JPH068340B2 - Matrix resin composition for prepreg - Google Patents
Matrix resin composition for prepregInfo
- Publication number
- JPH068340B2 JPH068340B2 JP8625585A JP8625585A JPH068340B2 JP H068340 B2 JPH068340 B2 JP H068340B2 JP 8625585 A JP8625585 A JP 8625585A JP 8625585 A JP8625585 A JP 8625585A JP H068340 B2 JPH068340 B2 JP H068340B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- prepreg
- cured product
- weight
- 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.)
- Expired - Lifetime
Links
- 239000011342 resin composition Substances 0.000 title claims description 12
- 239000011159 matrix material Substances 0.000 title claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 44
- 229920000647 polyepoxide Polymers 0.000 claims description 44
- -1 alkylene glycol Chemical compound 0.000 claims description 17
- 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 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004695 Polyether sulfone Substances 0.000 claims description 7
- 229920006393 polyether sulfone Polymers 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 14
- 239000004593 Epoxy Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 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 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N 1,5-Pentadiol Natural products OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- VNAWKNVDKFZFSU-UHFFFAOYSA-N 2-ethyl-2-methylpropane-1,3-diol Chemical compound CCC(C)(CO)CO VNAWKNVDKFZFSU-UHFFFAOYSA-N 0.000 description 1
- JVZZUPJFERSVRN-UHFFFAOYSA-N 2-methyl-2-propylpropane-1,3-diol Chemical compound CCCC(C)(CO)CO JVZZUPJFERSVRN-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- BWWHTIHDQBHTHP-UHFFFAOYSA-N 2-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=CC=C1C(Cl)=O BWWHTIHDQBHTHP-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 1
- 101100156289 Arabidopsis thaliana VICTR gene Proteins 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 101150093857 Ccn4 gene Proteins 0.000 description 1
- 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 1
- 102100028890 E3 ubiquitin-protein ligase synoviolin Human genes 0.000 description 1
- 101150081978 ELM1 gene Proteins 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 101000838967 Homo sapiens E3 ubiquitin-protein ligase synoviolin Proteins 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- NUUPJBRGQCEZSI-UHFFFAOYSA-N cyclopentane-1,3-diol Chemical compound OC1CCC(O)C1 NUUPJBRGQCEZSI-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
- 229950006800 prenderol Drugs 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000012779 reinforcing material Substances 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
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は高性能型炭素繊維プリプレグ用樹脂組成物に関
するものである。TECHNICAL FIELD The present invention relates to a resin composition for high performance carbon fiber prepreg.
炭素繊維強化プラスチックス（以下ＣＦＲＰと略す）は
比強度、比弾性率が大きいことから民間航空機分野に於
て、機体の一層の軽量化のため一次構造材として検討さ
れている。Since carbon fiber reinforced plastics (hereinafter abbreviated as CFRP) have large specific strength and specific elastic modulus, they are considered as a primary structural material in the field of civil aviation for further weight reduction of aircraft.
現在、ＣＦＲＰが一次構造材として使用されるために要
求されている最も重要な特性の一つは、高温吸湿下での
圧縮強度を維持しての優れた衝撃特性である。Currently, one of the most important properties required for CFRP to be used as a primary structural material is excellent impact property while maintaining the compressive strength under high temperature moisture absorption.
即ち、航空機が、高温多湿地方で使用されるとき、ＣＦ
ＲＰは吸湿する。さらに、地上待機中に機体温度が上昇
しその直後飛行する際に、最大の圧縮荷重が機体にかか
るため、高温吸湿下で圧縮強度が要求される。That is, when the aircraft is used in hot and humid areas, CF
RP absorbs moisture. Furthermore, since the maximum compressive load is applied to the airframe when the airframe temperature rises during standby on the ground and immediately after that, compressive strength is required under high temperature moisture absorption.
また、ＣＦＲＰは機体製造時の治具等の落下衝撃や、飛
行中の雹の衝撃等により、外観上異常がないにもかかわ
らず層間剥離を起こし強度低下をきたす。このため安全
上問題となり、この衝撃特性の向上がＣＦＲＰの一次構
造材として使用されるかどうかの鍵になっている。In addition, CFRP causes delamination due to delamination due to a drop impact of a jig or the like at the time of manufacturing an airframe, a hail impact during flight, and the like, although there is no abnormality in appearance, resulting in a decrease in strength. For this reason, it becomes a safety problem, and improvement of this impact property is the key to whether or not it is used as the primary structural material of CFRP.
