JP2007291227A - Flame-retardant carbon fiber reinforced composite - Google Patents
Flame-retardant carbon fiber reinforced composite Download PDFInfo
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- JP2007291227A JP2007291227A JP2006120425A JP2006120425A JP2007291227A JP 2007291227 A JP2007291227 A JP 2007291227A JP 2006120425 A JP2006120425 A JP 2006120425A JP 2006120425 A JP2006120425 A JP 2006120425A JP 2007291227 A JP2007291227 A JP 2007291227A
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- VBQRUYIOTHNGOP-UHFFFAOYSA-N O=P1Oc(cccc2)c2-c2c1cccc2 Chemical compound O=P1Oc(cccc2)c2-c2c1cccc2 VBQRUYIOTHNGOP-UHFFFAOYSA-N 0.000 description 1
- KMRIWYPVRWEWRG-UHFFFAOYSA-N Oc(cc1)cc(P2(Oc3ccccc3-c3c2cccc3)=O)c1O Chemical compound Oc(cc1)cc(P2(Oc3ccccc3-c3c2cccc3)=O)c1O KMRIWYPVRWEWRG-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明はそのマトリックス樹脂中にハロゲン原子を含有せず、火災時に有害なガス成分を発生する事がなく、優れた難燃性を有し、機械特性に優れた、炭素繊維強化複合材料を提供するものであり、レジャー及び生活関連用品、自動車、車両、船舶及び航空機等の交通関連用品、一般工業及び産業資材、電子・電気関連資材として広範囲の利用分野で使用される難燃性炭素繊維強化複合材料に関するものである。 The present invention provides a carbon fiber reinforced composite material that does not contain halogen atoms in its matrix resin, does not generate harmful gas components in the event of a fire, has excellent flame retardancy, and has excellent mechanical properties. Reinforced flame retardant carbon fiber used in a wide range of fields such as leisure and life-related products, transportation-related products such as automobiles, vehicles, ships and aircraft, general industrial and industrial materials, and electronic / electrical materials It relates to composite materials.
炭素繊維とマトリックス樹脂からなる炭素繊維強化複合材料は、機械特性、熱的特性に優れ、釣り竿、ゴルフシャフト、テニスラッケト等のレジャー用品、プロペラシャフト、エンジンフード、スポイラー等の自動車部品、工業用ローラー、圧力容器等の工業用部品、電車車体、座席等の鉄道車両、パソコン筐体等の電子材料、船舶、航空機等さまざまな用途に使用されている。 Carbon fiber reinforced composite material consisting of carbon fiber and matrix resin is excellent in mechanical and thermal properties, leisure goods such as fishing rods, golf shafts, tennis rackets, automobile parts such as propeller shafts, engine hoods, spoilers, and industrial rollers. It is used for various applications such as industrial parts such as pressure vessels, railway vehicles such as train bodies, seats, electronic materials such as personal computer cases, ships, and aircraft.
炭素繊維強化複合材料のマトリックス樹脂としては、機械的特性、熱的特性、炭素繊維との密着性に優れるエポキシ樹脂が好適に使用される。エポキシ樹脂としてはビスフェノールＡ型、ビスフェノールＦ型エポキシ樹脂が主として使用されてきたが、従来のエポキシ樹脂／炭素繊維強化複合材料では難燃性、燃焼時の発煙性に問題があった。特に電子材料用途、自動車部品、鉄道車両、航空機等の用途ではエポキシ樹脂／炭素繊維強化複合材料の難燃化、燃焼時の低発煙化への要求が近年高まってきている。 As the matrix resin of the carbon fiber reinforced composite material, an epoxy resin excellent in mechanical properties, thermal properties, and adhesion to carbon fibers is preferably used. As epoxy resins, bisphenol A type and bisphenol F type epoxy resins have been mainly used, but conventional epoxy resins / carbon fiber reinforced composite materials have problems in flame retardancy and smoke generation during combustion. In particular, in applications such as electronic materials, automobile parts, railway vehicles, and aircraft, there has been an increasing demand for flame retardancy of epoxy resin / carbon fiber reinforced composite materials and low smoke generation during combustion.
エポキシ樹脂／炭素繊維の難燃化方法としては、臭素化エポキシ樹脂を使用する方法（特許文献１）が広く採用されてきた。臭素化エポキシ樹脂は良好な難燃性を有するものの、火災時に発生するガスの毒性が問題となり、人体への安全性、地球環境保護の観点から代替方法が望まれている。 As a method for flame retarding epoxy resin / carbon fiber, a method using a brominated epoxy resin (Patent Document 1) has been widely adopted. Although brominated epoxy resins have good flame retardancy, the toxicity of gas generated in the event of a fire becomes a problem, and an alternative method is desired from the viewpoints of safety to the human body and protection of the global environment.
一方、臭素化エポキシ樹脂を代替する難燃化方法として、リン化合物を添加する方法（特許文献２）などがあるが、機械的強度の低下、プリプレグの安定性不良などの問題が多く改良が望まれている。 On the other hand, as a flame retardant method replacing brominated epoxy resin, there is a method of adding a phosphorus compound (Patent Document 2), but there are many problems such as a decrease in mechanical strength and poor stability of prepreg, and improvement is expected. It is rare.
本発明の目的は、マトリックス樹脂がハロゲン原子を含有せず、火災時に有害なガス成分を発生する事がなく、優れた難燃性を有し、機械特性に優れた、難燃性炭素繊維強化複合材料及び炭素繊維プリプレグを提供するものである。 The purpose of the present invention is that the matrix resin does not contain a halogen atom, does not generate harmful gas components in the event of a fire, has excellent flame retardancy, and has excellent mechanical properties, flame retardant carbon fiber reinforcement A composite material and a carbon fiber prepreg are provided.
本発明者は上記課題を解決するため鋭意研究の結果、マトリックス樹脂として特定の構造を有するリン原子含有エポキシ樹脂（Ａ）、非リン含有エポキシ樹脂（Ｂ）、エポキシ樹脂硬化剤（C）を必須とすることにより、難燃性に優れ、良好な機械的特性を有する炭素繊維プリプレグ、及び、難燃性炭素繊維強化複合材料を得ることを見出し本発明に至った。 As a result of diligent research, the present inventor required a phosphorus atom-containing epoxy resin (A), a non-phosphorus-containing epoxy resin (B), and an epoxy resin curing agent (C) having a specific structure as a matrix resin. Thus, the present inventors have found that a carbon fiber prepreg excellent in flame retardancy and good mechanical properties and a flame retardant carbon fiber reinforced composite material can be obtained.
