JPH0262144B2 - - Google Patents
Info
- Publication number
- JPH0262144B2 JPH0262144B2 JP60292813A JP29281385A JPH0262144B2 JP H0262144 B2 JPH0262144 B2 JP H0262144B2 JP 60292813 A JP60292813 A JP 60292813A JP 29281385 A JP29281385 A JP 29281385A JP H0262144 B2 JPH0262144 B2 JP H0262144B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- present
- resin composition
- thermoplastic resin
- polyether sulfone
- 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.)
- Expired - Lifetime
Links
- 229920005992 thermoplastic resin Polymers 0.000 claims description 17
- 239000003822 epoxy resin Substances 0.000 claims description 14
- 229920000647 polyepoxide Polymers 0.000 claims description 14
- 239000011342 resin composition Substances 0.000 claims description 13
- 239000004695 Polyether sulfone Substances 0.000 claims description 12
- 229920006393 polyether sulfone Polymers 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 8
- 229920001187 thermosetting polymer Polymers 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 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 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012783 reinforcing fiber Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011157 advanced composite material Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 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 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- RDIGYBZNNOGMHU-UHFFFAOYSA-N 3-amino-2,4,5-tris(oxiran-2-ylmethyl)phenol Chemical compound OC1=CC(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 RDIGYBZNNOGMHU-UHFFFAOYSA-N 0.000 description 1
- CXXSQMDHHYTRKY-UHFFFAOYSA-N 4-amino-2,3,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1=C(O)C(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 CXXSQMDHHYTRKY-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000002994 raw material 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
- 239000000779 smoke Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、先進複合材料として、強度、弾性
率、さらにはこれらを比重で除した、比強度、比
弾性率の大なることを要求される構造体に用いら
れるプリプレグに用いる樹脂組成物の製法に関す
る。さらに詳しくは、人体に有害な溶媒を用いる
ことなく、短時間で、熱的に不安定な熱硬化性樹
脂を含む樹脂組成物を製造する方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention is an advanced composite material that is required to have high strength, high elastic modulus, and high specific strength and high specific elastic modulus, which are obtained by dividing these by specific gravity. The present invention relates to a method for producing a resin composition used for a prepreg used in a structure. More specifically, the present invention relates to a method for producing a resin composition containing a thermally unstable thermosetting resin in a short time without using a solvent harmful to the human body.
［従来の技術］
先進複合材料は、強化繊維とマトリツクスから
なる不均一材料であり、一般にプリプレグとよば
れる中間基材が成形材料として便利なため、マト
リツクス樹脂としては、粘着性を有する積層の容
易なプリプレグを与える熱硬化性樹脂が、従来か
ら使用されている。マトリツクス樹脂は、強化繊
維の機械的性能を複合材料の構造体として発現さ
せるために重要な役目を担つており、特に、耐熱
性、耐水性、耐溶剤性、非繊維軸方向の機械的強
度といつた物性は、マトリツクス樹脂の物性を顕
著に反映する。従来から、特に耐熱性を要求され
る構造体は、テトラグリシジルジアミノジフエニ
ルメタンと、ジアミノジフエニルスルホンを主成
分とするエポキシ樹脂系が用いられてきている
が、この系は耐熱性が良好である半面、靭性に乏
しいため、耐衝撃性に劣るという欠点を有してい
る。近年、靭性の改良のため種々の熱可塑性樹脂
をエポキシ樹脂とブレンドすることによる改良が
試みられているが、その混合方法においては、溶
媒を用いたり、長時間または高温条件を要したり
していた。[Prior art] Advanced composite materials are non-uniform materials consisting of reinforcing fibers and matrices, and an intermediate base material called prepreg is generally convenient as a molding material. Thermosetting resins that provide prepregs with high properties are conventionally used. Matrix resin plays an important role in expressing the mechanical performance of reinforcing fibers as a composite material structure, especially heat resistance, water resistance, solvent resistance, and mechanical strength in the non-fiber axial direction. The changed physical properties significantly reflect the physical properties of the matrix resin. Traditionally, epoxy resin systems containing tetraglycidyl diaminodiphenyl methane and diaminodiphenylsulfone as main components have been used for structures that require particularly high heat resistance, but this system has good heat resistance. On the other hand, it has the disadvantage of poor impact resistance due to its poor toughness. In recent years, attempts have been made to improve toughness by blending various thermoplastic resins with epoxy resins, but these mixing methods often require the use of solvents or long-term or high-temperature conditions. Ta.