現在、航空機用ＣＦＲＰに使用されているエポキシ樹脂
は、N,N,Ｎ′，Ｎ′−テトラグリシジルジアミノジフェ
ニルメタンを主成分とし硬化剤は、ジアミノジフェニル
スルホンが使用されている。この樹脂組成物は高弾性率
を有し耐熱性は高いが、樹脂伸度が小さく脆い硬化物に
なる。この樹脂組成物から得られるＣＦＲＰは優れた、
高温吸湿下での圧縮強度は発現するが、衝撃特性は低
く、一次構造材としては使用できない。Currently, the epoxy resin used for CFRP for aircraft has N, N, N ', N'-tetraglycidyldiaminodiphenylmethane as a main component, and diaminodiphenylsulfone is used as a curing agent. This resin composition has a high elastic modulus and high heat resistance, but has a small resin elongation and becomes a brittle cured product. CFRP obtained from this resin composition is excellent,
Although it exhibits compressive strength under high temperature moisture absorption, it has low impact properties and cannot be used as a primary structural material.
そこで本発明者らは、ＣＦＲＰの高湿吸湿下の圧縮強度
を損うことなく優れた衝撃特性を発現するマトリックス
樹脂を見い出すべく鋭意検討した結果、本発明に到達し
た。Therefore, the present inventors have arrived at the present invention as a result of extensive studies to find a matrix resin that exhibits excellent impact properties without impairing the compressive strength of CFRP under high humidity absorption.
すなわち、本発明は次の構成を有する。 That is, the present invention has the following configurations.
(1)N,N,Ｎ′，Ｎ′−テトラグリシジルジアミノジフェ
ニルメタン、ビスフェノールＡ型エポキシ樹脂、ブロム
化エポキシ樹脂、一般式（１） （式中、Ｒは炭素数３〜８のアルキレングリコール、ま
たは、炭素数５〜１４の脂環式ジオールの残基である。
残基とは、アルキレングリコール、または、脂環式ジオ
ールの水酸基を除いたものである。）で示される化合物
を硬化剤として含有するエポキシ樹脂組成物と一般式
（２） で示されるポリエーテルサルホンを含有して成るプリプ
レグ用マトリックス樹脂組成物。(1) N, N, N ', N'-tetraglycidyldiaminodiphenylmethane, bisphenol A type epoxy resin, brominated epoxy resin, general formula (1) (In the formula, R is a residue of an alkylene glycol having 3 to 8 carbon atoms or an alicyclic diol having 5 to 14 carbon atoms.
The residue is an alkylene glycol or an alicyclic diol excluding a hydroxyl group. And an epoxy resin composition containing a compound represented by the formula (2) as a curing agent A matrix resin composition for prepreg, comprising the polyether sulfone represented by
本発明に用いられるエポキシ樹脂は、分子内に２個以上
のエポキシ基を含有するエポキシ樹脂、例えばN,N,
Ｎ′，Ｎ′−テトラグリシジルジアミノジフェニルメタ
ン、N,N,O−トリグリシジルアミノフェノールに代表さ
れるアミノ型エポキシ樹脂、ビスフェノールＡ型エポキ
シ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノ
ールＳ型エポキシ樹脂、フェノールノボラック型エポキ
シ樹脂、クレゾールノボラック型エポキシ樹脂、グリセ
リンのグリシジル誘導体等に代表される反応希釈剤、脂
環族エポキシ樹脂などである。これらのエポキシ樹脂を
単独または２〜３種混合して使用するが、本発明の効果
を十分発現させるには、以下のような添加量で種々のエ
ポキシ樹脂を配合するのがより好ましい。The epoxy resin used in the present invention is an epoxy resin containing two or more epoxy groups in the molecule, such as N, N,
N ', N'-tetraglycidyldiaminodiphenylmethane, amino type epoxy resin represented by N, N, O-triglycidylaminophenol, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac Type epoxy resin, cresol novolac type epoxy resin, reaction diluent typified by glycidyl derivative of glycerin, alicyclic epoxy resin and the like. These epoxy resins are used alone or as a mixture of 2 to 3 kinds, and in order to sufficiently bring out the effect of the present invention, it is more preferable to mix various epoxy resins with the following addition amounts.