即ち本発明は、リン含有エポキシ樹脂（Ａ）、非リン含有エポキシ樹脂（Ｂ）、とエポキシ樹脂硬化剤（C）を必須成分とするマトリックス樹脂中のリン含有量が０．４〜５．０％であって、リン含有エポキシ樹脂（Ａ）が、一般式（１）及び（２）で表される少なくとも1種のリン化合物と、エポキシ樹脂との反応物であることを特徴とする炭素繊維プリプレグ及び難燃性炭素繊維強化複合材料を提供するものである。 That is, in the present invention, the phosphorus content in the matrix resin containing the phosphorus-containing epoxy resin (A), the non-phosphorus-containing epoxy resin (B), and the epoxy resin curing agent (C) as essential components is 0.4 to 5.0. %, Wherein the phosphorus-containing epoxy resin (A) is a reaction product of at least one phosphorus compound represented by the general formulas (1) and (2) and an epoxy resin. A prepreg and a flame retardant carbon fiber reinforced composite material are provided.
（式中Ｒ１、Ｒ２はＣ１〜Ｃ１２の脂肪族炭化水素基、アリール基、置換アリール基であり、互いに結合して環状構造を形成していても良い。ｎは０又は１）
(Wherein R 1 and R 2 are a C 1 to C 12 aliphatic hydrocarbon group, aryl group, and substituted aryl group, and may be bonded to each other to form a cyclic structure. N is 0 or 1)
本発明の炭素繊維プリプレグは硬化させることにより炭素繊維強化複合材料として、優れた機械的強度を維持し、有害なハロゲン系ガスを発生することなく、難燃性を付与することができる。 The carbon fiber prepreg of the present invention is cured to maintain excellent mechanical strength as a carbon fiber reinforced composite material, and can impart flame retardancy without generating harmful halogen-based gas.
本発明で必須とするリン含有エポキシ樹脂（Ａ）は、前記の一般式（１）又は（２）で表される少なくとも1種のリン化合物と、エポキシ樹脂とを付加反応させて得ることができる。 The phosphorus-containing epoxy resin (A) essential in the present invention can be obtained by addition reaction of at least one phosphorus compound represented by the general formula (1) or (2) with an epoxy resin. .
一般式（１）で表される化合物は活性水素を一個もつリン化合物であり、式中のＲ１、Ｒ２が炭素数１から１２の脂肪族炭化水素基、アリール基または置換アリール基であって、Ｒ１とＲ２が直接結合して環状構造を形成しても良いものである。また、ｎの数は０または１である。Ｒ１、Ｒ２の具体的な例としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、１−メチルブチル基、１−メチルヘプチル基、オクチル基、ノニル基、ドデシル基、ウンデシル基、ドデシル基、ベンジル基、フェニル基、トルイル基、キシリル基等が挙げられ、Ｒ１とＲ２は同一でも異なっていてもかまわない。また、Ｒ１とＲ２が結合して環状構造を形成しているものの例としては、例えば、テトラメチレン、シクロペントレン、シクロヘキシレン、シクロヘブチレン、シクロオクチレン、シクロデシレン、ノルボルニレン基、ビフェニレン基等が挙げられる。これらの中では、一般式（５）で表される９，１０−ジヒドロ−９−オキサ−１０−フォスフォフェナントレン−１０−オキサイドが好ましい。 The compound represented by the general formula (1) is a phosphorus compound having one active hydrogen, and R 1 and R 2 in the formula are an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an aryl group or a substituted aryl group. Thus, R 1 and R 2 may be directly bonded to form a cyclic structure. The number of n is 0 or 1. Specific examples of R 1 and R 2 include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and neopentyl. Group, tert-pentyl group, 1-methylbutyl group, 1-methylheptyl group, octyl group, nonyl group, dodecyl group, undecyl group, dodecyl group, benzyl group, phenyl group, toluyl group, xylyl group, etc. 1 and R 2 may be the same or different. Examples of those in which R 1 and R 2 are bonded to form a cyclic structure include, for example, tetramethylene, cyclopentylene, cyclohexylene, cyclohexylene, cyclooctylene, cyclodecylene, norbornylene group, biphenylene group Etc. Among these, 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide represented by the general formula (5) is preferable.
一般式（２）で表される化合物は、Xが一般式（３）又は（４）で示される活性水素を二個もつリン化合物であり、式中のＲ１、Ｒ２が炭素数１から１２の脂肪族炭化水素基、アリール基または置換アリール基であって、Ｒ１とＲ２が直接結合して環状構造を形成しても良いものである。また、ｍの数は０または１である。R1及びR2の具体例は前記〔００１２〕と同じものを例示できる。Ｒ１とＲ２が直接結合して環状構造を形成している例として一般式（５）で表わされるリン化合物である９，１０−ジヒドロ−９−オキサ−１０−フォスフォフェナントレン−１０−オキサイドであり、Xが一般式（３）又は（４）で示されるリン含有化合物である。これらのリン含有化合物は一般式（５）の化合物と単環又は多環キノン化合物との反応によって得られる。これらのキノン化合物の具体例としては、１，４−ベンゾキノン、１，４−ナフトキノン等を例示できるが、これらに限定されるものではない。 The compound represented by the general formula (2) is a phosphorus compound in which X has two active hydrogens represented by the general formula (3) or (4), and R 1 and R 2 in the formula are from 1 carbon atom. 12 aliphatic hydrocarbon group, an aryl group or a substituted aryl group are those R 1 and R 2 may form a ring structure directly bonded. The number m is 0 or 1. Specific examples of R 1 and R 2 can be the same as the above [0012]. As an example in which R 1 and R 2 are directly bonded to form a cyclic structure, 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, which is a phosphorus compound represented by the general formula (5) And X is a phosphorus-containing compound represented by the general formula (3) or (4). These phosphorus-containing compounds are obtained by reacting the compound of the general formula (5) with a monocyclic or polycyclic quinone compound. Specific examples of these quinone compounds include 1,4-benzoquinone and 1,4-naphthoquinone, but are not limited thereto.
本発明に使用される好ましいリン含有化合物としては、９，１０−ジヒドロ−９−オキサ−１０−フォスフォフェナントレン−１０−オキサイドと１，４−ベンゾキノンの付加反応物である一般式（６）で示されるリン含有化合物であり、商品名「ＨＣＡ−ＨＱ」（三光化学株式会社製、以下ＨＣＡ−ＨＱ略記）として入手することができる。 A preferable phosphorus-containing compound used in the present invention is represented by the general formula (6) which is an addition reaction product of 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide and 1,4-benzoquinone. It is a phosphorus-containing compound shown and can be obtained as a trade name “HCA-HQ” (manufactured by Sanko Chemical Co., Ltd., hereinafter abbreviated as HCA-HQ).
