JPS63301221A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPS63301221A JPS63301221A JP62138400A JP13840087A JPS63301221A JP S63301221 A JPS63301221 A JP S63301221A JP 62138400 A JP62138400 A JP 62138400A JP 13840087 A JP13840087 A JP 13840087A JP S63301221 A JPS63301221 A JP S63301221A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- moles
- composition
- epoxy
- phenolic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 31
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims description 28
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 7
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 7
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 125000003700 epoxy group Chemical group 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 5
- -1 phenol compound Chemical class 0.000 claims description 5
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 2
- 229940018563 3-aminophenol Drugs 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- DBFYESDCPWWCHN-UHFFFAOYSA-N 5-amino-2-methylphenol Chemical compound CC1=CC=C(N)C=C1O DBFYESDCPWWCHN-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000006835 compression Effects 0.000 abstract description 4
- 238000007906 compression Methods 0.000 abstract description 4
- 230000002787 reinforcement Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000004593 Epoxy Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229910002019 Aerosil® 380 Inorganic materials 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical group NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- PLIKAWJENQZMHA-UHFFFAOYSA-N p-hydroxyphenylamine Natural products NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は優れた耐湿熱特性、耐衝撃後圧縮特性を与える
プリプレグ用エポキシ樹脂組成物に関するものであり、
当該樹脂組成物から得られる複合材料は航空機を始め自
動車、一般工業用途に使用しうるものである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an epoxy resin composition for prepregs that provides excellent heat and humidity resistance and impact resistance and compression properties.
Composite materials obtained from the resin composition can be used in aircraft, automobiles, and general industrial applications.
従来複合材料用マトリックス樹脂としてはエポキシ樹脂
がその接着性、高剛性の為多用されて来た。中でも高性
能構造用マトリックス樹脂としてはＮ、Ｎ、Ｎ’、Ｎ’
−テトラグリシジル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ホンを主成分とする組成
物が１９７２年来広年来用されて来たところでありた。Epoxy resins have traditionally been widely used as matrix resins for composite materials due to their adhesive properties and high rigidity. Among them, N, N, N', N' are used as matrix resins for high-performance structures.
-tetraglycidyldiaminodiphenylmethane, 4.
Compositions containing 4'-diaminodiphenylsulfone as a main component have been in use for many years since 1972.
しかるにこの組成物から得られる複合材料は吸湿後の高
温圧縮強度は比較的高いもののマトリックス樹脂の伸び
が小さい為に最近の高伸度補強用繊維、例えば１．５％
以上の破断伸度を有する炭素繊維、アラミド繊維、ガラ
ス繊維等に追従出来ず引張り伸度が補強用繊維より低い
欠点を有していた。又衝撃後の圧縮強度が極めて低く、
−次構造用素材として用いるには全く不十分な材料であ
った。However, although the composite material obtained from this composition has a relatively high high-temperature compressive strength after moisture absorption, the elongation of the matrix resin is low, so it cannot be used with recent high-elongation reinforcing fibers such as 1.5%.
It had the disadvantage that it could not follow carbon fibers, aramid fibers, glass fibers, etc., which have elongation at break above the above, and its tensile elongation was lower than that of reinforcing fibers. Also, the compressive strength after impact is extremely low.
-The material was completely inadequate for use as a material for the next structure.
本発明者らは上記に鑑み、優れた耐湿熱特性、高い補強
材利用率、耐衝撃後圧縮特性を有する複合材を与えるプ
リプレグ用エポキシ樹脂組成物に関し、鋭意検討の結果
、本発明に到達したものである。In view of the above, the present inventors have arrived at the present invention as a result of intensive studies regarding an epoxy resin composition for prepreg that provides a composite material having excellent heat and humidity resistance, high reinforcement utilization rate, and impact resistance and compression properties. It is something.
Ｌ問題点を解決するための手段〕
即ち本発明の要旨とするところは
悼） ２官能エポキシ樹脂
（Ｂ）３官能エポキシ樹脂
（Ｃ１下式で示されるフェノール化合物（但し、Ｘ、〜
Ｘ、はＢｒ、 ＣＩ、 Ｈを示し、そのうち４以上はＢ
ｒ又はＣＪ％ Ｒ，、Ｒ，はＨ又はＣＨ，を各表す）
（ＤＪ ４．４’−ジアミノジフェニルスルホン又は
３．３’−ジアミノジフェニルスルホンを必須成分とし
て含有するエポキシ樹脂組成物である。Means for Solving the L Problems] In other words, the gist of the present invention is as follows: Bifunctional epoxy resin (B) Trifunctional epoxy resin (C1 A phenolic compound represented by the following formula (However, X, ~
X indicates Br, CI, H, of which 4 or more are B
r or CJ% R,, R, each represents H or CH. (DJ) An epoxy resin composition containing 4.4'-diaminodiphenylsulfone or 3.3'-diaminodiphenylsulfone as an essential component.
