JP7424990B2 - 繊維強化複合材料用樹脂組成物及びそれを用いた繊維強化複合材料 - Google Patents
繊維強化複合材料用樹脂組成物及びそれを用いた繊維強化複合材料 Download PDFInfo
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- JP7424990B2 JP7424990B2 JP2020548505A JP2020548505A JP7424990B2 JP 7424990 B2 JP7424990 B2 JP 7424990B2 JP 2020548505 A JP2020548505 A JP 2020548505A JP 2020548505 A JP2020548505 A JP 2020548505A JP 7424990 B2 JP7424990 B2 JP 7424990B2
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- CKDSFRWKHBYHHT-UHFFFAOYSA-N 4-bicyclo[2.2.1]heptanylmethanamine Chemical compound C1CC2CCC1(CN)C2 CKDSFRWKHBYHHT-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
- B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
- B29C70/48—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM], e.g. by vacuum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
- C08G59/46—Amides together with other curing agents
- C08G59/48—Amides together with other curing agents with polycarboxylic acids, or with anhydrides, halides or low-molecular-weight esters thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
- C08G59/46—Amides together with other curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
-
- C—CHEMISTRY; METALLURGY
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
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- B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
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- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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Description
(式中のR3~R22は水素原子、水酸基、炭素原子数1~20の直鎖もしくは分岐のアルキル基、炭素原子数6~20のアリール基、炭素原子数3~20のヘテロアリール基またはR23OCO-で表される基であり、アリール基、ヘテロアリール基またはR23OCO-基の場合、これらは芳香族骨格又は6員ラクトン骨格(R17の場合は、それが結合する炭素原子)に直接に結合しても、架橋基を介して結合してもよい。)
X-(CH2NH2)n (5)
(式中、Xは炭素数1~16のn価の有機基を表し、nは2又は3を表す。)
本発明の繊維強化複合材料用樹脂組成物は、これに強化繊維を配合してプリプレグとなり、このプリプレグを硬化又は成形することにより硬化物又は成形体となる。以下、繊維強化複合材料用樹脂組成物を樹脂組成物とも言い、繊維強化複合材料を複合材料、成形体または硬化物とも言う。
一般式(2)~(4)において、R3~R22は水素原子、水酸基、炭素原子数1~20の直鎖もしくは分岐のアルキル基、炭素原子数6~20のアリール基、炭素原子数3~20のヘテロアリール基またはR23OCO-で表される基であり、アリール基、ヘテロアリール基またはR23OCO-基の場合、これらは芳香族骨格又は6員ラクトン骨格に直接に結合しても、架橋基を介して結合してもよい。ここで、R17は環構成炭素原子に結合していないので、それが結合する炭素原子と直接又は架橋基を介して結合してもよい。R23は上記アルキル基又はアリール基と同意である。好ましい架橋基は、炭素数1~3のアルキレン基等である。
上記アルキル基、アリール基、またはヘテロアリール基(R23がアルキル基またはアリール基である場合を含む)である場合は、これらは置換基を有することができ、好ましい置換基は、水酸基、カルボキシ基、チオール基、エステル基(OCO)等である。
これらは、主剤および硬化剤に含まれる成分との反応性や粘度等を考慮して、いずれかに配合することができる。主剤又は硬化剤に含まれる成分と反応する配合は、避けることになる。また、溶剤は成形体の生産性を低下させるので、含まないか少量とすることが望ましい。
注入温度が低いと流動性が低下し、成形型及び繊維への充填不良が起こり好ましくない。また、注入温度が高いとバリが発生したり、注入時に樹脂の硬化が始まりタンク内や成形型内での樹脂が硬化し充填不良が発生するため好ましくない。また、成形時間は短すぎると十分に充填されず、長すぎると型内での樹脂が硬化し成形不良が起こるとともに生産性の低下が起こるため好ましくない。本発明のプリプレグに含まれる樹脂組成物は、上記の様な比較的低い注入温度にて成形型への注入、含浸が可能となり、また短い硬化時間で型からの離形ができる硬化物を得ることができる。
(A)成分
YD-128:ビスフェノールA型エポキシ樹脂(新日鉄住金化学社製)
YDF-170:ビスフェノールF型エポキシ樹脂(新日鉄住金化学社製)
(B)成分
DHCM:ジヒドロクマリン
SAPE:サリチル酸フェニル
(C)成分
NBDA:ビス(アミノメチル)ノルボルナン
1,3-BAC:1,3-ビスアミノメチルシクロヘキサン
TETA:トリエチレンテトラミン
(D)成分(その他成分)
4tBP:4-tert-ブチルフェノール
2E4MZ:2-エチル-4-メチルイミダゾール
DICY:ジシアンジアミド
E型粘度計コーンプレートタイプ(東機産業株式会社:RE80H)を用いて25℃で測定した。測定開始から60秒経過後の値を、粘度の値とした。
