JP2010100834A5 - - Google Patents

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JP2010100834A5
JP2010100834A5 JP2009216684A JP2009216684A JP2010100834A5 JP 2010100834 A5 JP2010100834 A5 JP 2010100834A5 JP 2009216684 A JP2009216684 A JP 2009216684A JP 2009216684 A JP2009216684 A JP 2009216684A JP 2010100834 A5 JP2010100834 A5 JP 2010100834A5
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epoxy resin
block
skeleton
resin composition
composition according
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JP2010100834A (en
JP5564870B2 (en
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本発明はかかる課題を解決するために以下の構成を有する。すなわち、
（１）下記［Ａ］〜［Ｃ］を含み、かつ、［Ａ］エポキシ樹脂が、［Ａａ］、および、［Ａｂ］を含むエポキシ樹脂組成物。
［Ａ］エポキシ樹脂
［Ａａ］縮合多環骨格、ビフェニル骨格、オキサゾリドン環の骨格から選ばれる少なくとも１つの骨格を有するエポキシ樹脂；［Ａ］エポキシ樹脂１００質量％のうち３０〜８０質量％
［Ａｂ］多官能アミン型エポキシ樹脂；［Ａ］エポキシ樹脂１００質量％のうち２０〜７０質量％
［Ｂ］芳香族アミン系硬化剤
［Ｃ］Ｓ−Ｂ−Ｍ、Ｂ−ＭおよびＭ−Ｂ−Ｍからなる群から選ばれる少なくとも１種のブロック共重合体
（ここで、前記の各ブロックは共有結合によって連結されるか、一方のブロックに一つの共有結合形成を介して結合され、他方のブロックに他の共有結合形成を介して結合された中間分子によって連結されており、ブロックＭはポリメタクリル酸メチルのホモポリマーまたは、メタクリル酸メチルを少なくとも５０重量％含むコポリマーからなるブロックであり、ブロックＢはブロックＭに非相溶で、そのガラス転移温度が２０℃以下であり、ブロックＳはブロックＢおよびＭに非相溶で、かつ、そのガラス転移温度が、ブロックＢのガラス転移温度よりも高いブロックである）。 In order to solve this problem, the present invention has the following configuration. That is,
(1) An epoxy resin composition comprising the following [A] to [C], and the [A] epoxy resin comprising [Aa] and [Ab].
[A] epoxy resin 100 wt% 30 to 80 of the weight%; that [A] epoxy resins [Aa] condensed polycyclic skeleton, a biphenyl skeleton, an epoxy resin having at least one skeleton selected from the backbone of the oxazolidone ring
[Ab] Polyfunctional amine type epoxy resin; [A] 20 to 70% by mass of 100% by mass of epoxy resin
[B] Aromatic amine-based curing agent [C] At least one block copolymer selected from the group consisting of SBM, BM, and MBM (where each block is The block M is linked by an intermediate molecule that is linked by a covalent bond or is linked to one block via one covalent bond formation and to the other block via another covalent bond formation. A block made of a homopolymer of methyl methacrylate or a copolymer containing at least 50% by weight of methyl methacrylate, Block B is incompatible with Block M, its glass transition temperature is 20 ° C. or lower, and Block S is a block B is a block that is incompatible with B and M and has a glass transition temperature higher than that of block B).

（４）［Ａａ］が、オキサゾリドン環の骨格、またはナフタレン骨格を有するエポキシ樹脂である、前記（１）〜（３）のいずれかに記載のエポキシ樹脂組成物。 (4) The epoxy resin composition according to any one of (1) to (3), wherein [Aa] is an epoxy resin having an oxazolidone ring skeleton or a naphthalene skeleton.

（８）前記（１）〜（６）のいずれかに記載のエポキシ樹脂組成物を硬化させたエポキシ樹脂硬化物であって、曲げ弾性率が３．６ＧＰａ以上であり、かつガラス転移温度が１８０℃以上であるエポキシ樹脂硬化物。 (8) A cured epoxy resin obtained by curing the epoxy resin composition according to any one of (1) to ( 6 ), having a flexural modulus of 3.6 GPa or more and a glass transition temperature of 180. Epoxy resin cured product that is ℃ or higher.

（９）前記（１）〜（６）のいずれかに記載のエポキシ樹脂組成物を強化繊維に含浸させてなるプリプレグ。 (9) A prepreg obtained by impregnating a reinforcing fiber with the epoxy resin composition according to any one of (1) to ( 6 ).

（１１）前記（１）〜（６）のいずれかに記載のエポキシ樹脂組成物を硬化させた硬化物と強化繊維基材を含む繊維強化複合材料。
（１２）前記（７）または（８）に記載のエポキシ樹脂硬化物と、強化繊維基材を含む繊維強化複合材料。 (11) A fiber reinforced composite material comprising a cured product obtained by curing the epoxy resin composition according to any one of (1) to ( 6 ) and a reinforced fiber substrate.
(12) A fiber-reinforced composite material comprising the cured epoxy resin according to (7) or (8) and a reinforcing fiber substrate.

