JPS61277681A - Addition curing type quinoxaline resin oligomer and intermediate material for fiber-reinforced composite material using said oligomer - Google Patents
Addition curing type quinoxaline resin oligomer and intermediate material for fiber-reinforced composite material using said oligomerInfo
- Publication number
- JPS61277681A JPS61277681A JP11770885A JP11770885A JPS61277681A JP S61277681 A JPS61277681 A JP S61277681A JP 11770885 A JP11770885 A JP 11770885A JP 11770885 A JP11770885 A JP 11770885A JP S61277681 A JPS61277681 A JP S61277681A
- Authority
- JP
- Japan
- Prior art keywords
- oligomer
- formula
- resin
- expressed
- tables
- 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
- 239000011347 resin Substances 0.000 title claims abstract description 39
- 229920005989 resin Polymers 0.000 title claims abstract description 39
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 title claims description 32
- 239000000463 material Substances 0.000 title claims description 12
- 238000013006 addition curing Methods 0.000 title claims description 9
- 239000003733 fiber-reinforced composite Substances 0.000 title description 6
- -1 alicyclic imide Chemical class 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 4
- 150000005215 alkyl ethers Chemical class 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 8
- 101100072408 Mus musculus Il21r gene Proteins 0.000 claims 2
- 230000002787 reinforcement Effects 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 18
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 239000012783 reinforcing fiber Substances 0.000 abstract description 9
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 7
- 239000004917 carbon fiber Substances 0.000 abstract description 7
- 238000012643 polycondensation polymerization Methods 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 150000004985 diamines Chemical class 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 abstract 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 238000000465 moulding Methods 0.000 description 11
- 238000005452 bending Methods 0.000 description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000009719 polyimide resin Substances 0.000 description 5
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BWSIKGOGLDNQBZ-LURJTMIESA-N (2s)-2-(methoxymethyl)pyrrolidin-1-amine Chemical compound COC[C@@H]1CCCN1N BWSIKGOGLDNQBZ-LURJTMIESA-N 0.000 description 1
- FUEGWHHUYNHBNI-UHFFFAOYSA-N 1-[4-(2-oxo-2-phenylacetyl)phenyl]-2-phenylethane-1,2-dione Chemical compound C=1C=CC=CC=1C(=O)C(=O)C(C=C1)=CC=C1C(=O)C(=O)C1=CC=CC=C1 FUEGWHHUYNHBNI-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 125000003431 oxalo group Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Plural Heterocyclic Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は耐熱性および強化繊維との接着性の優れた易成
形性ポリキノキサリン樹脂に関する。ざらに詳しくはキ
ノキサリン樹脂のオリゴマの両末端の脂環式エンド化合
物によって付加硬化する熱硬化型キノキサリン樹脂オリ
ゴマに関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an easily moldable polyquinoxaline resin having excellent heat resistance and adhesion to reinforcing fibers. More specifically, the present invention relates to a thermosetting quinoxaline resin oligomer that is addition-cured by alicyclic end compounds at both ends of the quinoxaline resin oligomer.
（従来の技術）
近年の航空宇宙機器や電子産業の急速な進歩にともなっ
て耐熱高分子の需要は急速に伸びている。(Prior Art) Demand for heat-resistant polymers is rapidly increasing with the rapid progress of aerospace equipment and the electronics industry in recent years.
特に炭素繊維複合材料に代表される繊維強化複合材料の
進展は著しい。In particular, the progress of fiber-reinforced composite materials, typified by carbon fiber composite materials, is remarkable.
現在繊維強化複合材料用高耐熱性マトリックス樹脂とし
てはポリイミド樹脂が最も広く使われている。そのため
、ポリイミド樹脂に関しては、成形性や耐熱性の向上に
関して多くの努力がなされてきた。しかしながら、ポリ
イミド樹脂は、高温下での耐酸化性や耐水性が不充分で
あるため、これら欠点のないポリイミド樹脂に代わる耐
熱樹脂の開発が望まれていた。Currently, polyimide resin is most widely used as a highly heat-resistant matrix resin for fiber-reinforced composite materials. Therefore, many efforts have been made to improve the moldability and heat resistance of polyimide resins. However, since polyimide resins have insufficient oxidation resistance and water resistance at high temperatures, it has been desired to develop a heat-resistant resin to replace polyimide resins that does not have these drawbacks.
