JP2009079073A5

JP2009079073A5 -

Info

Publication number: JP2009079073A5
Application number: JP2007247230A
Authority: JP
Filing date: 2007-09-25
Publication date: 2011-09-22
Anticipated expiration: 2027-09-25

Description

また、本発明の繊維強化複合材料用エポキシ樹脂組成物は、前記ポリアミド樹脂（ＩＩ）が、重合脂肪酸類から誘導されるポリアミド類、及び／又は、下記式（４）で示される、前記
ポリアミド類と、ポリエーテル類、ポリエステル類、ポリエーテルエステル類からなる群から選択される１つ以上との共重合等により得られるポリアミドエラストマー類であるのが好ましい。 Moreover, the epoxy resin composition for fiber-reinforced composite materials of the present invention is such that the polyamide resin (II) is derived from polymerized fatty acids and / or the polyamides represented by the following formula (4): And polyamide elastomers obtained by copolymerization with one or more selected from the group consisting of polyethers, polyesters and polyetheresters.

重合脂肪酸から誘導されたポリアミド樹脂類としては、例えば、富士化成工業社製ＰＡシリーズ（ＰＡ−１００、ＰＡ−１００Ａ、ＰＡ−１０２Ａ、ＰＡ−１０５Ａ、ＰＡ−１００Ａ）が挙げられる。
また、ポリアミド樹脂（ＩＩ）としては、下記式（４）で示されるポリエーテルエステルアミド（ポリエーテルエステルアミドブロック共重合体）が好ましい。該ポリエーテルエステルアミドは、ポリアミド成分と、ポリオキシアルキレングリコール及びジカルボン酸からなるポリエーテルエステル成分との反応で得られ、分子鎖中にアミド結合とエーテル結合とエステル結合とを有する重合体であり、エポキシ樹脂に高い相溶性を示す。そのため、エポキシ樹脂（Ｉ）と微細な海島構造を形成でき、その結果、優れた力学的特性を維持したまま耐衝撃性を向上させる効果が大きい。 Examples of polyamide resins derived from polymerized fatty acids include PA series (PA-100, PA-100A, PA-102A, PA-105A, PA-100A) manufactured by Fuji Kasei Kogyo Co., Ltd.
Moreover, as polyamide resin (II), the polyetheresteramide (polyetheresteramide block copolymer) shown by following formula (4 ) is preferable. The polyether ester amide is a polymer obtained by reacting a polyamide component with a polyether ester component comprising polyoxyalkylene glycol and dicarboxylic acid, and having an amide bond, an ether bond and an ester bond in the molecular chain. High compatibility with epoxy resin. Therefore, a fine sea-island structure can be formed with the epoxy resin (I). As a result, the effect of improving the impact resistance while maintaining excellent mechanical properties is great.

１８０℃で硬化反応が行えるジアミノジフェニルメタン等の硬化剤は、該硬化過程においてポリアミド樹脂が相分離を起こすおそれがあるため好ましくない。また、１００℃以下で硬化反応が行えるアミノ化合物やイミダゾール類では、ポリアミド樹脂末端とエポキシ樹脂中の官能基との結合形成が充分に進行しないおそれがあるため好ましくない。ただし、これらの硬化剤をマイクロカプセル化したものを、プリプレグの保存安定性を高めるために用いることは構わない。 Curing agent such as diaminodiphenyl methane that allows the curing reaction at 180 ° C. is not preferable because the polyamide resin in the cured process is likely to undergo phase separation. In addition, amino compounds and imidazoles that can undergo a curing reaction at 100 ° C. or less are not preferable because there is a possibility that the bond formation between the end of the polyamide resin and the functional group in the epoxy resin may not proceed sufficiently. However, those obtained by encapsulating these curing agents may be used for enhancing the storage stability of the prepreg.