例えば、特公昭46−17067や、特公昭48−5107
では、熱的に安定であるが耐熱性の乏しいビスフ
エノールＡ型エポキシ樹脂を用いて、溶媒を用い
ずにポリスルホンを溶解させているが、当然なが
ら耐熱性の低い硬化物しか得られていない。ま
た、特開昭58−134126では、ポリエーテルスルホ
ンを耐熱性の良好なテトラグリシジルジアミノジ
フエニルメタンに溶媒を用いて溶させている。ま
た、バツクナル（C.B.Bucknall）らも、ポリマ
ー（Polymer）第24巻第３号 639−644ページ
（1983年）において、テトラグリシジルジアノジ
フエニルメタンにポリエーテルスルホンを塩化メ
チレンを用いて溶解させている。また、セフエリ
ス（J.C.Seferis）らは、ポリマー・プレプリント
（Polymer Preprints）第26巻第２号 277−278
ページ（1985年）においてテトラグリシジルジア
ミノジフエニルメタンにポリエーテルスルホンを
無溶媒で溶解させているが、190℃という高温で
行ない、なおかつ170℃では均一な溶解ができな
かつたと述べている。 For example, Special Public Interest Publication No. 46-17067, Special Public Interest Publication No. 48-5107
In this method, polysulfone is dissolved without using a solvent using a bisphenol A type epoxy resin which is thermally stable but has poor heat resistance, but as a matter of course, only a cured product with low heat resistance is obtained. Furthermore, in JP-A-58-134126, polyether sulfone is dissolved in tetraglycidyldiaminodiphenylmethane, which has good heat resistance, using a solvent. Also, CBBucknall et al., in Polymer Vol. 24, No. 3, pp. 639-644 (1983), dissolved polyether sulfone in tetraglycidyl dianodiphenylmethane using methylene chloride. . In addition, JCSeferis et al., Polymer Preprints, Vol. 26, No. 2, 277-278
Page (1985) states that polyether sulfone was dissolved in tetraglycidyldiaminodiphenylmethane without a solvent, but the process was carried out at a high temperature of 190°C, and uniform dissolution was not possible at 170°C.
［発明が解決しようとする問題点］
以上のような樹脂組成物の製法上の欠点を改良
したものが本発明である。本発明においては、熱
可塑性樹脂を十分に検討された粉砕方法を用いる
ことにより目的に適した粒度とすることかでき、
溶媒を使用することなく最高160℃において短時
間でエポキシ樹脂に溶解させ、目的とする樹脂組
成物を得ることができる。[Problems to be Solved by the Invention] The present invention improves the above-mentioned drawbacks in the manufacturing method of the resin composition. In the present invention, the thermoplastic resin can be made into a particle size suitable for the purpose by using a well-examined pulverization method,
It is possible to obtain the desired resin composition by dissolving it in an epoxy resin in a short time at a maximum of 160°C without using a solvent.
［問題点を解決するための手段］
下記Ａ、Ｂ、Ｃを必須成分とするプリプレグ用
樹脂組成物の製法において、成分Ａを衝撃式粉砕
機により粒径150μｍ以下に粉砕した後、成分Ｂ
及びＣと混合することを特徴とする繊維強化プリ
プレグ用樹脂組成物の製法。[Means for solving the problem] In a method for producing a prepreg resin composition having the following essential components A, B, and C, component A is crushed to a particle size of 150 μm or less using an impact crusher, and then component B is crushed.
A method for producing a resin composition for fiber-reinforced prepreg, characterized by mixing with and C.