ｏｅｒｇｅｎｒｏｔｈｅｒらの開発したポリキノキサリ
ン樹脂〔ジャアナル オブ ポリマー サイエンスＡ−
１１５巻１４５４−頁（Ｊ、Ｐｏｌｙｍ、ｓｃｉ、Ａ−
１１５゜１４５３（１９６７）） ）はポリイミドに比
べ、耐酸化性、耐水性に優れているため、高性能繊維強
化複合材料のマトリックス樹脂として期待されている。Polyquinoxaline resin developed by Oergenrother et al.
Volume 115, page 1454 (J, Polym, sci, A-
115°1453 (1967))) has superior oxidation resistance and water resistance compared to polyimide, and is therefore expected to be used as a matrix resin for high-performance fiber-reinforced composite materials.
しかしながら高分子量のポリキノキサリン樹脂は、溶融
粘度が高いために強化繊維に含浸しにくい、成形に高温
・高圧が必要などといった欠点があった。そこで、ポリ
イミド樹脂の場合によく知られているように付加反応性
の化合物を末端に有するオリゴマを用いることによって
成形性を改良する方法が検討されてきた。However, high-molecular-weight polyquinoxaline resins have drawbacks such as being difficult to impregnate into reinforcing fibers due to their high melt viscosity, and requiring high temperatures and pressures for molding. Therefore, as is well known in the case of polyimide resins, studies have been conducted on methods of improving moldability by using oligomers having addition-reactive compounds at their ends.
この方法によれば、樹脂の溶融粘度が低下し、成形時の
樹脂の流動性が向上するため成形が容易になる。According to this method, the melt viscosity of the resin is reduced and the fluidity of the resin during molding is improved, making molding easier.
付加硬化型キノキサリン樹脂オリゴマの研究例としては
、アセチレン基を導入したもの（ＩＩＩ）（ＵＳＰ、
３，９７５，４４４）、ニトリル基を導入したもρ〔ｌ
ｖ〕〔サンへ 第８巻第１１４頁（ＳＡＭＰ’Ｅ、ｖ
ｏｌ ８． Ｐ、 １１４．（１９７Ｂ）） ）などが
知られている。しかしこれらの樹脂は反応温度が３５０
〜４００’Ｃと高いため成形がしにくいという欠点があ
った。このためより低温で反応する付加硬化型キノキサ
リン樹脂としてアリシリツク基を導入したキノキサリン
オリゴマ（Ｖ）が研究された（ＵＳＰ３、７４８．３０
７、ＵＳＰ ３，７４８，３１０）。Examples of research on addition-curing quinoxaline resin oligomers include those with acetylene groups introduced (III) (USP,
3,975,444), ρ[l
v] [SAMP'E, v.
ol 8. P, 114. (197B))) etc. are known. However, these resins have a reaction temperature of 350
It had the disadvantage that it was difficult to mold because it was as high as ~400'C. For this reason, quinoxaline oligomer (V) into which an alisilic group was introduced was researched as an addition-curing quinoxaline resin that reacts at lower temperatures (USP 3, 748.30).
7, USP 3,748,310).
しかし、これらの樹脂は成形性は向上しているものの複
合材料としては、機械的特性たとえば曲げ強度や層間せ
ん面強度が低いという欠点があった。However, although these resins have improved moldability, they have the disadvantage that mechanical properties such as bending strength and interlaminar shear strength are low when used as composite materials.
そこで本発明者らは、付加硬化型ポリキノキサリン樹脂
をマトリックスとする複合材料物性の向上に関して鋭意
研究した結果本発明に到達した。すなわち、複合材料物
性が低い原因は樹脂と強化繊維との接着性が悪いためで
あり、この原因はポリキノキサリン樹脂が主鎖中に、接
着に寄与する官能基を持たないためであり、このことは
ポリキノキサリン樹脂にとっては宿命的ともいえるもの
である。Therefore, the present inventors conducted extensive research on improving the physical properties of a composite material using an addition-curing polyquinoxaline resin as a matrix, and as a result, they arrived at the present invention. In other words, the reason for the poor physical properties of the composite material is the poor adhesion between the resin and reinforcing fibers, and the reason for this is that the polyquinoxaline resin does not have functional groups that contribute to adhesion in its main chain. This can be said to be fateful for polyquinoxaline resins.