これらの組成物のうち、一部もしくはすべての（Ａｌお
よびすべての（Ｂ）とすべての（Ｃ）とを、予め（Ｃ１
のフェノール性ＯＨの８０％以上を（４）、（Ｂ）のエ
ポキシ基と予備反応させることは好ましいことである。Of these compositions, some or all (Al and all (B) and all (C)
It is preferable to pre-react at least 80% of the phenolic OH of (4) and (B) with the epoxy groups.
更に本発明は上記エポキシ樹脂組成物に強化繊維を含む
エポキシ樹脂組成物にある。Furthermore, the present invention resides in an epoxy resin composition containing reinforcing fibers in the above-mentioned epoxy resin composition.
本発明において用いられる（Ａｌ ２官能エポキシ樹脂
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、ツレらのブロム化エポキシ樹
脂、ビスフェノールＳ型エポキシ樹脂等が挙げられる。Examples of the Al difunctional epoxy resins used in the present invention include bisphenol A epoxy resins, bisphenol F epoxy resins, brominated epoxy resins of Tsure et al., and bisphenol S epoxy resins.
靭性向上の為には、中でもビスフェノールＡ型エポキシ
樹脂、ビスフェノールＡ型エポキシ樹脂を主成分として
用いることが望ましい。又これらの成分（５）のその他
エポキシ樹脂（Ｂｌとのモル比は囚／（Ｂｌ ＝ ｌ
１０．１〜１／１．２であり、好ましくは１ ／ ０．
２〜ｌ ／ １． Ｏである。この範囲より多い場合に
は耐熱性が低下する他、耐薬品性が低下する為好ましく
ない。又この範囲より少ない場合には靭性伸びが不足す
る為好ましくない。In order to improve toughness, it is desirable to use bisphenol A epoxy resin or bisphenol A epoxy resin as the main component. In addition, the molar ratio of these components (5) to other epoxy resins (Bl) is /(Bl = l
10.1 to 1/1.2, preferably 1/0.
2~l/1. It is O. If the amount exceeds this range, heat resistance and chemical resistance will decrease, which is not preferable. Moreover, if it is less than this range, it is not preferable because the toughness and elongation will be insufficient.
本発明に用いられる３官能エポキシ樹脂（Ｂｌとしては
、グリシジルアミン呈エポキシ樹脂、例えばＮ、Ｎ、Ｏ
−）リグリシジル−ｐ−又はｍ−アミンフェノール、
Ｎ、Ｎ、０− ）リグリシジル−４−アミノ−ｍ−又は
−５−アミノ−〇−クレゾール、１，１．１− （）リ
グリシジルオキシフェニル）メタン等が挙げられる。The trifunctional epoxy resin used in the present invention (Bl is a glycidylamine-bearing epoxy resin, such as N, N, O
-) liglycidyl-p- or m-aminephenol,
N,N,0-)liglycidyl-4-amino-m- or -5-amino-〇-cresol, 1,1.1-()liglycidyloxyphenyl)methane, and the like.
中でもＮ、Ｎ、０−）リグリシジル−ｐ−又はｍ−アミ
ノフェノール、Ｎ、Ｎ、Ｏ−トリグリシジル−４−アミ
ノ−ｍ−又は−５−アミノ−〇−クレゾールが好ましく
用いられる。Among them, N,N,0-)liglycidyl-p- or m-aminophenol, N,N,O-triglycidyl-4-amino-m- or -5-amino-〇-cresol are preferably used.
本発明で用いられるフェノール化合物（Ｃ）としては、
ナト２ブロムビスフエノールＡ１テト２ブロムビスフエ
ノールＦ、オクタクロムビスフェノールＡ、ヘキサブロ
ムビスフェノールｈ％が挙げられる。As the phenol compound (C) used in the present invention,
Nato 2 bromo bisphenol A1 te 2 bromo bisphenol F, octachrome bisphenol A, hexabromo bisphenol h%.
■）成分の硬化剤としては、 ４．４’−ジアミノジフ
ェニルスルホンが好ましく用いられる。As the curing agent for component (2), 4,4'-diaminodiphenylsulfone is preferably used.
（Ｅｌ成分の補強用繊維としては、炭素繊維、ガラス繊
維、アラミド繊維、ボロン繊維、シリコンカーバイド繊
維等が挙げられる。(Examples of reinforcing fibers for the El component include carbon fibers, glass fibers, aramid fibers, boron fibers, silicon carbide fibers, etc.