すなわち、本発明に用いられるN,N,Ｎ′，Ｎ′−テトラ
グリシジルジアミノジフェニルメタンは、ＥＬＭ４３
４、ＹＬ９１３、ＹＨ４３４などの商品名で市販されて
いる。このエポキシ樹脂は四官能エポキシ樹脂であるた
め、架橋密度が高くなり、高弾性率かつ高耐熱性の硬化
物が得られるといいう長所がある。だが、硬化物の伸度
が小さく耐水性が悪い欠点がある。これらの特性を考慮
して、N,N,Ｎ′，Ｎ′−テトラグリシジルジアミノジフ
ェニルメタンの添加量はエポキシ樹脂成分中２０〜７０
重量％であり、より好ましくは２０〜５０重量％であ
る。この範囲より多くすると、得られる硬化物は脆くな
り耐水性も悪くなる。少なくすると、硬化物の耐熱性及
び弾性率が低下する。硬化樹脂の弾性率が低下すると得
られるＣＦＲＰの圧縮強度は低いものになってしまう。That is, N, N, N ', N'-tetraglycidyldiaminodiphenylmethane used in the present invention is ELM43.
4, YL913, YH434 and the like. Since this epoxy resin is a tetrafunctional epoxy resin, it has the advantages that the crosslink density is high and a cured product having a high elastic modulus and high heat resistance can be obtained. However, it has a drawback that the elongation of the cured product is small and the water resistance is poor. Considering these characteristics, the addition amount of N, N, N ', N'-tetraglycidyldiaminodiphenylmethane is 20 to 70 in the epoxy resin component.
%, More preferably 20 to 50% by weight. When the amount is more than this range, the obtained cured product becomes brittle and the water resistance becomes poor. If it is too small, the heat resistance and elastic modulus of the cured product will decrease. If the elastic modulus of the cured resin decreases, the compressive strength of CFRP obtained will be low.
本発明に使用されているブロム化エポキシ樹脂は、ブロ
ム化ビスフェノールＡのグリシジルエーテル型エポキシ
樹脂及びブロム化フェノールノボラック樹脂のグリシジ
ルエーテル型エポキシ樹脂で、ブロム含有量が１６〜５
０重量％のものであり、エピクロン１５２、エピクロン
１１２０ＥＳＢ３４０、Ｅｐ１０５０、ＢＲＥＮ−Ｓの
商標名で市販されている。このブロム化エポキシ樹脂は
耐水性及び弾性率の高い硬化物になるが、ブロム原子に
起因する立体障害を有するため、伸度が小さく脆い硬化
物になる。これらの特性を考慮して、ブロム化エポキシ
樹脂の添加量は、エポキシ樹脂成分中１０〜５０重量％
であり、より好ましくは１０〜４０重量％である。この
範囲より多くすると硬化物の耐熱性が低下すると共に伸
度が小さく脆くなる。少なくすると硬化物の耐水性及び
弾性率が低下する。The brominated epoxy resin used in the present invention is a glycidyl ether type epoxy resin of brominated bisphenol A and a glycidyl ether type epoxy resin of brominated phenol novolac resin and has a brom content of 16 to 5.
It is 0% by weight, and is commercially available under the trade names of Epiclon 152, Epiclon 1120ESB340, Ep1050, and BREN-S. This brominated epoxy resin is a cured product having a high water resistance and a high elastic modulus, but it has a steric hindrance due to the bromine atom, and is a cured product having a small elongation and a brittleness. Considering these characteristics, the amount of the brominated epoxy resin added is 10 to 50% by weight in the epoxy resin component.
And more preferably 10 to 40% by weight. If it is more than this range, the heat resistance of the cured product will be reduced and the elongation will be small and brittle. If the amount is reduced, the water resistance and elastic modulus of the cured product decrease.