更に、本発明に使用される好ましいリン含有化合物としては、９，１０−ジヒドロ−９−オキサ−１０−フォスフォフェナントレン−１０−オキサイドと１，４−ナフトキノンの付加反応物である一般式（７）で示されるリン含有化合物（以下ＨＣＡ−ＮＱと略記）である。 Furthermore, as a preferable phosphorus-containing compound used in the present invention, a general formula (7) which is an addition reaction product of 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide and 1,4-naphthoquinone is used. ) -Containing compound (hereinafter abbreviated as HCA-NQ).
本発明でマットリック樹脂に使用されるリン含有エポキシ樹脂（Ａ）は、好ましくは前記のリン化合物（５）から（７）の少なくとも１種と、非リン含有エポキシ樹脂であるビスフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂から選ばれた少なくとも1種以上のエポキシ樹脂との付加反応させて得られるが、ＨＣＡ−ＨＱ及びＨＣＡ−ＮＱを使用した場合、分子末端エポキシ官能基は維持できるが、ＨＣＡを使用した場合は減少するので、ＨＣＡは主として当該リン含有エポキシ樹脂の粘度、分子量、リン含有量を調整する目的で使用される。 The phosphorus-containing epoxy resin (A) used for the matric resin in the present invention is preferably a bisphenol-type epoxy resin which is at least one of the phosphorus compounds (5) to (7) and a non-phosphorus-containing epoxy resin, It can be obtained by addition reaction with at least one epoxy resin selected from novolak type epoxy resins, but when HCA-HQ and HCA-NQ are used, molecular terminal epoxy functional groups can be maintained, but HCA is used. Therefore, HCA is mainly used for the purpose of adjusting the viscosity, molecular weight, and phosphorus content of the phosphorus-containing epoxy resin.
リン含有エポキシ樹脂（Ａ）の出発原料となるエポキシ樹脂はグリシジルエーテル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、グリシジルエステル型エポキシ樹脂が挙げられ、これらのなかではグリシジルエーテル型エポキシ樹脂が好ましい。 Examples of the epoxy resin that is a starting material for the phosphorus-containing epoxy resin (A) include glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, and glycidyl ester type epoxy resins. Among these, glycidyl ether type epoxy resins are preferred.
グリシジルエーテル型エポキシ樹脂としては、ビスフェノール型エポキシ樹脂、ビフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、レゾルシン型エポキシ樹脂、ジフェニルエーテル型エポキシ樹脂、ナフトール型エポキシ樹脂が挙げられ、これらのなかではビスフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂が好ましい。 Examples of glycidyl ether type epoxy resins include bisphenol type epoxy resins, biphenol type epoxy resins, novolac type epoxy resins, hydroquinone type epoxy resins, resorcin type epoxy resins, diphenyl ether type epoxy resins, and naphthol type epoxy resins. Bisphenol type epoxy resins and novolac type epoxy resins are preferred.
ビスフェノール型エポキシ樹脂としてはビスフェノール型エポキシ樹脂としてはビスフェノール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、テトラメチルビスフェノールＦ型エポキシ樹脂等が挙げられ、これらのなかではビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂が好ましい。またノボラック型エポキシ樹脂としてはフェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂、フェノールアラルキルノボラック型エポキシ樹脂、ナフトールアラルキルノボラック型エポキシ樹脂、フェノールビフェニルノボラック型エポキシ樹脂等が挙げられるが、これらのなかではフェノールノボラック型エポキシ樹脂が好ましい。 Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetramethylbisphenol F type epoxy resin, and the like. Among these, bisphenol A type epoxy resin Resin and bisphenol F type epoxy resin are preferable. Examples of novolak type epoxy resins include phenol novolak type epoxy resins, orthocresol novolak type epoxy resins, phenol aralkyl novolak type epoxy resins, naphthol aralkyl novolak type epoxy resins, and phenol biphenyl novolak type epoxy resins. Phenol novolac type epoxy resins are preferred.
リン含有エポキシ樹脂（Ａ）の出発原料となるビスフェノール型エポキシ樹脂としては、分子量の低いものが好ましく、例えば商品名「エポトートＹＤ−８１２５」、「エポトートＹＤ−１２７」、「エポトートＹＤ−１２８」、「エポトートＹＤ−１３４」、「エポトートＹＤ−０１１」等のビスフェノールＡ型エポキシ樹脂、商品名「エポトートＹＤＦ−８１７０」、「エポトートＹＤＦ−８１７０Ｃ」、「エポトートＹＤＦ−１７０」、「エポトートＹＤＦ−２００１」等のビスフェノールＦ型樹脂、また、ノボラック型エポキシ樹脂としては例えば商品名「エポトートＹＤＰＮ−６３８」（いずれも東都化成製）等が挙げられるがこれらに限定されるものではない。 As the bisphenol type epoxy resin used as a starting material for the phosphorus-containing epoxy resin (A), those having a low molecular weight are preferable. For example, trade names “Epototo YD-8125”, “Epototo YD-127”, “Epototo YD-128”, Bisphenol A type epoxy resins such as “Epototo YD-134” and “Epototo YD-011”, trade names “Epototo YDF-8170”, “Epototo YDF-8170C”, “Epototo YDF-170”, “Epototo YDF-2001” Examples of the bisphenol F-type resin and the novolak-type epoxy resin include, for example, “Epototo YDPN-638” (all manufactured by Toto Kasei) and the like, but are not limited thereto.