（発明が解決しようとする問題点）
そこで本発明者らは、ポリキノキサリン樹脂の開発に当
って、成形性改善のための付加硬化型樹脂への改質と同
時に、強化繊維との接着性を向上させる方法に関して鋭
意研究した結果、本発明に到達したものである。(Problems to be Solved by the Invention) Therefore, in developing polyquinoxaline resin, the present inventors modified it into an addition-curing resin to improve moldability, and at the same time improved its adhesion to reinforcing fibers. The present invention was achieved as a result of intensive research into methods for improving this.
（問題点を解決するための手段）
本発明は特許請求の範囲の欄に記載のとおりキノキサリ
ンオリゴマの両末端に脂環式イミド化合物を有すること
を特徴とする。すなわち、本発明による付加硬化型キノ
キサリン樹脂オリゴマは、主鎖中にイミド基を有するた
め、強化繊維とりわけ炭素繊維と樹脂との接着力が向上
し、複合材料としたときの曲げ強度や層閲せん断強度な
どの機械的特性が向上する。(Means for Solving the Problems) The present invention is characterized in that a quinoxaline oligomer has an alicyclic imide compound at both ends, as described in the claims section. In other words, since the addition-curing quinoxaline resin oligomer according to the present invention has an imide group in its main chain, it improves the adhesive strength between reinforcing fibers, especially carbon fibers, and the resin, and improves the bending strength and laminar shear when used as a composite material. Mechanical properties such as strength are improved.
キノキサリン樹脂オリゴマの両末端に脂環式イミド化合
物を導入するためには、（Ｖｌ）で表される脂環式イミ
ド化合物含有ジアミンもしくは一般式〔■〕で表される
脂環式イミド化合物含有グリオキサリル化合物が有用で
ある。In order to introduce an alicyclic imide compound to both ends of the quinoxaline resin oligomer, an alicyclic imide compound-containing diamine represented by (Vl) or an alicyclic imide compound-containing glycan represented by the general formula [■] is used. Oxalyl compounds are useful.
但し Ｘ：ＣＨ２、Ｏ
Ｙ１〜Ｙ６：ハロゲン、Ｈ，ＮＯ２、
アリル、炭素数１〜６の
アリールアルキル
リル、、炭素数の１〜６の
アルキルエーテル
Ｚ：Ｈ、■
（１、（ ＶＩ ）の化合物中、ＸとしてはＣＨ２のも
のを用いたときに、３００℃前後で硬化する樹脂が得ら
れるが、ＸとしてＯのものを用いたときにはざらに低温
の２５０℃前後で硬化する樹脂が得られるため、成形温
度を下げることができる。However, X: CH2, O Y1 to Y6: halogen, H, NO2, allyl, arylalkyllyl having 1 to 6 carbon atoms, alkyl ether having 1 to 6 carbon atoms Z: H, ■ (1, (VI) When CH2 is used as X in the compound, a resin that hardens at around 300°C is obtained, but when O is used as X, a resin that hardens at a much lower temperature of around 250°C is obtained. Therefore, the molding temperature can be lowered.
（ＶＩ）および〔■〕としては次の化合物が例示できる
。Examples of (VI) and [■] include the following compounds.
（Ｖｌ） ； １．２−ジアミノ−４−（２．５−エ
ンドメチレン−１．２，５．６−チトラヒドロフタルイ
ミド）ベンゼン
１、２−ジアミノ−４−（２．５−エンドキソー１。(Vl); 1,2-diamino-4-(2,5-endomethylene-1,2,5,6-titrahydrophthalimide)benzene 1,2-diamino-4-(2,5-endoxo 1.