本発明に用いられるビスフェノールＡ型エポキシ樹脂
は、Ｅｐ８２８、Ｅｐ８２５、Ｅｐ１００１、ＹＤ１２
８、エピクロン８５５、エピクロン１０５０、ＤＥＲ３
３１、ＤＥＲ３３７などの商品名で市販されている。こ
の樹脂から得られる硬化物は、樹脂伸度が大きい反面、
弾性率が低い。これらの特性を考慮してビスフェノール
Ａ型エポキシ樹脂の添加量はエポキシ樹脂成分中１０〜
６０重量％であり、より好ましくは２０〜５０重量％で
ある。この範囲より多くすると硬化物の弾性率は低下す
る。少なくすると硬化物の伸度が小さくなり脆くなる。
また、ビスフェノールＡ型エポキシ樹脂と類似の構造と
性能を有するエピクロン８３０、Ｅｐ８０７等の商品名
で市販されているビスフェノールＦ型エポキシ樹脂にか
えても良い。The bisphenol A type epoxy resin used in the present invention is Ep828, Ep825, Ep1001, YD12.
8, Epicron 855, Epicron 1050, DER3
31 and DER337 are commercially available. The cured product obtained from this resin has a large resin elongation,
Low elastic modulus. Considering these characteristics, the addition amount of the bisphenol A type epoxy resin is 10 to 10 in the epoxy resin component.
It is 60% by weight, and more preferably 20 to 50% by weight. If it exceeds this range, the elastic modulus of the cured product will decrease. If the amount is reduced, the elongation of the cured product becomes small and the product becomes brittle.
Further, it may be replaced with a bisphenol F type epoxy resin marketed under the trade name of Epicron 830, Ep807 or the like having a structure and performance similar to the bisphenol A type epoxy resin.
さらに、本発明のマトリックス樹脂組成物に、ＥＬＭ１
２０、ＹＤＭ１２０の商品名で市販されている、N,N,O
−トリグリシジルメタアミノフェノールの添加は、硬化
の促進及び硬化物の弾性率向上をもたらす。しかしこの
樹脂の添加は硬化物の耐水性を低下させるため添加量は
エポキシ樹脂成分中５〜２０重量％である。Furthermore, the matrix resin composition of the present invention has ELM1
20, N, N, O marketed under the trade name of YDM120
-The addition of triglycidyl metaaminophenol promotes curing and improves the elastic modulus of the cured product. However, the addition of this resin reduces the water resistance of the cured product, so the addition amount is 5 to 20% by weight in the epoxy resin component.
また、Ｅｐ１５２、Ｅｐ１５４、ＤＥＮ４３１、ＤＥＮ
４３８等の商品名で市販されているフェノールノボラッ
ク型エポキシ樹脂の添加は、硬化物の耐熱性を向上させ
ることから好ましい。しかしこの樹脂の添加は、得られ
る硬化物の弾性率を低下させるため、添加量はエポキシ
樹脂成分中４０重量％以下である。Also, Ep152, Ep154, DEN431, DEN
The addition of a phenol novolac type epoxy resin marketed under the trade name of 438 or the like is preferable because it improves the heat resistance of the cured product. However, the addition of this resin lowers the elastic modulus of the obtained cured product, so the addition amount is 40% by weight or less in the epoxy resin component.
さらに、低粘度のエポキシ樹脂である、ＥＬＡ３０１等
の商品名で市販されている反応希釈剤及びＥＲＬ４２２
１、ＥＲＬ４２０６等の商品名で市販されている脂環族
エポキシ樹脂の添加は、本発明マトリックス樹脂組成物
のタック及びドレープ性を向上させることから好まし
い。しかし、これらのエポキシ樹脂の添加は、得られる
硬化物の耐水性を低下させるため、添加量はエポキシ成
分中３０重量％以下であり、より好ましくは２０重量％
以下である。Furthermore, a low-viscosity epoxy resin, such as ELA301 and other commercially available reaction diluents and ERL422
1, the addition of an alicyclic epoxy resin marketed under the trade name of ERL4206 or the like is preferable because it improves the tack and drape properties of the matrix resin composition of the present invention. However, the addition of these epoxy resins lowers the water resistance of the resulting cured product, so the addition amount is 30% by weight or less in the epoxy component, and more preferably 20% by weight.
It is the following.