Ａ ガラス転移温度が100℃以上の熱可塑性樹脂
Ｂ エポキシ樹脂
Ｃ エポキシ硬化剤
熱可塑性樹脂と熱硬化性樹脂をブレンドしてプ
リプレグ用樹脂とすることは、特公昭46−17067、
特公昭48−5107、特開昭58−134126、特開昭60−
4526、特開昭60−58424などにより公知であるが、
その方法は、特開昭58−134126のように熱可塑性
樹脂を熱硬化性樹脂とともに溶媒に溶かした後、
溶媒を乾燥除去することが一般的であり、あるい
は、熱的に安定であるが耐熱性に劣るビスフエノ
ールＡ型エポキシ樹脂に高温で溶解させる方法な
どがとられていた。耐熱性にすぐれるが、自己硬
化性を有するテトラグリシジルジアミノジフエニ
ルメタンは、特に190℃という高温でなければ、
ガラス転移温度の高い熱可塑性樹脂であるポリエ
ーテルスルホンを無溶媒で溶解できないとの報告
もなされている。むろん混合温度が高ければ熱硬
化性樹脂の劣化を引き起すため、実用性に乏しい
プロセスしか、これまでには開発されていなかつ
た。A Thermoplastic resin with a glass transition temperature of 100°C or higher B Epoxy resin C Epoxy curing agent Blending a thermoplastic resin and a thermosetting resin to make a prepreg resin is known from Japanese Patent Publication No. 46-17067.
Special Publication No. 48-5107, No. 58-134126, No. 60-
4526, which is known from Japanese Patent Application Laid-Open No. 60-58424, etc.
The method is as in JP-A-58-134126, after dissolving the thermoplastic resin in a solvent together with the thermosetting resin,
It is common practice to remove the solvent by drying, or to dissolve it in bisphenol A type epoxy resin, which is thermally stable but has poor heat resistance, at high temperatures. Although it has excellent heat resistance, tetraglycidyldiaminodiphenylmethane, which has self-curing properties, cannot be used unless the temperature is particularly high, 190℃.
It has also been reported that polyether sulfone, which is a thermoplastic resin with a high glass transition temperature, cannot be dissolved without a solvent. Of course, high mixing temperatures cause deterioration of the thermosetting resin, so only impractical processes have been developed to date.
本発明においては、熱可塑性樹脂を衝撃式粉砕
機により粉砕した後に用いることを特徴としてい
る。 The present invention is characterized in that the thermoplastic resin is used after being crushed by an impact crusher.
本発明に用いる熱可塑性樹脂は、硬化物の耐熱
性を高めるために、用いる熱可塑性樹脂のガラス
転移温度（Tg）は、100℃以上の熱可塑性樹脂で
あるが、好ましくは、150℃以上の熱可塑性樹脂
である。主鎖中にSO2基を有するポリマーや、ポ
リアミドイミド、ポリイミドは特に好ましく用い
られる。これらは、一般にエンジニアリングプラ
スチツクに属し耐衝撃性が良好なため粉砕されに
くいポリマーである。 The thermoplastic resin used in the present invention is a thermoplastic resin with a glass transition temperature (Tg) of 100°C or higher, preferably 150°C or higher, in order to improve the heat resistance of the cured product. It is a thermoplastic resin. Polymers having SO 2 groups in the main chain, polyamideimide, and polyimide are particularly preferably used. These polymers generally belong to engineering plastics and have good impact resistance, making them difficult to crush.
本発明では、これら熱可塑性樹脂を衝撃式粉砕
機により粉砕する。熱可塑性樹脂を細かくするに
は、衝撃式粉砕機による方法と、ジエツト粉砕機
による方法と、沈澱法による方法が可能である
が、本発明により衝撃式粉砕機による方法が、最
も適していることが判明した。沈澱法によると細
かい粉末を容易に得ることができるが多量の溶媒
と沈澱剤を必要とするために、スケールを大きく
した時に製造コストを高めるため不適当である。
また、得られた粉末は、凝集しやすく取り扱いに
くい欠点を有する。また、ジエツト粉砕機による
方法では、目的に足るだけの細かい粉砕品は得ら
れない。これに対して、衝撃式粉砕機によると、
本発明にもつとも適した粉末を能率よく得ること
ができる。また、衝撃式粉砕機は、粉砕時に液体
窒素やドラスアイス等により冷却を行なうもの
が、本発明の目的により適している。衝撃式粉砕
機は、特にそのタイプを限定しないが、ブレード
（羽根）をモーターで回転し、ライナー（ブレー
ドのぶつかる壁）とブレードとのあいだで粉末が
衝撃を受けるタイプの粉砕機、具体的には、たと
えば、リンレツクスミルLX−Ｏ（ホソカワミクロ
ン(株)／大阪ガス社製、商標）、フアインビクトリ
−ミルFVP−１（ホソカワミクロン(株)製、商標）
などが好ましく使用される。 In the present invention, these thermoplastic resins are pulverized using an impact pulverizer. The thermoplastic resin can be pulverized by using an impact pulverizer, a jet pulverizer, or a precipitation method, but according to the present invention, the method using an impact pulverizer is the most suitable. There was found. Although fine powder can be easily obtained by the precipitation method, it requires a large amount of solvent and precipitant, which increases production costs when the scale is increased, making it unsuitable.