エポキシ樹脂（Ａｌ （Ｂ）に対する（Ｃ）は、エポキ
シ基／フェノール性ＯＨ基の比が１１０．１〜Ｉ１０．
７であることが好ましく、フェノール性ＯＨ基が１７０
、１より太きいと充分な耐水性と靭性が得られない為適
当でなく、１１０．１より小さいと架橋度が低下して耐
熱性、耐溶剤性が低下する為好ましくない。より好まし
くは１／ ０．３〜１ ／ ０．６である。The epoxy resin (C) to Al (B) has an epoxy group/phenolic OH group ratio of 110.1 to I10.
7, and the phenolic OH group is 170
If it is thicker than 1, it is not suitable because sufficient water resistance and toughness cannot be obtained, and if it is smaller than 110.1, it is not preferable because the degree of crosslinking decreases, resulting in a decrease in heat resistance and solvent resistance. More preferably it is 1/0.3 to 1/0.6.
又、エポキシ樹脂（Ａ）のすべてもしくは一部と申）の
すべてとすべての（Ｃ１とを、予め（Ｃ１の７エノール
性ＯＨの８０％以上、より好ましくは９０％以上とを反
応させることが好ましい。これより低い反応率では樹脂
組成物の耐衝撃性が低下する為、上記の程度予備反応さ
せることが好ましい。In addition, all or part of the epoxy resin (A) and all (C1) may be reacted in advance with 80% or more, more preferably 90% or more of the 7-enolic OH of (C1). Preferably. If the reaction rate is lower than this, the impact resistance of the resin composition will be lowered, so it is preferable to pre-react to the above-mentioned extent.
（Ｃ１との予備反応に使用する一部もしくはすべての囚
、すべての（Ｂ）とのエポキシ基のモル比は囚／（Ｂｌ
＝１１０．２〜１／１．４、より好ましくは１ ／ ０
．４〜１／１，２である。ｌ ／ ０．２より大きいと
充分な耐熱性、耐水性、耐溶剤性が得られず好ましくな
い。又、１ ／ ｌ、 ４より小さいと予備反応下にゲ
ル化を起こす為好ましくない。(The molar ratio of epoxy groups to some or all of the reactants and all (B) used in the preliminary reaction with C1 is
=110.2 to 1/1.4, more preferably 1/0
．． It is 4 to 1/1,2. If it is larger than l/0.2, sufficient heat resistance, water resistance, and solvent resistance cannot be obtained, which is not preferable. Moreover, if it is less than 1/l, 4, gelation will occur during the preliminary reaction, which is not preferable.
更に予備反応に使用するエポキシ総モル数と（Ｃｌフェ
ノール性ＯＨモル数の比、即ち１ ／ ０．２〜１／１
とすることが好ましく、より好ましくは１１０．３
〜１１０．８ である。Ｉｌｏ、２より大きいと充分
な耐水性や靭性が得られず好ましくない。又、ｌ／ｌ
より小さいと予備反応時粘度が高（なり扱い性に難があ
る。Furthermore, the ratio of the total number of moles of epoxy used in the preliminary reaction to the number of moles of (Cl phenolic OH, i.e., 1/0.2 to 1/1
preferably 110.3, more preferably 110.3
~110.8. When Ilo is larger than 2, sufficient water resistance and toughness cannot be obtained, which is not preferable. Also, l/l
If it is smaller, the viscosity during preliminary reaction will be high (and difficult to handle).
一方（４）（８１（Ｃ１に対する口）の使用量は全エポ
キシ基のモル数から（Ｃ）のフェノール性ＯＨのモル数
を差し引いたものとＣＤＩのＮＨ基のモル数の比を１７
０．５〜１／１．２として用いることが好ましい。ｌ
／ ０．５より大きいと硬化が不十分となり、耐溶剤性
、耐熱性に難があり、１／１，２より小であると耐水性
が低下すると共に耐溶剤性が低下するので難がある。On the other hand, the amount of (4) (81 (percentage relative to C1) used is the ratio of the number of moles of phenolic OH in (C) subtracted from the number of moles of total epoxy groups to the number of moles of NH group in CDI, which is 17
It is preferable to use it as 0.5 to 1/1.2. l
/ If it is larger than 0.5, curing will be insufficient and there will be problems in solvent resistance and heat resistance, and if it is smaller than 1/1 or 2, there will be problems as water resistance and solvent resistance will decrease. .
本発明の樹脂組成物には、他の成分として無機光てん剤
、例えばシリカ粉末、アエロジル、マイクロバルーンや
難燃剤としての三酸化アンチモン等の他、流れ性制御の
目的で末端フェノールのポリエーテルスルホン、ポリス
ルホン、ポリビニルブチラード、ポリエーテルイミド等
を併用することもさしつかえない。The resin composition of the present invention contains other components such as inorganic photonic agents such as silica powder, Aerosil, microballoons, antimony trioxide as a flame retardant, and polyether sulfone with a terminal phenol for the purpose of flow control. , polysulfone, polyvinyl butyralide, polyetherimide, etc. may be used in combination.