本発明の一般式（１）で示される化合物は公知の方法で
得ることができる。たとえば、炭素数３〜８のアルキレ
ングリコール、または炭素数５〜１４の脂環式ジオール
をニトロベンゾイルクロライドと反応させ、ついで生成
物をパラジウム触媒の存在下、ヒドラジンで還元するこ
とにより得ることができる。炭素数３〜８のアルキレン
グリコールとしては、１，２−プロパンジオール、１，
３−プロパンジオール、１，２−ブタンジオール、１，
４−ブタンジオール、１，５−ペンタジオール、ネオペ
ンチルグリコール、１，６−ヘキサンジオール、２−エ
チル−２−メチル−１，３−プロパンジオール、１，７
−ヘプタンジオール、２，２−ジエチル−１，３−プロ
パンジオール、２−メチル−２−プロピル−１，３−プ
ロパンジオール、１，８−オクタンジオールなどの直鎖
の、または、側鎖を有するアルキレングリコールなどが
挙げられる。アルキレングリコールは、酸素、イオウな
どの異核原子を含んでいても良く、たとえばジエチレン
グリコール、トリエチレングリコール、チオジエタノー
ルなどが挙げられる。炭素数５〜１４の脂環式ジオール
としては、１，３−シクロペンタンジオール、１，４−
シクロヘキサンジオール、１，４−シクロヘキサンジメ
チロール、１，５−デカリンジオール、トリシクロデカ
ンジメチロールなどのジオールが挙げられる。アミノ基
の位置は、エステル基に対してｍ位、ｐ位どちらでもか
まわない。この化合物の添加量は理論的にはエポキシ１
当量に対してアミン１重量になるよう添加すれば良い
が、硬化速度やシェルフライフの調整、及び、得られる
硬化物の耐熱性、耐水性、伸度などから、この化合物の
添加量はエポキシ１当量に対して０．４〜１．５当量で
ある。だが、一般式（２）で示されるポリエーテルサル
ホンの添加効率を最大にし、衝撃特性を大巾に向上させ
るには、一般式（１）で示される硬化剤の添加量は０．
５〜０．７当量がより好ましい。このように硬化剤の量
を減らした場合、１当量添加した場合のガラス転移温度
と同程度にするには硬化温度をより高温にするか硬化時
間を長くする必要がある。この欠点を補うために、三フ
ッ化ホウ素アミン錯体、ジシアンジアミド等の硬化促進
剤を添加することは非常に好ましい。The compound represented by the general formula (1) of the present invention can be obtained by a known method. For example, it can be obtained by reacting an alkylene glycol having 3 to 8 carbon atoms or an alicyclic diol having 5 to 14 carbon atoms with nitrobenzoyl chloride, and then reducing the product with hydrazine in the presence of a palladium catalyst. . As the alkylene glycol having 3 to 8 carbon atoms, 1,2-propanediol, 1,
3-propanediol, 1,2-butanediol, 1,
4-butanediol, 1,5-pentadiol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7
-Having a straight chain or a side chain such as heptanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 1,8-octanediol Examples thereof include alkylene glycol. The alkylene glycol may contain heteronuclear atoms such as oxygen and sulfur, and examples thereof include diethylene glycol, triethylene glycol and thiodiethanol. Examples of the alicyclic diol having 5 to 14 carbon atoms include 1,3-cyclopentanediol and 1,4-
Examples include diols such as cyclohexane diol, 1,4-cyclohexane dimethylol, 1,5-decalin diol, and tricyclodecane dimethylol. The position of the amino group may be either m-position or p-position with respect to the ester group. The theoretical amount of this compound added is epoxy 1
It may be added so that the amount of the amine is 1 weight per equivalent, but the addition amount of this compound is epoxy 1 because of the adjustment of the curing speed and shelf life, and the heat resistance, water resistance, and elongation of the obtained cured product. It is 0.4 to 1.5 equivalents relative to equivalents. However, in order to maximize the addition efficiency of the polyether sulfone represented by the general formula (2) and greatly improve the impact characteristics, the addition amount of the curing agent represented by the general formula (1) is 0.1.
5 to 0.7 equivalent is more preferable. When the amount of the curing agent is reduced as described above, the curing temperature needs to be higher or the curing time needs to be lengthened in order to reach the glass transition temperature of the case where one equivalent is added. In order to compensate for this drawback, it is highly preferable to add a curing accelerator such as a boron trifluoride amine complex or dicyandiamide.