In addition, the obtained powder has the disadvantage that it tends to aggregate and is difficult to handle. Furthermore, the method using a jet pulverizer cannot produce a pulverized product fine enough for the purpose. On the other hand, according to the impact crusher,
Powder suitable for the present invention can be obtained efficiently. Furthermore, impact type crushers that perform cooling with liquid nitrogen, glass ice, or the like during crushing are more suitable for the purpose of the present invention. The impact type crusher is not limited to any particular type, but it is a type of crusher in which the blades are rotated by a motor and the powder is impacted between the liner (the wall that the blades collide with) and the blades. For example, Linrex Mill LX-O (manufactured by Hosokawa Micron Co., Ltd./Osaka Gas Co., Ltd., trademark), Fine Victory Mill FVP-1 (manufactured by Hosokawa Micron Co., Ltd., trademark)
etc. are preferably used.
本発明に用いる熱可塑性樹脂は、後述の比較例
２の結果から明らかなように、粉砕により150μ
ｍ以下の粒径とすることが必要である。粉砕後に
ふるい、あるいは気流分級機により大きな粒子を
除くことは組成物中に未溶解の粒子をなくするこ
とに大きな効果がある。 As is clear from the results of Comparative Example 2 described below, the thermoplastic resin used in the present invention can be crushed to a
It is necessary to set the particle size to less than m. Removing large particles using a sieve or air classifier after pulverization is highly effective in eliminating undissolved particles in the composition.
本発明に適したエポキシ樹脂としては、テトラ
グリシジルジアミノジフエニルメタン、トリグリ
シジル−ｐ−アミノフエノール、トリグリシジル
−ｍ−アミノフエノール、ビスフエノールＡ型エ
ポキシ樹脂、ビスフエノールＦ型エポキシ樹脂、
フエノールノボラツク型エポキシ樹脂、クレゾー
ルノボラツク型エポキシ樹脂、ブロム化エポキシ
樹脂、脂環式エポキ樹脂等が挙げられる。テトラ
グリシジルジアミノフエニルメタンは耐熱性が良
好で、強化繊維との接着性が良好なため最も適し
ている。 Epoxy resins suitable for the present invention include tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, bisphenol A type epoxy resin, bisphenol F type epoxy resin,
Examples include phenol novolac type epoxy resin, cresol novolac type epoxy resin, brominated epoxy resin, and alicyclic epoxy resin. Tetraglycidyldiaminophenylmethane is most suitable because it has good heat resistance and good adhesion to reinforcing fibers.
本発明に用いられるエポキシ硬化剤は、一般に
プリプレグ用硬化剤として用いられる硬化剤をす
べて用いることができる。具体的に例をあげる
と、
ジシアンジアミド
ジアミノジフエニルスルホン
構造式［］の化合物
ただし、Ｒは次の構造より選ばれる。 As the epoxy curing agent used in the present invention, all curing agents generally used as curing agents for prepregs can be used. To give a specific example, dicyandiamide diaminodiphenylsulfone A compound with the structural formula [] However, R is selected from the following structure.
−（CH2）o− ｎは３〜６の整数。 -(CH 2 ) o - n is an integer from 3 to 6.