リン含有化合物（６）及び／又は（７）の活性水素、または必要に応じてリン化合物（５）の活性水素とエポキシ樹脂のエポキシ基との仕込比率は、エポキシ基が過剰である必要があり、エポキシ基１当量当たり、リン化合物の活性水素の合計が０．１〜０．９９当量が好ましく、更に好ましくは０．２〜０．９の範囲である。この反応は公知の方法によれば良く、例えばアルカリ金属水酸化物、三級アミン類、四級アンモニウム塩類、イミダゾール類、トリフェニルフォスフイン、ホスフォニウム塩類、等の触媒の存在下、反応温度５０〜２５０℃、反応時間０．５〜２０時間の条件で反応することができる。２種以上のリン化合物と２種以上のエポキシ樹脂を使用する場合、夫々同時に、或いは逐次に反応してもかまわない。 The active hydrogen of the phosphorus-containing compound (6) and / or (7) or, if necessary, the charge ratio of the active hydrogen of the phosphorus compound (5) and the epoxy group of the epoxy resin, the epoxy group must be excessive. The total active hydrogen of the phosphorus compound is preferably 0.1 to 0.99 equivalent, more preferably 0.2 to 0.9, per equivalent of epoxy group. This reaction may be performed by a known method. For example, in the presence of a catalyst such as an alkali metal hydroxide, a tertiary amine, a quaternary ammonium salt, an imidazole, triphenylphosphine, a phosphonium salt, a reaction temperature of 50 to The reaction can be carried out under the conditions of 250 ° C. and reaction time of 0.5 to 20 hours. When using 2 or more types of phosphorus compounds and 2 or more types of epoxy resins, you may react simultaneously or sequentially, respectively.
リン含有化合物、エポキシ樹脂の種類、リン含有化合物の活性水素とエポキシ樹脂のエポキシ基の仕込比率により、常温で液状から固形のエポキシ当量１６０〜２，０００ｇ／ｅｑ、リン含有量０．５〜７．０重量％のリン含有エポキシ樹脂（Ａ）を製造することができる。前記リン含有化合物の仕込み比率の小さい場合は、実質的にリン含有エポキシ樹脂（Ａ）と非リン含有エポキシ樹脂の混合物となる。マトリックス樹脂中のリン含有エポキシ樹脂（A）の含有比率はそのリン含有比率に因るが２５〜９５重量％、より好ましくは３０重量％から９０重量％である。 Phosphorus-containing compound, epoxy resin type, active hydrogen of phosphorus-containing compound and epoxy resin charge ratio of epoxy group, liquid to solid epoxy equivalent of 160 to 2,000 g / eq at room temperature, phosphorus content of 0.5 to 7 0.0% by weight of phosphorus-containing epoxy resin (A) can be produced. When the charging ratio of the phosphorus-containing compound is small, the mixture is substantially a mixture of the phosphorus-containing epoxy resin (A) and the non-phosphorus-containing epoxy resin. The content ratio of the phosphorus-containing epoxy resin (A) in the matrix resin is 25 to 95% by weight, more preferably 30% to 90% by weight, although it depends on the phosphorus content ratio.
本発明の炭素繊維プリプレグはリン含有エポキシ樹脂（Ａ）以外の非リン含有エポキシ樹脂（Ｂ）も必須である。係る非リン含有エポキシ樹脂の例としては、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、テトラメチルビスフェノールＦ型エポキシ樹脂、ビフェニル型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、レゾルシン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、アミノフェノール型エポキシ樹脂、トリグリシジルイソシアヌレート型樹脂、ジシクロペンタジエン型エポキシ樹脂、ウレタン変性エポキシ樹脂、オキサゾリドン環含有エポキシ樹脂等が挙げられるがこれらに限定されるものではない。 In the carbon fiber prepreg of the present invention, a non-phosphorus-containing epoxy resin (B) other than the phosphorus-containing epoxy resin (A) is also essential. Examples of such non-phosphorus-containing epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, tetramethylbisphenol F type epoxy resins, biphenyl type epoxy resins, hydroquinone type epoxy resins, and resorcin type epoxy resins. Resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, glycidyl amine type epoxy resin, aminophenol type epoxy resin, triglycidyl isocyanurate type resin, dicyclopentadiene type epoxy resin, urethane modified epoxy resin, oxazolidone ring containing epoxy Examples of the resin include, but are not limited to, resin.
本発明の炭素繊維プリプレグはリン含有エポキシ樹脂（Ａ）、非リン含有エポキシ樹脂（Ｂ）の他にフェノキシ樹脂（E）を配合することができる。フェノキシ樹脂は、マトリックス樹脂に、可撓性、耐衝撃性、接着力の付与、適度の粘性を目的に配合されるものであり、その配合量は全マトリックス樹脂に対して、０〜２０重量％の範囲で、より好ましくは０.５〜１５重量％、更に好ましくは１.０〜１３重量％である。フェノキシ樹脂（E）は、一般式（８）で示される。 The carbon fiber prepreg of the present invention can contain a phenoxy resin (E) in addition to a phosphorus-containing epoxy resin (A) and a non-phosphorus-containing epoxy resin (B). The phenoxy resin is blended in the matrix resin for the purpose of flexibility, impact resistance, adhesion, and moderate viscosity. The blending amount is 0 to 20% by weight based on the total matrix resin. More preferably, it is 0.5-15 weight%, More preferably, it is 1.0-13 weight%. The phenoxy resin (E) is represented by the general formula (8).