又、補強用繊維はミルドファイバー、チョツプドファイ
バー、一方向シート状、織物状の形態で用いることも可
能である。The reinforcing fibers can also be used in the form of milled fibers, chopped fibers, unidirectional sheets, or woven fabrics.
以下実施例により本発明を具体的に説明する。 The present invention will be specifically explained below using Examples.
部は五短部を表す。The part represents the five short parts.
実施例１
ビスフェノールＦジグリシジルエーテル（商品名 エ
ピコート８０７、エポキシ当量１７０、油化シェルエポ
キシ（株）製）１００部、Ｎ、Ｎ、０−トリグリシジル
−ｐ−アミノフェノ−／Ｉ／（工。Example 1 100 parts of bisphenol F diglycidyl ether (trade name: Epicote 807, epoxy equivalent: 170, manufactured by Yuka Shell Epoxy Co., Ltd.), N,N,0-triglycidyl-p-aminopheno-/I/ (trade name).
ボキシ当量１０６）１８．７部、２，２−ビス（３゜５
−’）７’ロモー４−ヒドロキシフェニル）フロパン４
１．６部を１２０℃で混合溶解した後、６０℃として４
．４′−ジアミノジフェニルスルホン３７．９部と酸化
珪素微粉末（Ａｅｒｏａｉｌ ３８０、日本アエロジ
ル（株）製）２．４部を加えニーダ−によりよく混合し
て樹脂組成物（１）を得た。この組成物（１）を２ｍ板
となる様ガラス板にはさみ、１８０℃で２時間硬化し樹
脂板を得た。又この樹脂組成物（１）を６０℃に加熱下
ドクターナイフで離型紙上に流延し、７８Ｐ／−のホッ
トメルトフィルムを作製した。このフィルム上に一方向
に引き揃えた炭素繊維（パイロフィルＭ−１、三菱レイ
ヨン（株）製商標）を当て、温度と圧力により樹脂を繊
維に含浸せしめ、糸目性１４５７７ｍ”、樹脂含有率３
５１に量％の一方向プリプレグを作成した。このプリプ
レグをＬＯｏ）ｔｓ 及ヒ（＋４５７００／−４ｓ°
／９０’ｌａｓの擬等方性に積層し、１８０℃で２時間
、圧力５ ｋｇＧ ／ｃａｔ”のオートクレーブ中で硬
化せしめ複合材料パネルを得た。それらについての試験
結果をｆ！１に示した。Boxy equivalent 106) 18.7 parts, 2,2-bis(3°5
-')7'romo4-hydroxyphenyl)furopane4
After mixing and dissolving 1.6 parts at 120°C, the mixture was heated to 60°C and 4
．． 37.9 parts of 4'-diaminodiphenylsulfone and 2.4 parts of silicon oxide fine powder (Aeroail 380, manufactured by Nippon Aerosil Co., Ltd.) were added and thoroughly mixed in a kneader to obtain a resin composition (1). This composition (1) was sandwiched between glass plates to form a 2 m plate and cured at 180° C. for 2 hours to obtain a resin plate. Further, this resin composition (1) was heated to 60°C and cast onto release paper using a doctor knife to prepare a 78P/- hot melt film. Carbon fibers (Pyrofil M-1, a trademark manufactured by Mitsubishi Rayon Co., Ltd.) aligned in one direction were placed on this film, and the fibers were impregnated with resin using temperature and pressure.
A unidirectional prepreg with a weight of 51% was prepared. This prepreg is LOo)ts and hee(+45700/-4s°
/90'las pseudo-isotropically laminated and cured in an autoclave at 180°C for 2 hours at a pressure of 5 kgG/cat'' to obtain composite panels.The test results for these are shown in f!1. .
複合材の耐熱水性は００１６層の積層材コンポジットな
７１℃の水中に１４日間放置した後ＡＳＴＭ Ｄ−３
４１０に従って８２℃で０９方向の圧縮試験をすること
により求めた。The hot water resistance of the composite material is ASTM D-3 after 14 days of 0016 layer laminate composite in water at 71°C.
It was determined by carrying out a compression test in the 09 direction at 82° C. according to 410.