２、５．６−チトラヒドロフタルイミド）ベンゼン
１、２−ジアミノ−４−（２−メチル−２，５−エンド
キラー１．２，５．６−チトラヒドロフタルイミド）ベ
ンゼン
（ＶＩ） ：４−（２．５−エンドメチレン−１．２，
５．６−チトラヒドロフ、タルイミド）ベンジル
４−（２．５エンドキソー１．２，５．６−チトラヒド
フタルイミド）ベンジル
ポリキノキサリン樹脂は、テトラアミンとグリオキサリ
ル化合物から縮合重合によって得られるポリマーである
。それ故、本発明による付加硬化型キノキサリン樹脂オ
リゴマは原料モノマとして〔■〕で表わされるテトラア
ミンと一般式（ＩＸ）で表わされるビスグリオキサリル
化合物と一般式（Ｖｌ）または（ ＶＩ ）で表わされ
る脂環式イミド化合物とから合成することができる。2,5,6-titrahydrophthalimide)benzene 1,2-diamino-4-(2-methyl-2,5-endokyler 1.2,5,6-titrahydrophthalimide)benzene (VI): 4-( 2.5-endomethylene-1.2,
5.6-titrahydrophthalimido)benzyl 4-(2.5 endoxo 1.2,5.6-titrahydrophthalimide)benzyl polyquinoxaline resin is a polymer obtained by condensation polymerization from a tetraamine and a glyoxalyl compound. Therefore, the addition-curable quinoxaline resin oligomer according to the present invention contains a tetraamine represented by [■], a bisglyoxalyl compound represented by the general formula (IX), and a resin represented by the general formula (Vl) or (VI) as raw material monomers. It can be synthesized from a cyclic imide compound.
Ｒ２：ＣＨ２ 、 Ｏ， Ｃ０， ８０２ 、 Ｓ
，ｎｉｌｚ：Ｈ，Ｑ。R2: CH2, O, C0, 802, S
, nilz:H,Q.
本発明による付加硬化型キノキサリン樹脂オリゴマの成
形性や耐熱性等は、一般式〔Ｉ〕または（ＩＩ）で表わ
されるオリゴマの分子量に依存するため、本発明の実施
にあたってはオリゴマの分子量を最適化する必要がある
。通常好ましい分子量は約１，０００−１０，０００の
範囲である。それ故、オリゴマの合成にあたっては、オ
リゴマの設計分子量に対して計算量の脂環式イミド化合
物（一般式（Ｖｌ）又は（ＶＩ））、テトラアミン（一
般式（■）、とヒスグリオキサリル化合物（一般式（Ｉ
Ｘ））をメタクレゾール、ジオキサン等の有機溶媒中で
縮合重合させる方法が一般的に採用される。得られたプ
レポリマは溶液の状態でワニスとして繊維強化複合材料
用中間素材の製造に使用することもできるし、溶液から
単離して成形用粉末を作ることも可能である。あるいは
、計算量の脂環式イミド化合物、テトラアミン、ビスグ
リオキサリル化合物をＮＭＰ、ジオキサン等の極性溶剤
に溶解し、いわゆる現場重合法（ｉｎ−ｓｉｔｕ ｐｏ
ｌｙｍｅｒｉｚａｔｉｏｎ ｏｆｍｏｎｏｍｅｒｉｃ
ｒｅａｃｔａｎｔｓ）によって、繊維強化複合材料用中
間素材を製造することも可能である。Since the moldability, heat resistance, etc. of the addition-curing quinoxaline resin oligomer according to the present invention depend on the molecular weight of the oligomer represented by general formula [I] or (II), the molecular weight of the oligomer is optimized when implementing the present invention. There is a need to. Usually preferred molecular weights are in the range of about 1,000-10,000. Therefore, when synthesizing an oligomer, the calculated amount of an alicyclic imide compound (general formula (Vl) or (VI)), tetraamine (general formula (■)), and hisglyoxalyl compound ( General formula (I
A method of condensation polymerization of X)) in an organic solvent such as metacresol or dioxane is generally employed. The obtained prepolymer can be used in the form of a varnish in the form of a solution to produce an intermediate material for fiber-reinforced composite materials, or can be isolated from the solution to produce a molding powder. Alternatively, a calculated amount of an alicyclic imide compound, tetraamine, or bisglyoxalyl compound is dissolved in a polar solvent such as NMP or dioxane, and the so-called in-situ polymerization method (in-situ polymerization method) is performed.
lymerization of monomeric
It is also possible to produce intermediate materials for fiber-reinforced composite materials using reactants).
なお本発明による成形用中間素材としては、中間素材中
のマトリックス樹脂の含有量が２５〜４５重量％の範囲
が好ましく、強化繊維としては炭素繊維、ガラス繊維、
有機繊維等が使用可能である。In the intermediate material for molding according to the present invention, the content of the matrix resin in the intermediate material is preferably in the range of 25 to 45% by weight, and the reinforcing fibers include carbon fiber, glass fiber,
Organic fibers etc. can be used.