具体的に本発明で使用される２価フェノール類を例示すると、ハイドロキノン、レゾルシン、カテコール、２，５−ジターシャリーブチルハイドロキノン等の２価単核フェノール類、ビスフェノールＡ（以下ＢＰＡと略記），ビスフェノールＢ、ビスフェノールＥ、ビスフェノールK、ビスフェノールＦ（以下ＢＰＦと略記）、ビスフェノールＳ（以下ＢＰＳと略記）、３，３’−５，５’−テトラメチルビスフェノールＦ等の２価多核ビスフェノール類、１，４−ナフタレンジオール、１，６−ナフタレンジオール等のナフタレンジオール類、４、４’−ビフェノール、３,３’−５，５’テトラメチルビフェノール等のビフェノール類、ビスフェノールフルオレイン等の環を有するビスフェノール類等である。フェノキシ樹脂は、係る２価フェノール類とアルカリ金属水酸化物の存在下にエピクロルヒドリンと反応させる直接製造法で有ってもよく、前記２価フェノール類と２官能のエポキシ樹脂との反応による間接製造法によるものであっても良い。係るフェノキシ樹脂の分子量としては、標準ポリスチレンを標準物質としてゲル浸透クロマトグラフィー（ＧＰＣ）によって測定された数平均分子量が３，０００〜１００，０００、更に好ましくは、５，０００〜８０，０００程度のものが好ましい。フェノキシ樹脂の具体的な市販品としては何れも東都化成株式会社製である「フェノトートＹＰ−４０」、「フェノトートＹＰ−５０」、「フェノトートＹＰ−５０S」等のＢＰＡ型フェノキシ樹脂、「フェノトートYP-７０」等のＢＰＡ／ＢＰＦ型フェノキシ樹脂、「フェノトートＥＲＦ−００１」等のリン含有フェノキシ樹脂、「フェノトートＹＰＳ−００７」等のビスフェノールスルフォン型フェノキシ樹脂を例示することが出来る。
また、フェノキシ樹脂以外の樹脂成分としてポリビニルホルマール、ポリスルフォン、ポリエーテルスルホン、ポリエーテルイミド、ポリフェニレンサルファイド等の熱可塑性樹脂を本発明の効果を損なわない範囲で配合することもできる。
Specific examples of dihydric phenols used in the present invention include dihydric mononuclear phenols such as hydroquinone, resorcin, catechol, 2,5-ditertiary butyl hydroquinone, bisphenol A (hereinafter abbreviated as BPA), bisphenol. B, bisphenol E, bisphenol K, bisphenol F (hereinafter abbreviated as BPF), bisphenol S (hereinafter abbreviated as BPS), divalent polynuclear bisphenols such as 3,3′-5,5′-tetramethylbisphenol F, 1, Naphthalenediols such as 4-naphthalenediol and 1,6-naphthalenediol, biphenols such as 4,4′-biphenol, 3,3′-5,5′tetramethylbiphenol, and bisphenol having a ring such as bisphenolfluorene Etc. The phenoxy resin may be a direct production method in which the dihydric phenol is reacted with epichlorohydrin in the presence of an alkali metal hydroxide, and indirect production by reaction of the dihydric phenol with a bifunctional epoxy resin. It may be by law. The molecular weight of the phenoxy resin is such that the number average molecular weight measured by gel permeation chromatography (GPC) using standard polystyrene as a standard substance is about 3,000 to 100,000, more preferably about 5,000 to 80,000. Those are preferred. As specific commercial products of phenoxy resin, BPA type phenoxy resins such as “Phenotote YP-40”, “Phenotote YP-50”, “Phenototo YP-50S”, etc., all manufactured by Tohto Kasei Co., Ltd., “ Examples thereof include BPA / BPF type phenoxy resins such as “phenototo YP-70”, phosphorus-containing phenoxy resins such as “phenototo ERF-001”, and bisphenol sulfone type phenoxy resins such as “phenototo YPS-007”.
Moreover, as a resin component other than the phenoxy resin, a thermoplastic resin such as polyvinyl formal, polysulfone, polyethersulfone, polyetherimide, polyphenylene sulfide, etc. can be blended within a range not impairing the effects of the present invention.
本発明の炭素繊維プリプレグはエポキシ樹脂硬化剤（C）を必須成分として含有する。好ましい硬化剤としては所謂、潜在性硬化剤とされるものが望ましい。係る硬化剤の例としては、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルスルフォン、３，３’−ジアミノジフェニルスルフォン、ジアミノエチルベンゼン等の芳香族アミン類、フェノールノボラック、アルキルフェノールノボラック、アラルキルフェノールノボラック、トリアジン環含有ノボラックフェノール、ビフェニルアラルキルフェノール、ナフタレンアラルキルフェノール、トリスフェニルメタン、テトラキスフェニルエタン等の多価フェノール類及びそれらのアルキルエステル類、アジピン酸ジヒドラジド、セバチン酸ジヒドラジド等のヒドラジド類、イミダゾール化合物類及びその塩類、ジシアンジアミド、アミノ安息酸エステル類、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、メタキシレンジアミン、イソホロンジアミン等の脂肪族アミン類等が挙げられるがこれらに限定するものではない。また、必要に応じて３−（３，４−ジクロロジフェニル）−１，１−ジメチルウレア、３−（４−クロロフェニル）−１，１−ジメチルウレア、３−フェニルー１，１―ジメチルウレア、イミダゾール類、三弗化硼素モノエチルアミン錯体、三塩化ホウ素モノエチル錯体等の促進剤を併用することもできる。 The carbon fiber prepreg of the present invention contains an epoxy resin curing agent (C) as an essential component. As a preferable curing agent, what is called a latent curing agent is desirable. Examples of such curing agents include aromatic amines such as 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, diaminoethylbenzene, phenol novolac, alkylphenol novolac, and aralkyl. Polyhydric phenols such as phenol novolak, triazine ring-containing novolak phenol, biphenyl aralkyl phenol, naphthalene aralkyl phenol, trisphenyl methane, tetrakis phenyl ethane and their alkyl esters, hydrazides such as adipic acid dihydrazide, sebacic acid dihydrazide, imidazole Compounds and salts thereof, dicyandiamide, aminobenzoic acid esters, diethylenetriamine, triethylenetetramine, tetraethylene Ntamin, meta-xylene diamine; and aliphatic amines such as isophorone diamine, and the like are not limited to. If necessary, 3- (3,4-dichlorodiphenyl) -1,1-dimethylurea, 3- (4-chlorophenyl) -1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, imidazole Further, accelerators such as boron trifluoride monoethylamine complex and boron trichloride monoethyl complex can be used in combination.
本発明の炭素繊維プリプレグに使用する炭素繊維としては、ＰＡＮ系炭素繊維、ピッチ系炭素繊維、レーヨン系炭素繊維が挙げられ、これらのなかではＰＡＮ系炭素繊維、ピッチ系炭素繊維が好ましい。 Examples of the carbon fiber used in the carbon fiber prepreg of the present invention include PAN-based carbon fiber, pitch-based carbon fiber, and rayon-based carbon fiber. Among these, PAN-based carbon fiber and pitch-based carbon fiber are preferable.
本発明の炭素繊維プリプレグを製造する方法は特に制限はなく、先ず、例えばリン含有エポキシ樹脂（Ａ）と非リン含有エポキシ樹脂（Ｂ）、フェノキシ樹脂（E）を攪拌により均一に混合後、エポキシ樹脂硬化剤成分（C）を添加して均一に混合しマトリックス樹脂組成物とする。成形後のボイドの発生を少なくする目的で、攪拌時しながら真空脱気する方法が好ましく採用される。その後、炭素繊維にマトリックス樹脂組成物を含浸して炭素繊維プリプレグとすることができる。またプリプレグの形態としてはヤーンプリプレグ、シートプリプレグが挙げられ、シートプリプレグとしては一方向プリプレグ、二方向プリプレグ、不織布プリプレグが挙げられる。 The method for producing the carbon fiber prepreg of the present invention is not particularly limited. First, for example, a phosphorus-containing epoxy resin (A), a non-phosphorus-containing epoxy resin (B), and a phenoxy resin (E) are uniformly mixed by stirring, and then an epoxy A resin curing agent component (C) is added and mixed uniformly to obtain a matrix resin composition. For the purpose of reducing the generation of voids after molding, a method of vacuum degassing while stirring is preferably employed. Thereafter, carbon fiber can be impregnated with a matrix resin composition to obtain a carbon fiber prepreg. Examples of the prepreg include yarn prepreg and sheet prepreg. Examples of the sheet prepreg include unidirectional prepreg, bidirectional prepreg, and non-woven prepreg.