また、耐衝撃性はＮＡＳＡ ＲＰ１０９２に準拠して
パネル寸法４′×ｅ の板を３’Ｘ５’の穴のあいた
台上に固定して、その中心にと′Ｒのノーズをつけた４
、 ９ ｋｇの分銅を落下せしめ、板厚１インチ当り１
５００ ｊｂ−１ｎの衝撃を加えた後そのパネルを圧縮
試験することにより求めた。In addition, the impact resistance was determined based on NASA RP1092 by fixing a board with panel dimensions of 4' x e on a stand with a 3' x 5' hole, and attaching a nose of 'R' to the center of the board.
, a weight of 9 kg is dropped, and the weight is 1 per inch of plate thickness.
It was determined by compression testing the panel after applying an impact of 500 jb-1n.
樹脂の扱い性は樹脂組成物（１）の室温での柔らかさに
より判定した。耐メチルエチルケトン性（耐ＭＥＫ性）
は樹脂硬化物の室温下７日メチルエチルケトン浸漬後の
外観変化により判定し、変化のないものを○、大のもの
を×とした。The handleability of the resin was determined by the softness of the resin composition (1) at room temperature. Methyl ethyl ketone resistance (MEK resistance)
was determined by the change in appearance of the cured resin product after immersion in methyl ethyl ketone at room temperature for 7 days, and those with no change were rated ◯, and those with large changes were rated ×.
実施例２〜６、比較例１〜６
実施例１のエピコート８０７、Ｎ、Ｎ、Ｏ−トリグリシ
ジル−ｐ−アミンフェノール、２，２−ビス（３，５−
ジブロー１ニー４−ヒドロキシフェニル）プロパン、４
．４’−ジアミノジフェニルスルホンの配合比を変えて
実施例１と同様の実験をして併せて表１に示した。Examples 2-6, Comparative Examples 1-6 Epicote 807 of Example 1, N,N,O-triglycidyl-p-aminephenol, 2,2-bis(3,5-
Dibro 1-4-hydroxyphenyl)propane, 4
．． The same experiment as in Example 1 was conducted by changing the blending ratio of 4'-diaminodiphenylsulfone, and the results are also shown in Table 1.
本結果よりＡ／Ｂエポキシモル比に適正域のあること、
Ａ＋Ｂ／Ｃ（ＡとＢの全エポキシモル数とＣのフェノー
ル性０１４モル数との比）、Ａ＋Ｂ−Ｃ／Ｄ （Ａ、
Ｂ全エポキシモル数からＣのフェノール性ＯＨモル数を
引いたものとＤのアミンのＮＨ官能基モル数の比）に適
性域のあることがわかる。From this result, there is an appropriate range for the A/B epoxy molar ratio,
A+B/C (ratio of the total number of epoxy moles of A and B to the number of phenolic 014 moles of C), A+B-C/D (A,
It can be seen that there is an appropriate range in the ratio between the total number of epoxy moles in B minus the number of moles of phenolic OH in C and the number of moles of NH functional groups in the amine in D.
実施例７
実施例１において、二ピコ−）８０７０代りに二ピフー
）８２Ｂ（ビスフェノールＡジグリシジルエーテル壓エ
ポキシ、油化シェルエポキシ（株）製画品名、エポキシ
当量１８８）とエピコート８０７のｌ：２！ｉ比の混合
物を用いる他は同様にして試験した結果を表１に示した
。Example 7 In Example 1, 2 Pifu) 82B (bisphenol A diglycidyl ether epoxy, manufactured by Yuka Shell Epoxy Co., Ltd., product name, epoxy equivalent weight 188) and Epicoat 807 were used in l:2 ! Table 1 shows the results of a test conducted in the same manner except that a mixture with a ratio of i was used.
実施例８
実施例７において、硬化剤として４，４′−ジアミノジ
フェニルスルホンの代りに４．４’−ジアミノジフェニ
ルスルホンとジシアンジアミドの１０／１重量比混合物
を用いる他は同様にして試験した結果を表１に示した。Example 8 The same test results as in Example 7 were obtained except that a 10/1 weight ratio mixture of 4,4'-diaminodiphenylsulfone and dicyandiamide was used instead of 4,4'-diaminodiphenylsulfone as the curing agent. It is shown in Table 1.
実施例９〜１５
実施例７ＯＮ、Ｎ、０− ）リグリシジル−ｐ−アミン
フェノールの代りにＮ、Ｎ、Ｏ−トリグリシジル−ｍ−
アミンフェノール、Ｎ、Ｎ、０− トリグリシジル−４
−アミノ−ｍ−クレゾール、Ｎ、Ｎ、０−トリグリシジ
ル−５−アミノ−０−フレジー＃、１，１．１− （ト
リグリシジルオキシフェニル）メタンを用いて配合比を
変えて同様の実験をし表２に示した。Examples 9-15 Example 7 ON,N,0-) N,N,O-triglycidyl-m- instead of liglycidyl-p-aminephenol
Aminephenol, N,N,0-triglycidyl-4
Similar experiments were carried out using -amino-m-cresol, N,N,0-triglycidyl-5-amino-0-frezy #, and 1,1.1-(triglycidyloxyphenyl)methane with different blending ratios. It is shown in Table 2.