ざらに強化繊維の形態としては、一方向に引揃えたもの
、あるいは二方向以上の定められた方向に引揃えられた
ものの他、織物、編物等が使用可能であり、強化繊維の
形態としてはとくに限定されるものではない。As for the form of the reinforcing fibers, in addition to those that are aligned in one direction or those that are aligned in two or more predetermined directions, woven fabrics, knitted fabrics, etc. can be used. It is not particularly limited.
（作用）
本発明ではオリゴマの両末端にイミド基を含有する脂環
式イミド化合物を導入することによって、成形性の向上
と同時に曲げ強度や、層間せん断強度などの複合材料物
性が向上する。そのため大型構造物の成形が可能となる
ので、航空機用途などに広く用いられている炭素繊維複
合材料などのＡＣＭ用マ下ワックス樹脂として極めて有
用である。(Function) In the present invention, by introducing an alicyclic imide compound containing imide groups at both ends of the oligomer, the physical properties of the composite material such as bending strength and interlaminar shear strength are improved at the same time as the moldability is improved. Therefore, it is possible to mold large structures, so it is extremely useful as a base wax resin for ACM such as carbon fiber composite materials that are widely used in aircraft applications.
（実施例） 以下の実施例によって本発明をざらに詳細説明する。(Example) The invention will be explained in greater detail by the following examples.
実施例１
３．３°、４，４−テトラアミンノジフェニルスルホン
を２モル、ｐ−ビス（フェニルグリオキサリル）ベンゼ
ンを３モルの割合でジオキサンに溶解し、沸点下で３時
間反応させた。次いでこの溶液に１，２−ジアミノ−４
−（２，５−エンドメチレン−１，２，５，６−テトラ
ヒドロフタルイミド）ベンゼンを２モル添加し、さらに
沸点下で３時間反応させた。得られた反応液からジオキ
サンを減圧留去し、ざらに真空乾燥してジオキサンを完
全に除去してキノキサリン樹脂オリゴマを得た。Example 1 2 moles of 3.3°, 4,4-tetraaminenodiphenylsulfone and 3 moles of p-bis(phenylglyoxalyl)benzene were dissolved in dioxane and reacted at the boiling point for 3 hours. Then, 1,2-diamino-4 was added to this solution.
-(2,5-endomethylene-1,2,5,6-tetrahydrophthalimide)benzene was added in an amount of 2 moles, and the mixture was further reacted at the boiling point for 3 hours. Dioxane was distilled off under reduced pressure from the resulting reaction solution, and the mixture was roughly dried under vacuum to completely remove dioxane, thereby obtaining a quinoxaline resin oligomer.
間プレス成形した。得られた成形品をさらに３１６°Ｃ
のオーブン中で６時間アフターキュアした後ＴＭＡでガ
ラス転移温度を測定したところ、丁ｑは３６６℃で耐熱
性の良好な成形品が得られた。Press molded. The obtained molded product is further heated to 316°C.
After curing in an oven for 6 hours, the glass transition temperature was measured using TMA, and the temperature was 366° C., and a molded product with good heat resistance was obtained.
実施例２
実施例１で得られたキノキサリン樹脂オリゴマのジオキ
サン溶液を用い、強化繊維として東し■製炭素繊維″ト
レカ”Ｔ４００を用いてドラムワインド法にてプリプレ
グを作成した。得られたプリプレグ中の樹脂の含有量は
３２．３％であった。Example 2 Using the dioxane solution of the quinoxaline resin oligomer obtained in Example 1, a prepreg was prepared by a drum winding method using carbon fiber "Torayka" T400 manufactured by Toshiki Co., Ltd. as a reinforcing fiber. The resin content in the obtained prepreg was 32.3%.
次に、得られたプリプレグを巾２０Ｃｍ長ざ２５ｃｍに
切断し、１０枚積層してオートクレーブ中で成形した。Next, the obtained prepreg was cut into pieces with a width of 20 cm and a length of 25 cm, and 10 sheets were laminated and molded in an autoclave.
成形は室温から２４０℃まで２．５°Ｃ／ｍｉｎの昇温
速度で昇温し、２４０℃に到達してから１時間保持した
。バッグ内圧力は２４０℃に到達してから１５分後に５
ｍｍ ＨＯ以下の真空にし、成形の最後まで保った。For molding, the temperature was raised from room temperature to 240°C at a rate of 2.5°C/min, and after reaching 240°C, the temperature was maintained for 1 hour. The pressure inside the bag was 5 minutes after reaching 240℃.
A vacuum of less than mm HO was achieved and maintained until the end of molding.