Claims (12)

下記［Ａ］〜［Ｃ］を含み、かつ、［Ａ］エポキシ樹脂が、［Ａａ］、および、［Ａｂ］を含むエポキシ樹脂組成物。
［Ａ］エポキシ樹脂
［Ａａ］縮合多環骨格、ビフェニル骨格、オキサゾリドン環の骨格から選ばれる少なくとも１つの骨格を有するエポキシ樹脂；［Ａ］エポキシ樹脂１００質量％のうち３０〜８０質量％
［Ａｂ］多官能アミン型エポキシ樹脂；［Ａ］エポキシ樹脂１００質量％のうち２０〜７０質量％
［Ｂ］芳香族アミン系硬化剤
［Ｃ］Ｓ−Ｂ−Ｍ、Ｂ−ＭおよびＭ−Ｂ−Ｍからなる群から選ばれる少なくとも１種のブロック共重合体
（ここで、前記の各ブロックは共有結合によって連結されるか、一方のブロックに一つの共有結合形成を介して結合され、他方のブロックに他の共有結合形成を介して結合された中間分子によって連結されており、ブロックＭはポリメタクリル酸メチルのホモポリマーまたは、メタクリル酸メチルを少なくとも５０重量％含むコポリマーからなるブロックであり、ブロックＢはブロックＭに非相溶で、そのガラス転移温度が２０℃以下であり、ブロックＳはブロックＢおよびＭに非相溶で、かつ、そのガラス転移温度が、ブロックＢのガラス転移温度よりも高いブロックである）。 An epoxy resin composition comprising the following [A] to [C], and the [A] epoxy resin comprising [Aa] and [Ab].
[A] epoxy resin 100 wt% 30 to 80 of the weight%; that [A] epoxy resins [Aa] condensed polycyclic skeleton, a biphenyl skeleton, an epoxy resin having at least one skeleton selected from the backbone of the oxazolidone ring
[Ab] Polyfunctional amine type epoxy resin; [A] 20 to 70% by mass of 100% by mass of epoxy resin
[B] Aromatic amine-based curing agent [C] At least one block copolymer selected from the group consisting of SBM, BM, and MBM (where each block is The block M is linked by an intermediate molecule that is linked by a covalent bond or is linked to one block via one covalent bond formation and to the other block via another covalent bond formation. A block made of a homopolymer of methyl methacrylate or a copolymer containing at least 50% by weight of methyl methacrylate, Block B is incompatible with Block M, its glass transition temperature is 20 ° C. or lower, and Block S is a block B is a block that is incompatible with B and M and has a glass transition temperature higher than that of block B). ［Ａａ］において、縮合多環骨格が、ナフタレン骨格、フルオレン骨格およびジシクロペンタジエン骨格から選ばれる少なくとも１つの骨格であり、かつ、［Ｂ］の芳香族アミン系硬化剤がジアミノジフェニルスルフォンである、請求項１に記載のエポキシ樹脂組成物。 In [Aa], the condensed polycyclic skeleton is at least one skeleton selected from a naphthalene skeleton, a fluorene skeleton, and a dicyclopentadiene skeleton, and the aromatic amine curing agent of [B] is diaminodiphenyl sulfone. The epoxy resin composition according to claim 1. ［Ａ］エポキシ樹脂が、［Ａｃ］として、液状ビスフェノール型エポキシを、［Ａ］エポキシ樹脂１００質量％のうち１０〜４０質量％含む、請求項１または２に記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 1 or 2, wherein the [A] epoxy resin contains, as [Ac], 10 to 40% by mass of liquid bisphenol type epoxy out of 100% by mass of the [A] epoxy resin. ［Ａａ］が、オキサゾリドン環の骨格、またはナフタレン骨格を有するエポキシ樹脂である、請求項１〜３のいずれかに記載のポキシ樹脂組成物。 The epoxy resin composition according to any one of claims 1 to 3, wherein [Aa] is an epoxy resin having an oxazolidone ring skeleton or a naphthalene skeleton. ［Ａａ］が、エポキシ当量が３００〜５００の範囲にあり、オキサゾリドン環の骨格を有する２官能エポキシであり、かつ、［Ｂ］の活性水素量が、［Ａ］エポキシ樹脂中のエポキシ基量の０．６〜１．２倍である、請求項４に記載のエポキシ樹脂組成物。 [Aa] is a bifunctional epoxy having an epoxy equivalent in the range of 300 to 500, having an oxazolidone ring skeleton, and the amount of active hydrogen in [B] is the amount of epoxy groups in [A] epoxy resin The epoxy resin composition according to claim 4, which is 0.6 to 1.2 times. ［Ｃ］が、Ｍ−Ｂ−Ｍで表されるブロック共重合体であり、Ｍブロックがメタクリル酸メチルよりもＳＰ値の高いモノマーを共重合成分として含有する、請求項１〜５のいずれかに記載のエポキシ樹脂組成物 [C] is a block copolymer represented by MBM, and the M block contains a monomer having a higher SP value than methyl methacrylate as a copolymerization component. The epoxy resin composition according to 請求項１〜６のいずれかに記載のエポキシ樹脂組成物を硬化させた相分離の大きさが１０ｎｍ以上１０００ｎｍ以下であるエポキシ樹脂硬化物。 The epoxy resin hardened | cured material whose magnitude | size of the phase separation which hardened the epoxy resin composition in any one of Claims 1-6 is 10 nm or more and 1000 nm or less. 請求項１〜６のいずれかに記載のエポキシ樹脂組成物を硬化させたエポキシ樹脂硬化物であって、曲げ弾性率が３．６ＧＰａ以上であり、かつガラス転移温度が１８０℃以上であるエポキシ樹脂硬化物。 An epoxy resin cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 6 , wherein the epoxy resin has a flexural modulus of 3.6 GPa or more and a glass transition temperature of 180 ° C or more. Cured product. 請求項１〜６のいずれかに記載のエポキシ樹脂組成物を強化繊維に含浸させてなるプリプレグ。 A prepreg obtained by impregnating a reinforcing fiber with the epoxy resin composition according to any one of claims 1 to 6 . 請求項９に記載のプリプレグを硬化させてなる繊維強化複合材料。 A fiber-reinforced composite material obtained by curing the prepreg according to claim 9. 請求項１〜６のいずれかに記載のいずれかに記載のエポキシ樹脂組成物を硬化させた硬化物と、強化繊維基材を含む繊維強化複合材料。 The fiber reinforced composite material containing the hardened | cured material which hardened the epoxy resin composition in any one of Claims 1-6, and a reinforced fiber base material. 請求項７または８に記載のエポキシ樹脂硬化物と、強化繊維基材を含む繊維強化複合材料。The fiber reinforced composite material containing the epoxy resin hardened | cured material of Claim 7 or 8, and a reinforced fiber base material.
JP2009216684A 2008-09-29 2009-09-18 Epoxy resin composition, prepreg, and fiber reinforced composite material Active JP5564870B2 (en)