−CH2−Ｃ（CH3）2CH2−
ジシアンジアミドはプリプレグの保存安定性に
優れるため好んで用いられる。またジアミノジフ
エニルスルホンは、耐熱性の良好な硬化物を与え
るため本発明には、最も適している。ジアミノジ
フエニルスルホンとしては、４，4′−、３，3′−
等種々の異性体や、異性体混合物が用いられる。 −CH 2 −C(CH 3 ) 2 CH 2 − Dicyandiamide is preferably used because it has excellent storage stability for prepregs. Furthermore, diaminodiphenylsulfone is most suitable for the present invention because it provides a cured product with good heat resistance. Diaminodiphenylsulfones include 4,4'-, 3,3'-
Various isomers and mixtures of isomers are used.
構造式［］の硬化剤としては、トリメチレン
グリコールジ−ｐ−アミノベンゾエートが市販さ
れており、ジアミノジフエニルスルホンに比較し
て、耐熱性に劣るものの、引張伸度に優れるた
め、好んで用いられる。 Trimethylene glycol di-p-aminobenzoate is commercially available as a curing agent with structural formula [], and although it has inferior heat resistance compared to diaminodiphenylsulfone, it is preferred because it has excellent tensile elongation. It will be done.
また、本発明において、三フツ化ホウ素モノエ
チルアミンなどの重合触媒を用いることも可能で
ある。 Further, in the present invention, it is also possible to use a polymerization catalyst such as boron trifluoride monoethylamine.
本発明の典型的な実施方法として、これら熱硬
化性樹脂を100℃〜160℃、好ましくは120℃〜150
℃に加熱し熱可塑性樹脂を加えて溶解させたのち
冷却して硬化剤や硬化触媒を加える方法を挙げる
ことができる。これより温度を上げると、樹脂の
劣化を招く傾向が出てくる。 In a typical practice of the present invention, these thermosetting resins are
An example of a method is to heat the resin to a temperature of 0.degree. C., add a thermoplastic resin, dissolve it, cool it, and then add a curing agent or curing catalyst. Raising the temperature higher than this tends to cause deterioration of the resin.
本発明のプリプレグ用樹脂組成物と組合せて用
いる強化繊維は、炭素繊維、アラミド繊維、アル
ミナ繊維、炭化ケイ素繊維、タングステンカーバ
イド繊維、ボロン繊維であるが、これらを複合す
ることも可能であり、これらの形状には限定され
ない。 The reinforcing fibers used in combination with the prepreg resin composition of the present invention are carbon fibers, aramid fibers, alumina fibers, silicon carbide fibers, tungsten carbide fibers, and boron fibers, but it is also possible to combine these fibers, and these It is not limited to the shape of.
以下に、実施例によりさらに詳細に本発明を説
明する。 Below, the present invention will be explained in more detail with reference to Examples.
［実施例］
実施例１、比較例１〜２
ポリエーテルスルホンの衝撃式粉砕機による粉
砕
実施例 １
三井東圧(株)から入手した、ポリエーテルスルホ
ン5003P ５Kgを、液体窒素を用いて冷却が可能
な衝撃式粉砕機である、リンレツクスミルLX−
Ｏ（ホソカワミクロン／大阪ガス商標）を用いて
粉砕した。この時内部の温度を−80℃に保つた。
粉砕には、1.5時間を要した。粉砕後ふるいによ
り、150μｍの分級を行なつた。分級によりふる
いを通過しなかつた粒子は１重量％以であつた。[Example] Example 1, Comparative Examples 1 to 2 Example of crushing polyether sulfone using an impact crusher 1 5 kg of polyether sulfone 5003P obtained from Mitsui Toatsu Co., Ltd. was cooled using liquid nitrogen. Rinrex Mill LX- is an impact-type crusher that can
It was pulverized using O (Hosokawa Micron/Osaka Gas trademark). At this time, the internal temperature was maintained at -80°C.
Grinding took 1.5 hours. After pulverization, classification was performed using a sieve of 150 μm. The amount of particles that did not pass through the sieve during classification was 1% by weight or more.
粉砕後の粒度分布（ふるいわけ以前のもの）を
粉砕前と共に図１に示す。 The particle size distribution after crushing (before sieving) is shown in Figure 1 as well as before crushing.