本発明に用いられる一般式（２）で示されるポリエーテ
ルサルホンは、ＩＣＩ（英国）で開発され、ＶＩＣＴＲ
ＥＸの商品名で市販されているものだけでなく、既知の
方法により合成されたオリゴマでもよい。このポリエー
テルサルホンの添加量は、エポキシ樹脂と硬化剤から成
るエポキシ樹脂組成物１００重量部に対して、５〜５０
重量部が良いが、より好ましくは、５〜３５重量部であ
る。この範囲より多くすると非常に粘度の高いマトリッ
クス樹脂組成物になるため樹脂の含浸が悪いうえ成形性
の悪いプリプレグしか得られない。この結果、得られる
ＣＦＲＰは物性の悪いものになる。また、この範囲より
少なくすると、ポリエーテルサルホンの添加効果がなく
衝撃特性の低いＣＦＲＰしか得られない。The polyether sulfone represented by the general formula (2) used in the present invention was developed by ICI (UK), and is VICTR.
Not only those sold under the trade name of EX but also oligomers synthesized by a known method may be used. The amount of the polyether sulfone added is 5 to 50 parts by weight with respect to 100 parts by weight of the epoxy resin composition including the epoxy resin and the curing agent.
The weight part is good, but more preferably 5 to 35 parts by weight. If the amount is more than this range, the resulting matrix resin composition has a very high viscosity, so that only prepreg having poor resin impregnation and poor moldability can be obtained. As a result, the obtained CFRP has poor physical properties. On the other hand, if the amount is less than this range, only CFRP having a low impact property without the effect of adding polyethersulfone can be obtained.
本発明のマトリックス樹脂組成物は、ＣＦＲＰとして好
ましく用いられるが、この場合に使用される炭素繊維と
は、一定方向に配列されたテープ、シート状物、マット
状物、織物などのような形態のものに適用できる。さら
に、アラミド繊維、ポロン繊維、炭化ケイ素繊維など先
進複合材料の補強材、さらに、これらのハイブリッドに
ついても使用できる。The matrix resin composition of the present invention is preferably used as CFRP, and the carbon fiber used in this case is in the form of a tape, a sheet, a mat, a woven fabric or the like arranged in a certain direction. It can be applied to things. Further, it can be used for reinforcing materials of advanced composite materials such as aramid fiber, polon fiber, silicon carbide fiber, and hybrids thereof.
〔発明の効果〕 本発明にかかるマトリックス樹脂組成物を用いたＣＦＲ
Ｐは、高温高湿下での圧縮強度を損うことなく、衝撃特
性を大巾に向上した。さらに、ＣＦＲＰにおいて向上が
望まれている９０°引張伸度も大巾に向上した。[Effects of the Invention] CFR using the matrix resin composition according to the present invention
P significantly improved impact properties without impairing the compressive strength under high temperature and high humidity. Further, the 90 ° tensile elongation, which is desired to be improved in CFRP, is also greatly improved.
以下、実施例によって本発明をさらに詳しく説明する。Hereinafter, the present invention will be described in more detail with reference to examples.
実施例１ N,N,Ｎ′，Ｎ−テトラグリシジルジアミノジフェニルメ
タン（エポキシ当量１２０）３５０ｇ、ブロム化エポキ
シ樹脂（エポキシ当量３６０）３００ｇ、ビスフェノー
ルＡ型エポキシ樹脂（エポキシ当量１８９）３５０ｇ、
ネオペンチルグリコールジｐ−アミノベンゾエート（ア
ミン当量８５．５）２８２ｇ（エポキシ１当量に対して
アミン０．６当量に相当）、三フッ化ホウ素モノエチル
アミン１５ｇ、ポリエーテルサルホン１００ｐ２５６４
ｇ（２０部添加）を塩化メチレン（５５）／クロロヘル
ム（４２）／メタノール（３）の混合溶媒３５９０ｇに
溶かした。この溶液をトレカＴ３００クロス＃７３７３
（東レ（株）商品名）に含浸させ、一晩放置後、１２０
℃、５分間乾燥してＷＲ４１％のクロスプリプレグを作
製した。このプリプレグを疑似等方に２４プライ積層し
た後、離型処理したアルミ板上に載せ、ナイロン製のバ
キュムバッグでオートクレーブ用にセットした。このセ
ットした物をオートクレーブに入れ６kg／cm2に加圧し
た後、１８０℃、２時間加熱して硬化板を得た。この硬
化板の厚さは、５．０mm、ガラス転移温度は１９１℃で
あった。この硬化板から縦１５０mm、横１００mmの試験
片を切り出した後、縦横厚さ方向が９０゜になるよう端
面加工した。この試験片に厚さ１０mmあたり６７５kg−
cm及び９００kg−cmの落錘衝撃を与えた後、縦方向に圧
縮荷重をかけ衝撃後の残存圧縮強度を測定した。この結
果を表１に示す。さらに、上記溶液を用い、トレカＴ３
００、３Ｋに含浸させドラムワインド法にてＷｐ３５％