本発明の炭素繊維プリプレグ中のリン含有量は０．４〜５．０重量％が好ましい。０．４重量%以下では難燃性が得られず、５.０重量%を超えるとコスト高となり経済性が低下する。本発明ではリン源として一般式（１）又は（２）のリン化合物を使用し、その後のエポキシ樹脂との反応でも、リン原子の損失は起らないので、（１）又は（２）のリン含有量から最終炭素繊維プリプレグ中のリン含有量が簡単な計算により求める事ができる。
因みに一般式（６）のＨＣＡ−ＨＱのリン含有量は９.５７重量％、一般式（７）のＨＣＡ−ＮＱは８．２７重量％、一般式（５）のＨＣＡは１４.４重量％である。
The phosphorus content in the carbon fiber prepreg of the present invention is preferably 0.4 to 5.0% by weight. If it is 0.4% by weight or less, flame retardancy cannot be obtained, and if it exceeds 5.0% by weight, the cost is increased and the economic efficiency is lowered. In the present invention, the phosphorus compound of the general formula (1) or (2) is used as the phosphorus source, and loss of phosphorus atoms does not occur even in the subsequent reaction with the epoxy resin. Therefore, the phosphorus of (1) or (2) The phosphorus content in the final carbon fiber prepreg can be determined from the content by simple calculation.
Incidentally, the phosphorus content of the HCA-HQ of the general formula (6) is 9.57% by weight, the HCA-NQ of the general formula (7) is 8.27% by weight, and the HCA of the general formula (5) is 14.4% by weight. It is.
本発明の炭素繊維プリプレグを硬化することにより得られる種々の炭素繊維強化複合材料も本発明の提供するものである。成形方法としては特に制限されるものではなく、プレス成形法、シートワインディング法、オートクレーブ成形法等によって行うことができる。 Various carbon fiber reinforced composite materials obtained by curing the carbon fiber prepreg of the present invention are also provided by the present invention. The molding method is not particularly limited, and can be performed by a press molding method, a sheet winding method, an autoclave molding method, or the like.
また、本発明難燃性炭素繊維複合材料は、フィラメントワインディング法またはプルトリュージョン法またはレジントランスファーモールディング法により成形、硬化させることによりプリプレグを経由しないで炭素繊維強化複合材料を得る方法も本発明の提供するものである。 In addition, the flame retardant carbon fiber composite material of the present invention is a method of obtaining a carbon fiber reinforced composite material without passing through a prepreg by molding and curing by a filament winding method, a pultrusion method, or a resin transfer molding method. It is to provide.
本発明の炭素繊維強化複合材料は、３ｍｍの厚みに成形した時の難燃性がＵＬ−９４に規定するV−０、V―１及びＶ−2のものを得ることができる。 The carbon fiber reinforced composite material of the present invention can obtain V-0, V-1 and V-2 whose flame retardancy when molded to a thickness of 3 mm is defined in UL-94.
〔実施例〕
次に実施例及び比較例にて本発明を具体的に説明するが、本発明は実施例のみに制限されるものではない。尚、実施例、比較例の「部」は重量部を意味する。また、エポキシ当量の測定法はＪＩＳ K−７２３６、プリプレグ中のマトリックス樹脂含有量の測定法はＪＩＳ K―７０７１、繊維体積含有率はＪＩＳ H-７４０１、引張り強度の測定はＪＩＳ K-７１１３に準じた。
〔Example〕
EXAMPLES Next, although an Example and a comparative example demonstrate this invention concretely, this invention is not restrict | limited only to an Example. In the examples and comparative examples, “parts” means parts by weight. Moreover, the measurement method of epoxy equivalent is JIS K-7236, the measurement method of the matrix resin content in the prepreg is JIS K-7071, the fiber volume content is JIS H-7401, and the measurement of tensile strength is according to JIS K-7113. It was.
〔合成例１〕 リン含有エポキシ樹脂（Ａ−１）の合成
攪拌装置、温度計、窒素導入管、コンデンサーを装備したガラス製セパラブルフラスコに、エポトートＹＤＦ−１７０（ビスフェノールF型エポキシ樹脂、エポキシ当量１６８ｇ／ｅｑ 東都化成株式会社製）７９６.１部、ＨＣＡ（三光化学株式会社）１３３．９部、ＨＣＡ−ＮＱ７０.０部及びトリフェニルホスフィン０．１５部を仕込み、窒素雰囲気下、攪拌しながら１６０℃まで昇温して４時間反応を行った。反応後、冷却して抜き出し、エポキシ当量２６７．１ｇ／ｅｑ、リン含有量２．５０重量％の常温で液状のリン含有エポキシ樹脂（Ａ−１）を得た。
[Synthesis Example 1] Synthesis of Phosphorus-Containing Epoxy Resin (A-1) A glass separable flask equipped with a stirrer, thermometer, nitrogen inlet tube and condenser was added to Epototo YDF-170 (bisphenol F type epoxy resin, epoxy equivalent). 168 g / eq Toto Kasei Co., Ltd.) 796.1 parts, HCA (Sanko Chemical Co., Ltd.) 133.9 parts, HCA-NQ 70.0 parts and triphenylphosphine 0.15 parts are charged with stirring in a nitrogen atmosphere. The temperature was raised to 160 ° C. and the reaction was carried out for 4 hours. After the reaction, the mixture was cooled and extracted to obtain a phosphorus-containing epoxy resin (A-1) that was liquid at room temperature with an epoxy equivalent of 267.1 g / eq and a phosphorus content of 2.50% by weight.