ニーダーに４KgのELM434（住友化学工業(株)製
のテトラグリシジルジアミノジフエニルメタン）
を入れ150℃に加熱した。そこに上述の徴粉末状
のポリエーテルスルホン1.5Kgを添加して0.5時間
強力に撹拌した。これにより熱可塑性樹脂が完全
に溶解したことを、位相差顕微鏡による観察で確
認した。 4Kg of ELM434 (tetraglycidyldiaminodiphenylmethane manufactured by Sumitomo Chemical Co., Ltd.) in the kneader
and heated to 150℃. 1.5 kg of the above-mentioned powdered polyether sulfone was added thereto, and the mixture was vigorously stirred for 0.5 hour. It was confirmed by observation using a phase contrast microscope that the thermoplastic resin was completely dissolved.
ニーダーを60℃に冷却した後、３，3′−ジアミ
ノジフエニルスルホン2.1Kgを加え、さらに撹拌
し樹脂組成物を得た。この組成物を20グラムと
り、オーブン中で180℃×２時間の硬化を行なつ
たが、硬化物は透明均一であつた。 After cooling the kneader to 60°C, 2.1 kg of 3,3'-diaminodiphenyl sulfone was added and further stirred to obtain a resin composition. 20 grams of this composition was taken and cured in an oven at 180°C for 2 hours, and the cured product was transparent and uniform.
比較例 １
沈澱法によるポリエーテルスルホンの微粉化50
グラムのポリエーテルスルホンを300グラムのジ
メチルスルホキシドに溶解させた。80℃に熱した
蒸溜水１リツトルをモーター式の撹拌装置により
強力に撹拌し、その中にポリマー溶液を細かい糸
状に流しこみ沈澱させた。沈澱剤中のジメチルス
ルホキシドが少ない時は、ポリマーは微粉末とな
つて沈澱したが、しだいに大きな粉末状となつ
た。沈澱したポリマーを150℃で24時間減圧乾燥
したが、二次凝集が起つた。このポリマー3.0グ
ラムをビーカーにはかりとり150℃のオイルバス
中で8.0グラムのELM434と混合したが、かすか
にジメチルスルホキシドの白煙がした。Comparative Example 1 Micronization of polyether sulfone by precipitation method50
Grams of polyether sulfone were dissolved in 300 grams of dimethyl sulfoxide. One liter of distilled water heated to 80°C was stirred vigorously using a motor-type stirring device, and the polymer solution was poured into it in the form of fine threads and precipitated. When the amount of dimethyl sulfoxide in the precipitant was low, the polymer precipitated as a fine powder, but gradually became a larger powder. The precipitated polymer was dried under reduced pressure at 150°C for 24 hours, but secondary aggregation occurred. 3.0 grams of this polymer was weighed into a beaker and mixed with 8.0 grams of ELM434 in an oil bath at 150°C, but a faint white smoke of dimethyl sulfoxide was produced.
比較例 ２
ポリエーテルスルホンのジエツト粉砕機による
粉砕
実施例１と同様の原料２KgをIDS−５（日本ニ
ユーマチツク(株)製）を用いて粉砕した。処理速度
は実施例１と同様であつたが150μｍを越えるの
粒子が25重量％含まれていた。このものを比較例
１と同様にオイドバス中でELM434に溶解させた
が、完全に溶解するために2.5時間を要した。Comparative Example 2 Grinding of polyether sulfone using a jet grinder 2 kg of the same raw material as in Example 1 was ground using IDS-5 (manufactured by Nippon Neumatic Co., Ltd.). The processing speed was the same as in Example 1, but with 25% by weight of particles larger than 150 μm. This material was dissolved in ELM434 in an oid bath in the same manner as in Comparative Example 1, but it took 2.5 hours to completely dissolve.
［発明の効果］
本発明の方法によりプリプレグ用樹脂組成物と
して用いる熱可塑性樹脂と熱硬化性樹脂からなる
樹脂組成物を用いることなく短時間にかつ大量に
作ることができる。[Effects of the Invention] By the method of the present invention, prepreg resin compositions can be produced in large quantities in a short time without using a resin composition consisting of a thermoplastic resin and a thermosetting resin.
図１は実施例１におけるポリエーテルスルホン
の粉砕前及び粉砕後（ふるいわけをする以前）の
粉度分布を示す。単位は重量％である。
FIG. 1 shows the fineness distribution of polyether sulfone in Example 1 before and after crushing (before sieving). The unit is weight %.
