JP4975610B2 - 低熱放出性低煙性強化繊維/エポキシ組成物 - Google Patents
低熱放出性低煙性強化繊維/エポキシ組成物 Download PDFInfo
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
- C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明の更なる目的は、強化繊維を割ったり拡散したりすることなしに、高温に耐える上記タイプの複合体を提供することにある。
エポキシ樹脂は接着性組成物の合計重量の約40〜約80重量%の範囲で存在する。代表的なエポキシ樹脂の例には、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、4,4’−ビスフェノール型エポキシ樹脂、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、ビスフェノールAノボラック型エポキシ樹脂、ビスフェノールFノボラック型エポキシ樹脂、フェノールサリシレートアルデヒドノボラック型エポキシ樹脂、脂環式エポキシ樹脂、脂肪族鎖状エポキシ樹脂、グリシジルエーテル型エポキシ樹脂、及び他化合物、たとえば2官能性フェノール基グリシジルエーテル化合物、2官能性アルコールグリシジルエーテル化合物、ポリフェノール基グリシジルエーテル化合物、及びポリフェノールグリシジルエーテル化合物及びその水和物がある。これらの樹脂の混合物も用いうる。
本発明の実施に有用な強化繊維の例としては、グラファイト繊維、ガラス繊維及び他の鉱物繊維、たとえば珪灰石繊維がある。これらのなかでグラファイト繊維が特に好ましい。グラファイト繊維はメソフェース又は非メソフェース石油ピッチ、又はコールタールピッチもしくは類似の炭素含有物質の処理でつくられうる炭素繊維として記載しうる。またPAN、アクリル又はレーヨン前駆体を用いてつくられる炭素繊維も用いうる。本発明で有用な炭素繊維の形状は紙、フェルト又はマット構造(織布又は不織布)からなる。
本発明の好ましい態様において、前記したように、アセトンやメチルエチルケトン等のエポキシ樹脂用溶媒を用いた前記エポキシ樹脂接着性組成物でグラファイト繊維マットを含浸処理することが好ましい。含浸技術の例としては浸漬、ブラッシング、スプレー等がある。このようにして含浸処理したマットを乾燥させてプリプレグ(接着剤約20〜約40%含有)をつくり、次いでオートクレーブ中での真空処理や約150〜約225℃で約1〜約2時間硬化を行う熱プレス処理で硬化させて実用的な航空機内装材として適する積層体をつくる。
〔実施例1〕
フェノール−ホルムアルデヒド樹脂(Schenectady International製のHRJ2210ブランド)11gを30mlの2−ブタノン溶媒に60℃で溶解させ、次いでエポキシノボラック樹脂(Bakelite AG製のRUETAPOX300ブランド)63.5gと反応性ポリ(m−フェニレンメチルホスフォネート)(nは約14、後記方法で製造)25gを加え60℃で上記溶媒に溶解させた。次いで2−メチルイミダゾール(Air Products製のAMI−2ブランド)0.5wt%を加えた。得られた温ワニスを平織りグラファイト布帛(Fibre Glast製のNo.530)に塗布した。得られたプリプレグを室温で1夜乾燥し、次いで90℃で30分乾燥した。このプリプレグ(4×4インチ)を16パイル積層し、130℃圧力8MPaで30分間予備硬化させ、次いで171℃圧力30MPaで70分間硬化させた。
ジフェニルメチルホスホネート124g(0.5モル)とレゾルシノール113g(1.03モル)とナトリウムメチレート0.54gを反応フラスコ中で230℃に加熱撹拌した。反応フラスコには、電熱テープ及び絶線体をまいてカラム中でフェノールや揮発したレゾルシノールが固化しないようにした高さ40cmのビグレックス(Vigreux)カラムを取りつけた。真空圧を625mmから5mmHgに徐々に下げた。4時間後に反応を止めた。フェノールを反応中蒸発除去し、冷トラップに留出分93g(フェノールとして計算して約1モル)を集め、反応フラスコには(ポリ)m−フェニレンメチルホスフォネート)生成物241gが残った。留出分はほとんどがフェノールであった。
この例では、フェノールホルムアルデヒド樹脂(Schenectady International製のHRJ2210ブランド)15gを30mlの2−ブタノン溶媒に60℃で溶解させ、次いでエポキシノボラック樹脂(Bakelite AG製のRUETAPOX300ブランド)84.5gを加え上記溶媒に60℃で溶解させた。次いで2−メチルイミダゾール(Air Product製のAMI−2ブランド)0.5wt%を加えた。次いで実施例1に記載したと同様にしてプリプレグと複合体を製造した。
この例では、フェノール−ホルムアルデヒド樹脂(Schenectady International製のHRJ2210ブランド)15gを、臭素化ビスフェノールAエポキシ樹脂(Dow Chemical製のD.E.R.530−A80ブランド)84.5gを含有するアセトン溶液100gに60℃で溶解させた。次いで、2−メチルイミダゾール(Air Products製のAMI−2ブランド)0.5wt%を加えた。次いで実施例1に記載法を同様にしてプリプレグと複合体を製造した。
実施例1及び(比較)実施例2及び3の各々でつくった複合体の燃焼性ISO/DP5660標準に従い、75KW/m2の熱フラックスにてコーン熱量計を用いて評価した。テスト結果次表に示す。
Claims (12)
- グラファイト繊維からなる強化繊維、及び、
エポキシ樹脂と、所望により含まれる樹脂硬化剤及び/又は硬化触媒と、反応性ホスフォネート難燃剤とからなる接着性組成物
からなることを特徴とする複合材料。 - 強化繊維の量が複合材料の合計重量の50〜90重量%である請求項1に記載の複合材料。
- 接着性組成物の量が複合材料の合計重量の20〜60重量%である請求項1又は2に記載の複合材料。
- エポキシ樹脂の量が接着性組成物の合計重量の40〜80重量%である請求項1から3のいずれか1項に記載の複合材料。
- 反応性ホスフォネート難燃剤の量が接着性組成物の合計重量の5〜60重量%である請求項1から4のいずれか1項に記載の複合材料。
- 硬化触媒の量が接着性組成物の合計重量の0.05〜1.0重量%である請求項1から5のいずれか1項に記載の複合材料。
- 任意成分である樹脂硬化剤の量が接着性組成物の合計重量の5〜10重量%である請求項1から6のいずれか1項に記載の複合材料。
- 反応性ホスフォネート難燃剤が(−OP(O)(R)−O−アリーレン−)nで示される反復単位(但しnは2〜30を示す)をもつ請求項1から7のいずれか1項に記載の複合材料。
- 反応性ホスフォネート難燃剤がポリ(m−フェニレンメチルホスフォネート)である請求項8の複合材料。
- グラファイト繊維からなる強化繊維に、エポキシ樹脂と所望により含まれる樹脂硬化剤及び/又は硬化触媒と反応性ホスフォネート難燃剤とからなる接着性組成物を含浸させることを特徴とする複合材料の製造方法。
- 反応性ホスフォネート難燃剤が(−OP(O)(R)−O−アリーレン−)nで示される反復単位(但しnは2〜30を示す)をもつ請求項10に記載の方法。
- 反応性ホスフォネート難燃剤がポリ(m−フェニレンメチルホスフォネート)である請求項11に記載の方法。
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WO2012165665A1 (ja) * | 2011-06-03 | 2012-12-06 | Arisawa Mfg. Co., Ltd. | 難燃性樹脂組成物、並びに該樹脂組成物を用いたフレキシブルプリント配線板用金属張積層板、カバーレイ、フレキシブルプリント配線板用接着シート及びフレキシブルプリント配線板 |
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