〔合成例２〕 リン含有エポキシ樹脂（Ａ−２）の合成
合成例１と同じ反応装置にエポトートＹＤＦ−８１７０（ビスフェノールF型エポキシ樹脂、エポキシ当量１５８ｇ／ｅｑ 東都化成株式会社製）２８６部、エポトートＹＤＰＮ−６３８（フェノールノボラック型エポキシ樹脂、エポキシ当量１６８ｇ／ｅｑ 東都化成株式会社製）４２９部、ＨＣＡ−ＮＱ７１部、ＨＣＡ（三光化学株式会社）２１４部及びトリフェニルホスフィン０．３部を仕込み、窒素雰囲気下、攪拌しながら１６０℃まで昇温して５時間反応を行った。反応後、冷却して抜き出し、エポキシ当量３５０ｇ／ｅｑ、リン含有量３.６６重量%の常温で半固形状のリン含有エポキシ樹脂（A−２）を得た。
[Synthesis Example 2] Synthesis of Phosphorus-Containing Epoxy Resin (A-2) In the same reactor as in Synthesis Example 1, 286 parts of Epototo YDF-8170 (bisphenol F type epoxy resin, epoxy equivalent 158 g / eq, manufactured by Toto Kasei Co., Ltd.), Epototo YDPN-638 (phenol novolac type epoxy resin, epoxy equivalent 168 g / eq, manufactured by Tohto Kasei Co., Ltd.) 429 parts, HCA-NQ 71 parts, HCA (Sanko Chemical Co., Ltd.) 214 parts and triphenylphosphine 0.3 part were charged, nitrogen While stirring, the temperature was raised to 160 ° C. and the reaction was carried out for 5 hours. After the reaction, it was cooled and extracted to obtain a semi-solid phosphorus-containing epoxy resin (A-2) at room temperature having an epoxy equivalent of 350 g / eq and a phosphorus content of 3.66% by weight.
〔合成例３〕リン含有エポキシ樹脂（Ａ−３）の合成
合成例１と同じ反応装置にエポトートYD―１２８（ビスフェノールＡ型エポキシ樹脂、 エポキシ当量１８７g/eq 東都化成株式会社製）２６７部、エポトートＹＤＰＮ−６３８ ４２９部、ＨＣＡ−ＨＱ（三光化学株式会社）１３３部、ＨＣＡ２００部及びトリフェニルホスフィン０．４３部を仕込み、攪拌しながら１６０℃まで昇温して６時間反応を行った。反応後、冷却して抜き出し、エポキシ当量５２０ｇ／ｅｑ、リン含有量４.１６重量%の常温で固形状のリン含有エポキシ樹脂（Ａ―３）を得た。
[Synthesis Example 3] Synthesis of Phosphorus-Containing Epoxy Resin (A-3) In the same reactor as Synthesis Example 1, 267 parts of Epototo YD-128 (bisphenol A type epoxy resin, epoxy equivalent 187 g / eq, manufactured by Tohto Kasei Co., Ltd.), Epototo 429 parts of YDPN-638, 133 parts of HCA-HQ (Sanko Chemical Co., Ltd.), 200 parts of HCA and 0.43 part of triphenylphosphine were charged, and the temperature was raised to 160 ° C. with stirring, and the reaction was performed for 6 hours. After the reaction, the mixture was cooled and extracted to obtain a phosphorus-containing epoxy resin (A-3) that was solid at room temperature with an epoxy equivalent of 520 g / eq and a phosphorus content of 4.16 wt%.
リン含有エポキシ樹脂（Ａ−１）８１部、エポトートYDF―１７０（B―２）１９部、ジシアンジアミド（以下ＤＩＣＹと略記する）４部及び３−（３，４−ジクロロジフェニル）−１，１−ジメチルウレア（以下ＤＣＭＵと略記する）３部を加熱ニーダーに入れて加熱混合し、リン含有量１.８９重量%のマトリックス樹脂（Ｒ−１）を得た。
次に市販の高強度炭素繊維（Ｔ７００ 引張強さ４．８ＧＰａ、引張弾性率２３５ＧＰａ 東レ株式会社製）を一方向に引き揃えた後に、（Ｒ−１）を加熱溶融し、圧力を加えて含浸させマトリックス樹脂含有率３５%の一方向炭素繊維プリプレグ（Ｐ−１）を得た。
（P−１）を長さ３０ｃｍ、幅３０ｃｍに裁断したものを繊維方向が同一になるように１７枚積層して積層体を形成し、リリースクロスを重ねた後、ブリーダークロスを重ね、更にブリーダークロスを重ね、ナイロンパックで包み、成形用スタックを形成した。この形成用スタックを１３０℃、１時間の条件下でオートクレーブ成形して厚み２mm、繊維体積含有率６０%の炭素繊維複合材料を得た。曲げ強度は１．５６ＧＰａ、曲げ弾性率は１２５ＧＰａであった。
また、（P−１）を２５枚重ね同様にスタック形成、硬化を行い長さ１２７ｍｍ、幅１２.７mm、厚み３mmに切り出した試験片を用いたＵＬ−９４の垂直燃焼試験による判定はＶ−０であった。
81 parts of phosphorus-containing epoxy resin (A-1), 19 parts of epototo YDF-170 (B-2), 4 parts of dicyandiamide (hereinafter abbreviated as DICY) and 3- (3,4-dichlorodiphenyl) -1,1- 3 parts of dimethyl urea (hereinafter abbreviated as DCMU) was placed in a heating kneader and mixed by heating to obtain a matrix resin (R-1) having a phosphorus content of 1.89% by weight.
Next, after aligning commercially available high-strength carbon fiber (T700 tensile strength 4.8 GPa, tensile elastic modulus 235 GPa Toray Co., Ltd.) in one direction, (R-1) is heated and melted, and pressure is applied to impregnate. A unidirectional carbon fiber prepreg (P-1) having a matrix resin content of 35% was obtained.
17 pieces of (P-1) cut to a length of 30 cm and a width of 30 cm are laminated so as to have the same fiber direction to form a laminate, and after a release cloth is overlaid, a bleeder cloth is overlaid, and further a bleeder The cloth was stacked and wrapped in a nylon pack to form a molding stack. This forming stack was autoclaved at 130 ° C. for 1 hour to obtain a carbon fiber composite material having a thickness of 2 mm and a fiber volume content of 60%. The bending strength was 1.56 GPa and the flexural modulus was 125 GPa.
In addition, the determination by the vertical combustion test of UL-94 using a test piece cut out to a length of 127 mm, a width of 12.7 mm, and a thickness of 3 mm by stacking and curing (P-1) in the same manner as 25 stacks is V- 0.
リン含有エポキシ樹脂（Ａ−２）３０部、エポトートＹＤ−１２８（B−１） ６０部、フェノトートＹＰ−５０Ｓ（E―１）（ビスフェノールA型フェノキシ樹脂）１０部を加熱ニーダーに入れ加熱混合した。更にＤＩＣＹ４部、ＤＣＭＵ３部を添加して混合し、リン含有量１.０１重量%のマトリックス樹脂（Ｒ−２）を得た。
以下実施例1と同様にスタック形成、オートクレーブ成形を行い曲げ強度試験片、燃焼試験片を得た。曲げ強度は１.６５GPa、曲げ弾性率は１３０GPa、燃焼性判定はUL―９４ V−１であった。
30 parts of phosphorus-containing epoxy resin (A-2), 60 parts of Epototo YD-128 (B-1), 10 parts of phenototo YP-50S (E-1) (bisphenol A type phenoxy resin) are placed in a heating kneader and mixed by heating. did. Further, 4 parts of DICY and 3 parts of DCMU were added and mixed to obtain a matrix resin (R-2) having a phosphorus content of 1.01% by weight.