２４０℃で１時間、温度を保持した後、２．５℃／ｍｉ
ｎの昇温速度で２９０℃まで昇温し、２９０℃で２時間
保持し、その後室温まで冷却した。After holding the temperature at 240℃ for 1 hour, 2.5℃/mi
The temperature was raised to 290°C at a heating rate of n, held at 290°C for 2 hours, and then cooled to room temperature.
缶内圧は、成形開始と同時にｏ、ａＫｙ／ｃｔｉ／ｍｒ
ｎの昇圧速度で１４Ｋｌ ／ ｃｉまで昇圧し、１４Ｋ
ｇ／ｃｉで成形の最後まで保った。オートクレーブ成形
（多、得られた成形品を３１６°Ｃのオーブン中で６時
間アフターキュアし、ＡＳＴＭ法に準じて曲げ強度を測
定したところ、曲げ強度２０５Ｋｇ／ｍ１Ｔ１２、曲げ
弾性率１３．６ｔｏｎ ／ｍｍ２、層間せん断強度１２
．２に９／ ｍｍ ２であった。またＴＭＡ法で測定し
たガラス転移温度は３６２°Ｃで２５０’Ｃで測定した
曲げ強度は室温強度の８４％で良好な耐熱性を有してい
た。The internal pressure of the can is o, aKy/cti/mr at the same time as the start of molding.
Boost to 14Kl/ci with a boost rate of n, 14K
g/ci was maintained until the end of molding. Autoclave molding (Top) The obtained molded product was after-cured in an oven at 316°C for 6 hours, and the bending strength was measured according to the ASTM method.The bending strength was 205Kg/m1T12, and the bending modulus was 13.6ton/mm2. , interlaminar shear strength 12
．． 2 to 9/mm2. Further, the glass transition temperature measured by the TMA method was 362°C, and the bending strength measured at 250'C was 84% of the room temperature strength, indicating good heat resistance.
比較例
１．２−ジアミノ−４−（２，５−エンドメチレン−１
−２゜５．６−テトラヒドロフタルイミド）ベンゼンの
代わりに２．５−エンドメチレン−１−α、β −ジア
ミノエタン−１，２，５，６−テトラヒドロベンゼンを
用いた他は実施例１と同様にして合成したキノキサリン
樹脂オリゴマを用い、実施例２と同様の方法で炭素繊維
複合材料を成形した。Comparative Example 1.2-diamino-4-(2,5-endomethylene-1
Same as Example 1 except that 2.5-endomethylene-1-α,β-diaminoethane-1,2,5,6-tetrahydrobenzene was used instead of -2゜5.6-tetrahydrophthalimido)benzene. A carbon fiber composite material was molded in the same manner as in Example 2 using the quinoxaline resin oligomer synthesized as described above.
ＴＭＡ法で測定したＴＣＩは３５４℃で良好な耐熱性を
有していた。しかし、ＡＳＴＭ法に準じて曲げ強度を測
定したところ、曲げ強度１５２Ｋｌ１ｍｍ ２、層間せ
ん断強度８．５に’ｊ／ ｍｍ ２であり、実施例２に
比べて機械的特性が大幅に劣っていた。TCI measured by TMA method had good heat resistance at 354°C. However, when the bending strength was measured according to the ASTM method, the bending strength was 152Kl1mm2, and the interlaminar shear strength was 8.5'j/mm2, and the mechanical properties were significantly inferior to Example 2.
（発明の効果）
樹脂の成形性向上と同時に曲げ強度や層間せん断強度な
どの複合材料物性の向上が実現する。(Effects of the Invention) At the same time as the moldability of the resin is improved, physical properties of the composite material such as bending strength and interlaminar shear strength are improved.