120℃に加熱しておいたゲル化試験機(日新科学製)のプレート上に二液硬化型樹脂組成物を添加し、フッ素樹脂棒を用いて一秒間に2回転の速度で攪拌し、樹脂組成物の硬化が進行し可塑性を失うまでに要した時間をゲル化時間とした。ゲル化しないときは×とした。
動的粘弾性試験機を用いて、ガラス転移温度測定用試験片を昇温速度5℃/分、曲げモード、測定周波数10Hzの条件で測定し、損失弾性率(E’’)の最大値をTgとした。
(A)成分としてYD-128を95部、(B)成分としてDHCMを5部、(C)成分としてNBDAを20.9部使用した。
(A)成分と(B)成分を混合して主剤とした。(C)成分と(D)成分を混合して硬化剤とした。
主剤と硬化剤を、真空ミキサーを用いて、室温下で5分間攪拌しながら混合して、樹脂組成物を得た。
この樹脂組成物を、平板形状にくり抜かれた4mm厚のスペーサーを設けた縦60mm×横80mmの120℃に加熱された金型へ流し込み、5分間硬化させた後、得られた硬化物を、卓上バンドソーを用いて50mm×10mmの大きさに切削して試験片を得て、これをTgの測定に用いた。
(A)~(D)成分として表1および表2に記載された組成(部)にて各原料を使用した以外は、実施例1と同様の混合条件にて樹脂組成物と試験片を作製した。
Claims (9)
- エポキシ樹脂(A)と下記一般式(2)~(4)のいずれかで表されるエステル化合物(B)を含む主剤と、下記式(6)~(8)のいずれかで表されるアミン化合物(C)を含む硬化剤で構成される二液硬化型の繊維強化複合材料用樹脂組成物。
式中、R3~R16は水素原子、水酸基、炭素原子数1~20の直鎖もしくは分岐のアルキル基、炭素原子数6~20のアリール基、炭素原子数3~20のヘテロアリール基またはR23OCO-で表される基であり、アリール基、ヘテロアリール基またはR23OCO-基の場合、これらはそれが結合する炭素原子に直接に結合しても、架橋基を介して結合してもよい。R17はフェニル基であり、R18~R22は水素原子又は水酸基であるが、いずれか一つは水酸基である。
- 主剤と硬化剤の質量比が90:10~70:30の範囲であることを特徴とする請求項1に記載の繊維強化複合材料用樹脂組成物。
- エステル化合物(B)が主剤中に2~30重量%含有されることを特徴とする請求項1に記載の繊維強化複合材料用樹脂組成物。
- 繊維強化複合材料用樹脂組成物の硬化物のガラス転移温度が100℃以上を示すことを特徴とする請求項1に記載の繊維強化複合材料用樹脂組成物。
- 請求項1~4のいずれか一項に記載の繊維強化複合材料用樹脂組成物に、強化繊維を配合してなることを特徴とするプリプレグ。
- 強化繊維の体積含有率が45~70%である請求項5に記載のプリプレグ。
- 請求項5に記載のプリプレグの硬化物。
- 請求項5に記載のプリプレグを、レジントランスファー成形法、またはリキッドコンプレッション成形法で成形することを特徴とする成形体の製造方法。
- 請求項1に記載の二液硬化型の繊維強化複合材料用樹脂組成物を用意すること、この繊維強化複合材料用樹脂組成物の二液と強化繊維を混合してプリプレグとすること、次いでこのプリプレグを金型にて加熱硬化、成形することからなる工程を有することを特徴とする成形体の製造方法。
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JP2008530321A (ja) | 2005-02-18 | 2008-08-07 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | ラクトンを含有する低収縮アミン硬化エポキシ樹脂組成物 |
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JPH032258A (ja) | 1989-05-30 | 1991-01-08 | Matsushita Electric Works Ltd | 樹脂組成物、プリプレグおよび積層板 |
JPH11158350A (ja) | 1997-09-24 | 1999-06-15 | Hitachi Chem Co Ltd | エポキシ樹脂組成物、これを用いたぺースト状組成物およびこれを用いて製造される半導体装置 |
WO2011157671A1 (de) * | 2010-06-15 | 2011-12-22 | Basf Se | Verwendung von cyclischen carbonaten in epoxidharzzusammensetzungen |
EP2920226B1 (en) | 2012-11-13 | 2016-12-28 | Dow Global Technologies LLC | Epoxy resin system containing polyethylene tetramines and triethylene diamine catalyst for resin transfer molding processes |
JP6570854B2 (ja) * | 2014-03-26 | 2019-09-04 | 三洋化成工業株式会社 | 繊維強化複合材料用樹脂組成物、繊維強化複合材料用樹脂組成物含浸強化繊維及び繊維強化複合材料 |
JP6593620B2 (ja) | 2014-11-21 | 2019-10-23 | Dic株式会社 | エポキシ樹脂組成物、硬化物、繊維強化複合材料、繊維強化樹脂成形品、及び繊維強化樹脂成形品の製造方法 |
EP3444291B1 (en) | 2016-04-12 | 2020-04-22 | Mitsubishi Gas Chemical Company, Inc. | Epoxy resin curing agent, epoxy resin composition, and carbon fiber-reinforced composite material |
CN110650989B (zh) * | 2017-05-24 | 2023-03-31 | 三菱化学株式会社 | 成型材料、及纤维增强复合材料 |
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JP2013032510A (ja) | 2011-06-29 | 2013-02-14 | Toray Ind Inc | エポキシ樹脂組成物、成形材料および繊維強化複合材料 |
JP2015535022A (ja) | 2012-11-13 | 2015-12-07 | ダウ グローバル テクノロジーズ エルエルシー | 樹脂移送成形プロセスのためのポリエチレンテトラアミン含有エポキシ樹脂系 |
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