ポリアミド樹脂（ＩＩ）
ＴＰＡＥ３２：ポリエーテルエステルアミド共重合体（富士化成工業（株）製） Polyamide resin (II)
TPAE32: Polyetheresteramide copolymer (Fuji Kasei Kogyo Co., Ltd.)

硬化促進剤
ＤＣＭＵ：３−（３，４−ジクロロフェニル）−１，１−ジメチル尿素（製品名：ＤＣＭＵ９９、保土谷化学社製）
熱可塑性樹脂
ＰＶＦ：ポリビニルフォルマール（製品名：ビニレックＥ、チッソ（株）製） Curing accelerator DCMU: 3- (3,4-dichlorophenyl) -1,1-dimethylurea (Product name: DCMU99, manufactured by Hodogaya Chemical Co., Ltd.)
Thermoplastic resin PVF: Polyvinyl formal (Product name: Vinylec E, manufactured by Chisso Corporation)

［実施例１］
表１に示す組成で樹脂組成物を調製した。
ＡＥＲ４１５２（５０ｇ）、ｊＥＲ８２８（１００ｇ）、ｊＥＲ１００１（５０ｇ）、及びＴＰＡＥ３２（５．６ｇ）をフラスコに順次投入後、１８０℃に調温したフラスコで均一になるまで溶解した。その後、５０℃〜６０℃に冷却した後、ＤＩＣＹ（１０．８ｇ）とＤＣＭＵ（７．２ｇ）とを投入し、均一になるまで撹拌混合して樹脂組成物を得た。ついで、フラスコ内部を減圧ポンプで減圧することにより樹脂組成物中の空気を脱泡してから、シリコン系の離型剤を用いて離型処理した２枚のガラス板間に挟み、１３０℃で、１．５時間加熱することで樹脂組成物を硬化させ、硬化樹脂物である硬化樹脂板を得た。ただし、樹脂組成物を挟み込む際に、スペーサーを入れることで、厚さ２ｍｍと厚さ３ｍｍの硬化樹脂板を得た。 [Example 1]
Resin compositions were prepared with the compositions shown in Table 1.
AER415 2 (50 g), jER828 (100 g), jER1001 (50 g), and TPAE 3 2 (5.6 g) were sequentially added to the flask, and then dissolved in a flask adjusted to 180 ° C. until uniform. Then, after cooling to 50 ° C. to 60 ° C., DICY (10.8 g) and DCMU (7.2 g) were added, and stirred and mixed until uniform to obtain a resin composition. Next, the air in the resin composition is degassed by reducing the pressure inside the flask with a vacuum pump, and then sandwiched between two glass plates that have been subjected to a release treatment using a silicon-based release agent. The resin composition was cured by heating for 1.5 hours to obtain a cured resin plate that was a cured resin product. However, when sandwiching the resin composition, a cured resin plate having a thickness of 2 mm and a thickness of 3 mm was obtained by inserting a spacer.

Claims

The polyamide resin (II) is a group of polyamides derived from polymerized fatty acids and / or the polyamides represented by the following formula (4) , polyethers, polyesters, and polyether esters: The epoxy resin composition for fiber-reinforced composite materials according to claim 1, which is a polyamide elastomer obtained by copolymerization with one or more selected from the above.
(In the formula (4), a is 1 to 10, b is 1 to 10, c is 1 to 20, and both are integers. PA is the following formula (5), and PE is the following formula (8). ).)
(In the formula (5), d is 0 to 2, e is 0 to 2, f is 1 to 10, and both are integers, provided that d and e are not 0 at the same time. (It is an integer of 2 to 40. Moreover, PA1 and PA2 are each independently the following formula (6) and / or the following formula (7).)
(In Formula (6) and Formula (7), β is 2 to 40, γ is 2 to 40, and both are integers. R7 and R8 are each independently a hydrogen atom or a methyl group.)
(In Formula (8), g is 3-20, h is 1-10, and all are integers. Moreover, (theta) is 2-8, (phi) is 2-40, and all are integers.