温で固体のビスフェノ
ールＡ型エポキシ樹脂（油化シェルエポキシ社製、°゛
エピコート１００９）、２１１重量部に硬化剤としてジ
シアンジアミド（油化シェルエポキシ社製、”ＤＩＣＹ
？ ” ）３．０重量部、硬化促進剤としてＮ−（３，
＋！−ジクロロフェニル）−Ｎ、Ｎ’−シメｆルウレア
（採土ケ谷化学社製、” ＤＣＭＵ ９ワ“）３０ｇｚ
量部を加えた樹脂組成物を作製した。この樹脂組成物の
グ０℃の粘度は乙、θ００ポイズであった。Comparative Example A bisphenol A type epoxy resin with a co-epoxy equivalent of 7 g/9 g that is liquid at room temperature (manufactured by Yuka Shell Epoxy Co., Ltd., “°
Epicor) g,! g '')? Parts by weight of A and epoxy equivalent 2: Bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 1009) that is solid at room temperature, 2 parts by weight of dicyandiamide (Yuka Shell Epoxy Co., Ltd.) as a hardening agent. Manufactured by Shell Epoxy, “DICY”
? ) 3.0 parts by weight, N-(3,
+! 30gz
A resin composition was prepared by adding a certain amount of the above amount. The viscosity of this resin composition at 0° C. was θ00 poise.
この樹脂組成物を用いて得られる一方向性プリプレグを
用い実施例と同様に、巻きつけ、積層をしようとしたと
ころ、これらの作業時にプリプレグシートが繊維配向に
対して９０”方向に引き裂は易く、作業性が悪かった。When we attempted to wrap and laminate the unidirectional prepreg obtained using this resin composition in the same manner as in the examples, we found that the prepreg sheet did not tear in the 90'' direction with respect to the fiber orientation during these operations. It was easy and the workability was poor.
（発明の効果）
本発明により作業性の優れた繊維強化プラスチック用樹
脂組成物を得ることができる。(Effects of the Invention) According to the present invention, a resin composition for fiber-reinforced plastics with excellent workability can be obtained.
Claims (1)
々、Ａ成分１００重量部に対し、Ｂ成分、２０〜５０重
量部、Ｃ成分１〜８重量部並びにＤ成分を含有してなる
繊維強化プラスチック用樹脂組成物。 Ａ：エポキシ当量が２５０以下で、かつ常温で液状のビ
スフェノールＡ型エポキシ樹脂 Ｂ：エポキシ当量が１５００〜５０００の範囲で、かつ
融点が１２０〜２００℃のビスフェノールＡ型エポキシ
樹脂 Ｃ：ニトリルゴム Ｄ：硬化剤(1) The following components A, B, C, and D are essential components, and each component contains 20 to 50 parts by weight of component B, 1 to 8 parts by weight of component C, and component D for 100 parts by weight of component A. A resin composition for fiber-reinforced plastics. A: Bisphenol A type epoxy resin with an epoxy equivalent of 250 or less and liquid at room temperature B: Bisphenol A type epoxy resin with an epoxy equivalent in the range of 1500 to 5000 and a melting point of 120 to 200°C C: Nitrile rubber D: hardening agent
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63040517A JP2650302B2 (en) | 1988-02-23 | 1988-02-23 | Resin composition for fiber reinforced plastic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63040517A JP2650302B2 (en) | 1988-02-23 | 1988-02-23 | Resin composition for fiber reinforced plastic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01215850A true JPH01215850A (en) | 1989-08-29 |
| JP2650302B2 JP2650302B2 (en) | 1997-09-03 |
Family
ID=12582707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63040517A Expired - Lifetime JP2650302B2 (en) | 1988-02-23 | 1988-02-23 | Resin composition for fiber reinforced plastic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2650302B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0436944A2 (en) * | 1990-01-08 | 1991-07-17 | Mitsubishi Chemical Corporation | Epoxy resin composition for fiber reinforced plastic |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5721450A (en) * | 1980-07-11 | 1982-02-04 | Toho Rayon Co Ltd | Epoxy resin composition |
-
1988
- 1988-02-23 JP JP63040517A patent/JP2650302B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5721450A (en) * | 1980-07-11 | 1982-02-04 | Toho Rayon Co Ltd | Epoxy resin composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0436944A2 (en) * | 1990-01-08 | 1991-07-17 | Mitsubishi Chemical Corporation | Epoxy resin composition for fiber reinforced plastic |
| US5302666A (en) * | 1990-01-08 | 1994-04-12 | Mitsubishi Kasei Corporation | Bisphenol A and novolak epoxy resins with nitrile rubber |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2650302B2 (en) | 1997-09-03 |
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