の一方向にプリプレグを作製した。このプリプレグを１
方向に５枚積層した後、クロスプリプレグと同様にして
オートクレープ成形により硬化板を得た。この硬化板か
らＡＳＴＭ、Ｄ６９５に準じて試験片を切り出し圧縮物
性を測定した。この結果を表２に示す。次に、この一方
向のプリプレグを１０枚一方向に積層し同様に硬化板を
作った。この硬化板から炭素繊維に対して９０°方向に
長さ２３０mm、巾２５４mmの９０゜引張用試験片を切り
出した。この試験片の中央に歪みゲージを貼り付け、引
張速度１mm／分で引張り、引張物性を測定した。この結
果を表２に示す。Example 1 350 g of N, N, N ', N-tetraglycidyldiaminodiphenylmethane (epoxy equivalent 120), 300 g of brominated epoxy resin (epoxy equivalent 360), 350 g of bisphenol A type epoxy resin (epoxy equivalent 189),
282 g of neopentyl glycol di-p-aminobenzoate (amine equivalent 85.5) (corresponding to 0.6 equivalent of amine to 1 equivalent of epoxy), 15 g of boron trifluoride monoethylamine, polyether sulfone 100p2564
g (20 parts added) was dissolved in 3590 g of a mixed solvent of methylene chloride (55) / chlorohelm (42) / methanol (3). This solution is used as a trading card T300 cloth # 7373
(Toray Co., Ltd. trade name) Impregnated and left overnight, then 120
The cloth was dried at 5 ° C. for 5 minutes to prepare a WR 41% cross prepreg. After stacking 24 plies of this prepreg in a pseudo isotropic manner, the prepreg was placed on a release-treated aluminum plate and set in a nylon bag for autoclaving. The set product was put into an autoclave, pressurized to 6 kg / cm 2 , and then heated at 180 ° C. for 2 hours to obtain a cured plate. The cured plate had a thickness of 5.0 mm and a glass transition temperature of 191 ° C. A test piece having a length of 150 mm and a width of 100 mm was cut out from this cured plate, and the end surface was processed so that the lengthwise and widthwise directions were 90 °. This test piece has a thickness of 675 kg per 10 mm-
After applying a falling weight impact of cm and 900 kg-cm, a compressive load was applied in the longitudinal direction and the residual compressive strength after impact was measured. The results are shown in Table 1. Furthermore, using the above solution, trading card T3
Wp 35% by drum wind method
A prepreg was produced in one direction. This prepreg is 1
After stacking 5 sheets in the same direction, a cured plate was obtained by autoclave molding in the same manner as the cross prepreg. A test piece was cut out from this cured plate according to ASTM and D695, and the compression properties were measured. The results are shown in Table 2. Next, ten unidirectional prepregs were laminated in one direction to prepare a cured plate in the same manner. From this cured plate, a 90 ° tensile test piece having a length of 230 mm and a width of 254 mm was cut in the 90 ° direction with respect to the carbon fiber. A strain gauge was attached to the center of the test piece and pulled at a pulling rate of 1 mm / min to measure the tensile properties. The results are shown in Table 2.
実施例２ トリシクロデカンジメチロールジｐ−アミノベンゾエー
トを用いて実施例１と同様にして、衝撃後の残存圧縮強
度、圧縮強度及び９０°引張物性を測定した。その結果
を表１及び表２に示す。Example 2 The residual compressive strength after impact, the compressive strength and the 90 ° tensile properties were measured in the same manner as in Example 1 using tricyclodecane dimethylol di-p-aminobenzoate. The results are shown in Tables 1 and 2.