Claims (1)
用樹脂組成物の製法において、成分Ａを衝撃式粉
砕機により粒径150μｍ以下に粉砕した後、成分
Ｂ及びＣと混合することを特徴とする繊維強化プ
リプレグ用樹脂組成物の製法。 Ａ ガラス転移温度が100℃以上の熱可塑性樹脂 Ｂ エポキシ樹脂 Ｃ エポキシ硬化剤 ２ 成分Ａがポリエーテルスルホンであり、成分
Ｂがテトラグリシジルジアミノジフエニルメタン
を主成分とするものである特許請求の範囲第１項
記載の繊維強化プリプレグ用樹脂組成物の製法。[Claims] 1. In the method for producing a prepreg resin composition containing the following A, B, and C as essential components, component A is crushed to a particle size of 150 μm or less using an impact crusher, and then mixed with components B and C. A method for producing a resin composition for fiber-reinforced prepreg, characterized by: A Thermoplastic resin with a glass transition temperature of 100°C or higher B Epoxy resin C Epoxy curing agent 2 Component A is polyether sulfone, and component B is mainly composed of tetraglycidyldiaminodiphenylmethane. 2. A method for producing a resin composition for fiber-reinforced prepreg according to item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29281385A JPS62153349A (en) | 1985-12-27 | 1985-12-27 | Production of resin composition for fiber-reinforced prepreg |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29281385A JPS62153349A (en) | 1985-12-27 | 1985-12-27 | Production of resin composition for fiber-reinforced prepreg |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62153349A JPS62153349A (en) | 1987-07-08 |
| JPH0262144B2 true JPH0262144B2 (en) | 1990-12-25 |
Family
ID=17786680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29281385A Granted JPS62153349A (en) | 1985-12-27 | 1985-12-27 | Production of resin composition for fiber-reinforced prepreg |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62153349A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0392348A3 (en) * | 1989-04-14 | 1991-12-27 | Cytec Technology Corp. | Toughened thermosetting structural materials |
| JPH0316877A (en) * | 1989-06-14 | 1991-01-24 | Aprica Kassai Inc | Baby carriage and hood for baby carriage |
| US5470622A (en) * | 1990-11-06 | 1995-11-28 | Raychem Corporation | Enclosing a substrate with a heat-recoverable article |
| US5250228A (en) * | 1991-11-06 | 1993-10-05 | Raychem Corporation | Conductive polymer composition |
| GB9612523D0 (en) | 1996-06-14 | 1996-08-14 | Fiberite Inc | Improvements relating to resin compositions |
| US6197898B1 (en) | 1997-11-18 | 2001-03-06 | General Electric Company | Melt-mixing thermoplastic and epoxy resin above Tg or Tm of thermoplastic with curing agent |
| CA2552053A1 (en) * | 2004-01-09 | 2005-07-21 | The University Of Sheffield | Self-healing composite material |
| JP4777638B2 (en) * | 2004-11-19 | 2011-09-21 | 三菱樹脂株式会社 | Reflective film |
| GB2421952B (en) * | 2005-01-07 | 2010-04-21 | Univ Sheffield | Damage Detection System |
| JP5411406B2 (en) | 2005-07-13 | 2014-02-12 | 三菱レイヨン株式会社 | Prepreg |
| JP5017886B2 (en) * | 2006-03-03 | 2012-09-05 | 横浜ゴム株式会社 | Method for producing epoxy resin composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5374532A (en) * | 1976-12-14 | 1978-07-03 | Daikin Ind Ltd | Fluororesin coating composition |
| JPS5951944A (en) * | 1982-09-17 | 1984-03-26 | Dainippon Ink & Chem Inc | Polyphenylene sulfide resin composition |
-
1985
- 1985-12-27 JP JP29281385A patent/JPS62153349A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5374532A (en) * | 1976-12-14 | 1978-07-03 | Daikin Ind Ltd | Fluororesin coating composition |
| JPS5951944A (en) * | 1982-09-17 | 1984-03-26 | Dainippon Ink & Chem Inc | Polyphenylene sulfide resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62153349A (en) | 1987-07-08 |
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