Thereafter, stack formation and autoclave molding were performed in the same manner as in Example 1 to obtain a bending strength test piece and a combustion test piece. The bending strength was 1.65 GPa, the flexural modulus was 130 GPa, and the flammability determination was UL-94 V-1.
リン含有エポキシ樹脂（A−３）４０部、YDF−１７０（B−２） ５０部、YDPN―６３８（B−３）１０部を加熱ニーダーに入れ加熱混合した。更にDICY ４部、DCMU ４部を添加して混合しリン含有量１.５４重量%のマトリックス樹脂（R−３）を得た。
以下実施例1と同様にスタック形成、オートクレーブ成形を行い曲げ強度試験片、燃焼試験片を得た。曲げ強度は１.５５ＧＰａ、曲げ弾性率は１２１ＧＰａ、燃焼性判定はＵＬ−９４でV−０であった。
40 parts of phosphorus-containing epoxy resin (A-3), 50 parts of YDF-170 (B-2) and 10 parts of YDPN-638 (B-3) were placed in a heating kneader and mixed by heating. Further, 4 parts of DICY and 4 parts of DCMU were added and mixed to obtain a matrix resin (R-3) having a phosphorus content of 1.54% by weight.
Thereafter, stack formation and autoclave molding were performed in the same manner as in Example 1 to obtain a bending strength test piece and a combustion test piece. The bending strength was 1.55 GPa, the flexural modulus was 121 GPa, and the flammability determination was UL-0 and V-0.
〔比較例1〕
リン含有エポキシ樹脂（A−１）の代わりに、エポキシ樹脂をＹＤＦ−１７０（B―２） １００部とした以外は実施例1と同様の操作を行いマトリックス樹脂（R−４）を得た。また、実施例1と同様にスタック形成、オートクレーブ成形を行い曲げ強度試験片、燃焼試験片を得た。曲げ強度は曲げ強度は１．４２ＧＰａ、曲げ弾性率は１４５ＧＰａ、燃焼性試験では燃焼した。
(Comparative Example 1)
A matrix resin (R-4) was obtained in the same manner as in Example 1, except that 100 parts of YDF-170 (B-2) was used instead of the phosphorus-containing epoxy resin (A-1). Further, in the same manner as in Example 1, stack formation and autoclave molding were performed to obtain a bending strength test piece and a combustion test piece. Regarding the bending strength, the bending strength was 1.42 GPa, the bending elastic modulus was 145 GPa, and burning occurred in the flammability test.
〔比較例２〕
リン含有エポキシ樹脂（Ａ−２）３０部の代わりにＹＤＦ−１７０（B−２） １５部、ＹＤＦ−２００１（B−４）（ビスフェノールF型固形エポキシ樹脂、エポキシ当量４７５g/eq）１５部とした以外は実施例２と同様の操作を行いエポキシ樹脂組成物（R−５）を得た。以下同様にスタック形成、オートクレーブ成形を行い試験片を得た。曲げ強度は１．５８ＧＰａ、曲げ弾性率は１３５ＧＰａ、燃焼性試験では燃焼した。
[Comparative Example 2]
15 parts of YDF-170 (B-2) instead of 30 parts of phosphorus-containing epoxy resin (A-2), 15 parts of YDF-2001 (B-4) (bisphenol F-type solid epoxy resin, epoxy equivalent 475 g / eq) Except having been performed, operation similar to Example 2 was performed and the epoxy resin composition (R-5) was obtained. Thereafter, stack formation and autoclave molding were similarly performed to obtain test pieces. The bending strength was 1.58 GPa, the flexural modulus was 135 GPa, and it burned in the flammability test.
〔比較例3〕
リン含有エポキシ樹脂（Ａ−３）４０部の代わりにエポトートＹＤ−０１１（B−５）（ビスフェノールＡ型固形エポキシ樹脂、エポキシ当量＝４７５ｇ／ｅｑ 東都化成株式会社製）とした以外は実施例3と同様の操作を行いマトリックス樹脂（R−６）を得た。以下同様にスタック形成、オートクレーブ成形を行い試験片を得た。曲げ強度は１．５２ＧＰａ、曲げ弾性率は１２３ＧＰａ、燃焼性試験では燃焼した。
(Comparative Example 3)
Example 3 except that 40 parts of phosphorus-containing epoxy resin (A-3) was replaced with Epototo YD-011 (B-5) (bisphenol A type solid epoxy resin, epoxy equivalent = 475 g / eq, manufactured by Toto Kasei Co., Ltd.) The matrix resin (R-6) was obtained by performing the same operation as. Thereafter, stack formation and autoclave molding were similarly performed to obtain test pieces. The bending strength was 1.52 GPa, the flexural modulus was 123 GPa, and it burned in the flammability test.
Claims (8)
（式中Ｒ１、Ｒ２はＣ１〜Ｃ１２の脂肪族炭化水素基、アリール基、置換アリール基であり、互いに結合して環状構造を形成していても良い。ｎは０又は１。）
（式中Ｒ３、Ｒ４はＣ１〜Ｃ１２の脂肪族炭化水素基、アリール基、置換アリール基であり、互いに結合して環状構造を形成していても良い。ｍは０又は１。式中Ｘは一般式（３）又は一般式（４）を示す。）
(Wherein R 1 and R 2 are a C 1 to C 12 aliphatic hydrocarbon group, aryl group, and substituted aryl group, and may be bonded to each other to form a cyclic structure. N is 0 or 1. )
(Wherein R 3 and R 4 are a C 1 to C 12 aliphatic hydrocarbon group, aryl group, and substituted aryl group, and may be bonded to each other to form a cyclic structure. M is 0 or 1. In the formula, X represents the general formula (3) or the general formula (4).
A flame retardant carbon fiber reinforced composite material obtained by curing the flame retardant carbon fiber prepreg according to claim 7.
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| JP2010100802A (en) * | 2008-09-24 | 2010-05-06 | Sekisui Chem Co Ltd | Epoxy-based resin composition, sheet-like molded product, prepreg, cured product, laminated plate, and multilayer laminated plate |
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