比較例１ N,N,Ｎ′，Ｎ′−テトラグリシジルジアミノジフェニル
メタン３５０ｇ、ブロム化エポキシ樹脂３００ｇ、ビス
フェノールＡ型エポキシ樹脂３５０ｇ、ネオペンチルグ
リコール、ジｐアミノベンゾエート４７０ｇ（エポキシ
１当量に対してアミン１当量に相当）をＭＥＫに溶し
た。この溶液を用いて実施例１と同様にして、衝撃後の
残存圧縮強度、圧縮強度９０°引張物性を測定した。そ
の結果を表１及び表２に示す。Comparative Example 1 350 g of N, N, N ', N'-tetraglycidyl diaminodiphenylmethane, 300 g of brominated epoxy resin, 350 g of bisphenol A type epoxy resin, neopentyl glycol, 470 g of di-p-aminobenzoate (1 amine to 1 equivalent of epoxy). Equivalent to) was dissolved in MEK. Using this solution, the residual compressive strength after impact and the 90 ° compressive strength tensile properties were measured in the same manner as in Example 1. The results are shown in Tables 1 and 2.
表１及び表２より、本発明にかかるマトリックス樹脂組
成物より得られるＣＦＲＰは、高温吸湿下の圧縮物性を
損わずに、しかも衝撃特性が非常に優れていることが確
認できたと共に、９０°引張伸度も優れていることが確
認できた。From Table 1 and Table 2, it was confirmed that the CFRP obtained from the matrix resin composition according to the present invention did not impair the compressive physical properties under high temperature moisture absorption and had very excellent impact properties. It was confirmed that the tensile elongation was also excellent.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｌ 63/00 ＮＫＡ 8830−4Ｊ (56)参考文献 特開 昭60−4526（ＪＰ，Ａ) 特開 昭60−58424（ＪＰ，Ａ) 特開 昭58−134126（ＪＰ，Ａ) 特開 昭51−58484（ＪＰ，Ａ)─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location C08L 63/00 NKA 8830-4J (56) Reference JP-A-60-4526 (JP, A) Special features Kai 60-58424 (JP, A) JP 58-134126 (JP, A) JP 51-58484 (JP, A)
Claims (1)
ノジフェニルメタン、ビスフェノールＡ型エポキシ樹
脂、ブロム化エポキシ樹脂、一般式（１） （式中、Ｒは炭素数３〜８のアルキレングリコール、ま
たは、炭素数５〜１４の脂環式ジオールの残基である。
残基とは、アルキレングリコール、または、脂環式ジオ
ールの水酸基を除いたものである。）で示される化合物
を硬化剤として含有するエポキシ樹脂組成物と一般式
（２） で示されるポリエーテルサルホンを含有して成るプリプ
レグ用マトリックス樹脂組成物。1. N, N, N ', N'-tetraglycidyldiaminodiphenylmethane, bisphenol A type epoxy resin, brominated epoxy resin, general formula (1) (In the formula, R is a residue of an alkylene glycol having 3 to 8 carbon atoms or an alicyclic diol having 5 to 14 carbon atoms.
The residue is an alkylene glycol or an alicyclic diol excluding a hydroxyl group. And an epoxy resin composition containing a compound represented by the formula (2) as a curing agent A matrix resin composition for prepreg, comprising the polyether sulfone represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8625585A JPH068340B2 (en) | 1985-04-24 | 1985-04-24 | Matrix resin composition for prepreg |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8625585A JPH068340B2 (en) | 1985-04-24 | 1985-04-24 | Matrix resin composition for prepreg |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61246224A JPS61246224A (en) | 1986-11-01 |
| JPH068340B2 true JPH068340B2 (en) | 1994-02-02 |
Family
ID=13881711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8625585A Expired - Lifetime JPH068340B2 (en) | 1985-04-24 | 1985-04-24 | Matrix resin composition for prepreg |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH068340B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5213886A (en) * | 1989-02-17 | 1993-05-25 | General Electric Company | Curable dielectric polyphenylene ether-polyepoxide compositions |
| US5162450A (en) * | 1989-02-17 | 1992-11-10 | General Electric Company | Curable dielectric polyphenylene ether-polyepoxide compositions |
| JP2016210860A (en) * | 2015-05-01 | 2016-12-15 | 三菱レイヨン株式会社 | Epoxy resin composition and prepreg for fiber-reinforced composite material |
-
1985
- 1985-04-24 JP JP8625585A patent/JPH068340B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61246224A (en) | 1986-11-01 |
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