実施例１６．１７
実施例１の系のフェノール化合物（Ｃ１、硬化剤の）を
変えて実験した結果を表２に示した。Example 16.17 Table 2 shows the results of an experiment in which the phenol compound (C1, curing agent) of the system of Example 1 was changed.
実施例１８
実施例１の組成を用いるが、エピコート８０７を２つに
分けて一部を予備重合せしめて使用した。即ち、エピコ
ート８０７ ３２部、Ｎ、Ｎ、０−トリグリシジル−ｐ
−アミノフェノ−／Ｉ／１８．７部、２，２−ビス（３
，５−ジブロモ−４−ヒドロキシフェニル）プロパン４
１．６ｉ１Ｓを１３０℃で２時間反応せしめて後、６０
℃迄冷却し、のこりのエピコー）８０７ ６８部、４，
４′−ジアミノジフェニルスルホン３７．９ 部を加ａ
ｔ、−１更にＡｅｒｏｓｉｌ ３８０ ２．４部を加え
てニーダ−（６０℃に保温）中でよく混合して樹脂組成
物（［１）を得た。この組成物（ＩＩ）を実施例１の組
成物（１）の代りに用いる他は同様にして樹脂板及びコ
ンポジットの試験に供した。結果を表３に示した。Example 18 The composition of Example 1 was used, except that Epikote 807 was divided into two parts and a portion was prepolymerized. That is, 32 parts of Epicote 807, N,N,0-triglycidyl-p
-aminopheno-/I/18.7 parts, 2,2-bis(3
,5-dibromo-4-hydroxyphenyl)propane 4
After reacting 1.6i1S at 130°C for 2 hours, 60
Cool to ℃ and recycle the remaining Epicor) 807 68 parts, 4,
Add 37.9 parts of 4'-diaminodiphenylsulfone a.
t, -1 Further, 2.4 parts of Aerosil 380 were added and mixed well in a kneader (kneaded at 60°C) to obtain a resin composition ([1)]. Resin plates and composites were tested in the same manner as in Example 1, except that this composition (II) was used in place of composition (1). The results are shown in Table 3.
実施例１９〜２６、比較例７〜１１
実施例１８の系のエピコート８０７、Ｎ、Ｎ、０−トリ
グリシジル−ｐ−アミンフェノール、２゜２−ビス（３
，５−ジブロモ−４−ヒドロキシフェニル）プロパン、
４，４′−ジアミノジフェニルスルホンの混合比を変え
て実施例１８と同様の実験をして併せて表３に示した。Examples 19 to 26, Comparative Examples 7 to 11 Epicote 807 of the system of Example 18, N,N,0-triglycidyl-p-aminephenol, 2゜2-bis(3
, 5-dibromo-4-hydroxyphenyl)propane,
The same experiment as in Example 18 was carried out by changing the mixing ratio of 4,4'-diaminodiphenylsulfone, and the results are also shown in Table 3.
実施例１と実施例１８，２３，２４．２５の対比より、
同様の系では予備反応反応率を８０％以上とすることが
衝撃後の圧縮強度の向上に有効であることがわかる。From the comparison between Example 1 and Examples 18, 23, 24.25,
It can be seen that in a similar system, setting the preliminary reaction rate to 80% or more is effective in improving the compressive strength after impact.
又、予備反応して使用する場合にもＡ／Ｂエポキシモル
比、Ａ十Ｂ／Ｃ（予備反応に用いるＡとＢの全エポキシ
モル数とＣのフェノール性ＯＨモル数との比）、Ａ＋Ｂ
＋Ａ’／Ｃ（予備反応及び予備反応をしないエポキシ全
モル数とＣのフェノール性ＯＨモル数との比）、Ａ十Ｂ
＋Ａ’−Ｃ／Ｄ （全エポキシモル数からＣのフェノ
ール性ＯＨモル数を差し引いたモル数とＤのアミンのＮ
Ｈ官能基モル数の比）に適正域のあることがわかる。In addition, when used after preliminary reaction, the A/B epoxy molar ratio, A + B/C (ratio of the total number of epoxy moles of A and B used in the preliminary reaction and the number of moles of phenolic OH of C), A + B
+A'/C (ratio of total number of moles of epoxy without pre-reaction and pre-reaction to number of moles of phenolic OH of C), A0B
+A'-C/D (number of moles obtained by subtracting the number of moles of phenolic OH of C from the number of total epoxy moles and N of amine of D)
It can be seen that there is an appropriate range for the ratio of the number of moles of H functional groups.