Claims (2)
に脂環式イミド化合物を有することを特徴とする付加硬
化型キノキサリン樹脂オリゴマ。 ▲数式、化学式、表等があります▼〔 I 〕 ▲数式、化学式、表等があります▼〔II〕 但しＡｒ：▲数式、化学式、表等があります▼（ｍ：０
〜３） ｎ：０〜１０ Ｒ＿１：ＣＨ＿２、Ｏ、ＣＯ、ＳＯ＿２、Ｓ、ｎｉｌＲ
＿２：ＣＨ＿２、Ｏ、ＣＯ、ＳＯ＿２、Ｓ、ｎｉｌＸ：
ＣＨ＿２、Ｏ、 Ｙ＿１〜Ｙ＿６：ハロゲン、Ｈ、ＮＯ＿２、アリル、炭
素数１〜６のアリールアルキル アルカリル、炭素数１〜６の アルキルエーテル Ｚ：Ｈ、▲数式、化学式、表等があります▼(1) An addition-curing quinoxaline resin oligomer characterized by having an alicyclic imide compound at both ends represented by the general formula [I] or [II]. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ II ] However, Ar: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (m: 0
~3) n: 0~10 R_1: CH_2, O, CO, SO_2, S, nilR
_2: CH_2, O, CO, SO_2, S, nilX:
CH_2, O, Y_1 to Y_6: halogen, H, NO_2, allyl, arylalkyl alkaryl having 1 to 6 carbon atoms, alkyl ether having 1 to 6 carbon atoms Z: H, ▲Mathematical formulas, chemical formulas, tables, etc. are available▼
に脂環式イミド化合物を有することを特徴とする付加硬
化型キノキサリン樹脂オリゴマまたはそのモノマを含浸
させたことを特徴とする繊維強化複合材料用中間素材。 ▲数式、化学式、表等があります▼〔 I 〕 ▲数式、化学式、表等があります▼〔II〕 但しＡｒ：▲数式、化学式、表等があります▼（ｍ：０
〜３） ｎ：０〜１０ Ｒ＿１：ＣＨ＿２、Ｏ、ＣＯ、ＳＯ＿２、Ｓ、ｎｉｌＲ
＿２：ＣＨ＿２、Ｏ、ＣＯ、ＳＯ＿２、Ｓ、ｎｉｌＸ：
ＣＨ＿２、Ｏ、 Ｙ＿１〜Ｙ＿６：ハロゲン、Ｈ、ＮＯ＿２、アリル、炭
素数１〜６のアリールアルキル アルカリル、炭素数１〜６の アルキルエーテル Ｚ：Ｈ、▲数式、化学式、表等があります▼(2) Fiber reinforcement characterized by being impregnated with an addition-curing quinoxaline resin oligomer having an alicyclic imide compound at both ends represented by general formula [I] or [II] or its monomer Intermediate material for composite materials. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ II ] However, Ar: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (m: 0
~3) n: 0~10 R_1: CH_2, O, CO, SO_2, S, nilR
_2: CH_2, O, CO, SO_2, S, nilX:
CH_2, O, Y_1 to Y_6: halogen, H, NO_2, allyl, arylalkyl alkaryl having 1 to 6 carbon atoms, alkyl ether having 1 to 6 carbon atoms Z: H, ▲Mathematical formulas, chemical formulas, tables, etc. are available▼
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11770885A JPS61277681A (en) | 1985-06-01 | 1985-06-01 | Addition curing type quinoxaline resin oligomer and intermediate material for fiber-reinforced composite material using said oligomer |
| US06/841,862 US4670536A (en) | 1985-06-01 | 1986-03-20 | Addition-curable quinoxaline resin oligomer and intermediate material for fiber-reinforced composite |
| US07/014,925 US4739075A (en) | 1985-06-01 | 1987-02-13 | Reactive end-capping agent, addition-curable quinoxaline resin oligomer and intermediate material for fiber-reinforced composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11770885A JPS61277681A (en) | 1985-06-01 | 1985-06-01 | Addition curing type quinoxaline resin oligomer and intermediate material for fiber-reinforced composite material using said oligomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61277681A true JPS61277681A (en) | 1986-12-08 |
| JPH03418B2 JPH03418B2 (en) | 1991-01-08 |
Family
ID=14718341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11770885A Granted JPS61277681A (en) | 1985-06-01 | 1985-06-01 | Addition curing type quinoxaline resin oligomer and intermediate material for fiber-reinforced composite material using said oligomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61277681A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010059242A (en) * | 2008-09-01 | 2010-03-18 | Asahi Kasei E-Materials Corp | Epoxy resin curable composition, resin varnish, prepreg, metal-clad laminate, and cured product |
-
1985
- 1985-06-01 JP JP11770885A patent/JPS61277681A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010059242A (en) * | 2008-09-01 | 2010-03-18 | Asahi Kasei E-Materials Corp | Epoxy resin curable composition, resin varnish, prepreg, metal-clad laminate, and cured product |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03418B2 (en) | 1991-01-08 |
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