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JP5381869B2 (en) * 2010-03-31 2014-01-08 住友ベークライト株式会社 Epoxy resin precursor composition, prepreg, laminate, resin sheet, printed wiring board, and semiconductor device
RU2013118705A (en) * 2010-09-24 2014-10-27 Торэй Индастриз, Инк. EPOXY RESIN COMPOSITION FOR FIBER REINFORCED COMPOSITE MATERIAL, PREPRAID AND FIBER REINFORCED COMPOSITE MATERIAL
JP5811883B2 (en) * 2011-02-25 2015-11-11 東レ株式会社 Epoxy resin composition for fiber reinforced composite material, prepreg and fiber reinforced composite material
EP2886576A4 (en) * 2012-08-20 2015-09-02 Mitsubishi Rayon Co Epoxy resin composition and film, prepreg, and fiber-reinforced plastic using same
EP2975088A4 (en) * 2013-03-11 2017-02-22 Toray Industries, Inc. Epoxy resin composition, prepreg, and fiber-reinforced composite material
JP5804222B1 (en) 2014-02-25 2015-11-04 東レ株式会社 Carbon fiber reinforced composite and prepreg
JP2016084372A (en) * 2014-10-22 2016-05-19 旭化成イーマテリアルズ株式会社 Prepreg and fiber reinforced plastic
KR20180048454A (en) 2015-09-03 2018-05-10 도레이 카부시키가이샤 Epoxy resin composition, prepreg and carbon fiber reinforced composite material
CN111295406A (en) 2017-11-02 2020-06-16 日铁化学材料株式会社 Epoxy resin composition and cured product thereof
JP2019157057A (en) * 2018-03-16 2019-09-19 三菱ケミカル株式会社 Curable resin composition, and prepreg, film and fiber-reinforced plastic including the same
JP7338130B2 (en) * 2018-03-23 2023-09-05 三菱ケミカル株式会社 Epoxy resin composition and prepreg for fiber reinforced composites
JP2020050833A (en) 2018-09-28 2020-04-02 日鉄ケミカル＆マテリアル株式会社 Prepreg and molded article thereof

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JP2008031193A (en) * 2006-07-26 2008-02-14 Toray Ind Inc Epoxy resin composition, prepreg, and fiber-reinforced composite
JP2008189794A (en) * 2007-02-05 2008-08-21 Toray Ind Inc Epoxy resin composition, prepreg and fiber-reinforced composite material

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