実施例２７
実施例１８において、予備反応に使用する２官能エポキ
シ樹脂、エピコート８０７０代りにエピコート８２８を
用いる他は同様にして試験し結果を表３に併せて示した
。Example 27 Tests were conducted in the same manner as in Example 18, except that Epicote 828 was used instead of Epicote 8070 as the bifunctional epoxy resin used in the preliminary reaction, and the results are also shown in Table 3.
比較例１２
実施例１において、樹脂組成物（１）の代りにＮ、Ｎ、
Ｎ；Ｎ’−テトラグリシジルジアミノジフェニルメタン
１００部、 ４．４’−ジアミノジフェニルスルホン５
５部を１３０℃で３０分混合攪拌したものを用いる他は
実施例１と同様にして実験した結果を表２に示した。Comparative Example 12 In Example 1, N, N,
N; 100 parts of N'-tetraglycidyldiaminodiphenylmethane, 4.4'-diaminodiphenylsulfone 5
Table 2 shows the results of an experiment conducted in the same manner as in Example 1, except that 5 parts were mixed and stirred at 130° C. for 30 minutes.
Claims (1)
て含有することを特徴とするエポキシ樹脂組成物 （Ａ）２官能エポキシ樹脂 （Ｂ）３官能エポキシ樹脂 （Ｃ）下式で示されるフェノール化合物 ▲数式、化学式、表等があります▼ （但し、Ｘ＿１〜Ｘ＿８はＢｒ、Ｃｌ、Ｈを示し、その
うち４以上はＢｒ又はＣｌ、Ｒ＿１、Ｒ＿２はＨ又はＣ
Ｈ＿３を各表す） （Ｄ）４，４′−ジアミノジフェニルスルホン又は３，
３′−ジアミノジフェニルスルホン ２、（Ａ）２官能エポキシ樹脂がビスフェノールＡ型お
よびもしくはビスフェノールＦ型のエポキシ樹脂である
ことを特徴とする特許請求の範囲第１項記載の組成物 ３、（Ｂ）３官能エポキシ樹脂がＮ，Ｎ，Ｏ−トリグリ
シジル−ｐ−又はｍ−アミノフェノール、 ｌ，ｌ，ｌ−（トリグリシジルオキシフェニル）メタン
、Ｎ，Ｎ，Ｏ−トリグリシジル−４−アミノ−ｍ−又は
５−アミノ−ｏ−クレゾールの一種もしくは二種以上の
混合物であることを特徴とする特許請求の範囲第１項記
載の組成物 ４、（Ｃ）成分としてテトラブロムビスフェノールＡを
用いることを特徴とする特許請求の範囲第１項記載の組
成物 ５、（Ａ）／（Ｂ）のエポキシ基のモル比が１／０．１
〜１／１．２、好ましくは１／０．２〜１／１．０であ
ることを特徴とする特許請求の範囲第１項記載の組成物 ６、（Ｃ）の使用量は（Ａ）と（Ｂ）のエポキシ基に対
する（Ｃ）のフェノール性ＯＨに対する比が１／０．１
〜１／０．７であることを特徴とする特許請求の範囲第
１項記載の組成物 ７、（Ｄ）の使用量は（Ａ）、（Ｂ）のエポキシ基モル
数から（Ｃ）のフェノール性ＯＨ基モル数を差し引いた
ものと（Ｄ）のＮＨ基のモル数の比を１／０．５〜１／
１．２として用いることを特徴とする特許請求の範囲第
１項記載の組成物 ８、（Ａ）のすべてもしくは一部と（Ｂ）のすべてとを
混合し、これと（Ｃ）のすべてとを予備反応せしめ、少
なくとも（Ｃ）のフェノール性ＯＨの８０％を予備反応
せしめて使用することを特徴とする特許請求の範囲第１
項記載の組成物 ９、予備反応して使用する（Ａ）／（Ｂ）のエポキシ基
のモル比は１／０．２〜１／１．４とし、（Ｃ）の使用
量を（Ａ）、（Ｂ）のエポキシ基のモル数の和と（Ｃ）
のフェノール性ＯＨとのモル比を１／０．２〜１／１と
することを特徴とする特許請求の範囲第８項記載の組成
物 １０、（Ｄ）の使用量がすべての（Ａ）および（Ｂ）の
エポキシ基モル数から（Ｃ）のフェノール性ＯＨ基モル
数を差し引いたものと（Ｄ）のＮＨ基のモル数の比を１
／０．５〜１／１．２として用いることを特徴とする特
許請求の範囲第１項記載の組成物 １１、下記成分（Ａ）（Ｂ）（Ｃ）（Ｄ）（Ｅ）を必須
成分として含有することを特徴とするエポキシ樹脂組成
物 （Ａ）２官能エポキシ樹脂 （Ｂ）３官能エポキシ樹脂 （Ｃ）下式で示されるフェノール化合物 ▲数式、化学式、表等があります▼ （但し、Ｘ＿１〜Ｘ＿８はＢｒ、Ｃｌ、Ｈを示し、その
うち４以上はＢｒ又はＣｌ、Ｒ＿１、Ｒ＿２はＨ又はＣ
Ｈ＿３を各表す） （Ｄ）４，４′−ジアミノジフェニルスルホン又は３，
３′−ジアミノジフェニルスルホン （Ｅ）補強用繊維[Claims] 1. An epoxy resin composition characterized by containing the following components (A), (B), (C), and (D) as essential components (A) a bifunctional epoxy resin (B) a trifunctional epoxy Resin (C) Phenolic compound represented by the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. C
(D) 4,4'-diaminodiphenylsulfone or 3,
3'-diaminodiphenylsulfone 2, composition 3 according to claim 1, characterized in that (A) the bifunctional epoxy resin is a bisphenol A type and/or bisphenol F type epoxy resin; (B) The trifunctional epoxy resin is N,N,O-triglycidyl-p- or m-aminophenol, l,l,l-(triglycidyloxyphenyl)methane, N,N,O-triglycidyl-4-amino-m Composition 4 according to claim 1, characterized in that it is one or a mixture of two or more of - or 5-amino-o-cresol, wherein tetrabromobisphenol A is used as component (C). Composition 5 according to claim 1, characterized in that the molar ratio of epoxy groups in (A)/(B) is 1/0.1
Composition 6 according to claim 1, characterized in that the amount of (C) used is 1/1.2, preferably 1/0.2 to 1/1.0. and the ratio of the epoxy group of (B) to the phenolic OH of (C) is 1/0.1
Composition 7 according to claim 1, characterized in that the ratio is 1/0.7, the amount of (D) to be used is the same as the number of moles of epoxy groups in (A) and (B) to the number of moles of epoxy groups in (C). The ratio of the number of moles of phenolic OH groups minus the number of moles of NH groups in (D) is 1/0.5 to 1/
Composition 8 according to claim 1, characterized in that it is used as 1.2, in which all or part of (A) and all of (B) are mixed, and this and all of (C) are mixed. Claim 1 characterized in that the phenolic OH of (C) is pre-reacted and at least 80% of the phenolic OH of (C) is used.
Composition 9 described in section 9, the molar ratio of the epoxy groups of (A)/(B) used by preliminary reaction is 1/0.2 to 1/1.4, and the amount of (C) used is , the sum of the number of moles of epoxy groups in (B) and (C)
Composition 10 according to claim 8, characterized in that the molar ratio of (D) to phenolic OH is 1/0.2 to 1/1, the amount of (D) used is all of (A) And the ratio of the number of moles of epoxy groups in (B) minus the number of moles of phenolic OH groups in (C) to the number of moles of NH groups in (D) is 1.
/0.5 to 1/1.2, the composition 11 according to claim 1, wherein the following components (A), (B), (C), (D), and (E) are essential components. An epoxy resin composition characterized by containing (A) a bifunctional epoxy resin (B) a trifunctional epoxy resin (C) a phenol compound represented by the following formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (However, X_1 ~X_8 represents Br, Cl, H, 4 or more of which are Br or Cl, R_1, R_2 are H or C
(D) 4,4'-diaminodiphenylsulfone or 3,
3'-diaminodiphenylsulfone (E) reinforcing fiber
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13840087A JPH075709B2 (en) | 1987-06-02 | 1987-06-02 | Epoxy resin composition |
| PCT/JP1988/001212 WO1990006334A1 (en) | 1987-06-02 | 1988-11-30 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13840087A JPH075709B2 (en) | 1987-06-02 | 1987-06-02 | Epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63301221A true JPS63301221A (en) | 1988-12-08 |
| JPH075709B2 JPH075709B2 (en) | 1995-01-25 |
Family
ID=15221068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13840087A Expired - Fee Related JPH075709B2 (en) | 1987-06-02 | 1987-06-02 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH075709B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6620510B1 (en) | 1998-12-25 | 2003-09-16 | Mitsubishi Rayon Co., Ltd. | Epoxy resin composition, prepreg, and roll made of resin reinforced with reinforcing fibers |
-
1987
- 1987-06-02 JP JP13840087A patent/JPH075709B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6620510B1 (en) | 1998-12-25 | 2003-09-16 | Mitsubishi Rayon Co., Ltd. | Epoxy resin composition, prepreg, and roll made of resin reinforced with reinforcing fibers |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH075709B2 (en) | 1995-01-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |