JPH069871A - Fiber-reinforced polyimide resin composition - Google Patents

Abstract

PURPOSE:To provide a fiber-reinforced polyimide resin composition comprising a new polyimide resin, an aromatic polyetherketone and fibers and having heat resistance capable of being largely improved by its crystallization without deteriorating its surface smoothness, because the surface of a molded product is not roughened even when crystallized after the production of the molded product. CONSTITUTION:The composition comprises 99-50 pts.wt. of a resin composition comprising (A) 50-99wt.% of a polyimide resin having repeating units of the formula (X is direct bond, 1-10C divalent hydrocarbon, etc.; R is the tetravalent group of a >=2C aliphatic group, a monocyclic aromatic group, etc.), (B) 50-1wt.% of an aromatic polyetherketone, and (C) 1-50 pts.wt. of fibers (e.g. carbon fibers, glass fibers). The composition is usually prepared by a method comprising mixing the powder of the component A, the powder of component B and the component C with a mixer such as a Henschel mixer and subsequently kneading the mixture with an extruder, etc. The component A is preferably produced from an ether diamine such as bis[4-(3-aminophenoxy)phenyl]sulfide and a tetracarboxylic acid dianhydride such as pyromellitic dianhydride.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、新規なポリイミド樹脂
と芳香族ポリエーテルケトン及び繊維からなる繊維強化
ポリイミド系樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber-reinforced polyimide resin composition comprising a novel polyimide resin, an aromatic polyether ketone and a fiber.

【０００２】[0002]

【従来の技術】炭素繊維、ガラス繊維といった強化繊維
を樹脂に添加することは機械的物性を向上させることを
目的として広く行なわれている。一方、樹脂を結晶化さ
せることにより耐熱性を向上させ得ることもまた広く知
られている。しかしながら繊維で強化したポリイミド樹
脂成形物を成形後結晶化させると表面平滑性を損ない、
表面が荒れるため成形後結晶化させるとには問題があっ
た。2. Description of the Related Art Addition of reinforcing fibers such as carbon fibers and glass fibers to resins is widely carried out for the purpose of improving mechanical properties. On the other hand, it is also widely known that heat resistance can be improved by crystallizing a resin. However, when the fiber-reinforced polyimide resin molded product is crystallized after molding, the surface smoothness is impaired,
There is a problem in crystallizing after molding because the surface is rough.

【０００３】[0003]

【発明が解決しようとする課題】本発明の目的は、成形
後結晶化させても表面が荒れることのない繊維強化ポリ
イミド系樹脂組成物を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a fiber reinforced polyimide resin composition which does not have a rough surface even when crystallized after molding.

【０００４】[0004]

【課題を解決するための手段】本発明者らは前記課題を
解決する為に種々検討した結果、ポリイミド樹脂に芳香
族ポリエーテルケトンを添加することにより、成形後結
晶化しても表面が荒れず成形直後の表面平滑性が保持さ
れることを見いだし、本発明を完成するに到った。Means for Solving the Problems As a result of various studies for solving the above problems, the present inventors have found that the addition of aromatic polyether ketone to a polyimide resin does not cause the surface to become rough even after crystallization after molding. It was found that the surface smoothness immediately after molding was maintained, and the present invention was completed.

【０００５】即ち式（１）で表わされる繰り返し単位を
有するポリイミド樹脂５０〜９９重量％と芳香族ポリエ
ーテルケトン５０〜１重量％で構成される樹脂組成物９
９〜５０重量部と繊維１〜５０重量部とからなることを
特徴とする。That is, a resin composition 9 composed of 50 to 99% by weight of a polyimide resin having a repeating unit represented by the formula (1) and 50 to 1% by weight of an aromatic polyether ketone.
It is characterized by comprising 9 to 50 parts by weight and 1 to 50 parts by weight of fibers.

【０００６】本発明で用いられるポリイミド樹脂は式
（１）で表わされる繰返し単位を有するポリイミド樹脂
である。The polyimide resin used in the present invention is a polyimide resin having a repeating unit represented by the formula (1).

【０００７】[0007]

【化３】 （式中、Ｘは直接結合、炭素数１ないし１０の２価の炭
化水素基、六フッ素化されたイソプロピリデン基、カル
ボニル基、チオ基、およびスルホニル基からなる群より
選ばれた基を表わす。又、Ｒは炭素数２以上の脂肪族
基、環式脂肪族基、単環式芳香族基、縮合多環式芳香族
基、および、芳香族基が直接または架橋員により相互に
連結された非縮合多環式芳香族基からなる群より選ばれ
た４価の基を表わす。）上記ポリイミド樹脂は、式
（３）に示すエーテルジアミンと式（４）に示す１種以
上のテトラカルボン酸二無水物とを通常公知の方法によ
って容易に製造できる。[Chemical 3] (In the formula, X represents a group selected from the group consisting of a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, and a sulfonyl group. Further, R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group directly or by a cross-linking member. Represents a tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups.) The above polyimide resin is an etherdiamine represented by formula (3) and one or more tetracarboxylic groups represented by formula (4). The acid dianhydride can be easily produced by a generally known method.

【０００８】[0008]

【化４】 （式中、Ｘは前述と同様である）[Chemical 4] (In the formula, X is the same as above)

【０００９】[0009]

【化５】 （式中、Ｒは前述と同様である。）本発明で用いられる
芳香族ポリエーテルケトンとしては、式（２）で表わさ
れる繰返し単位を有する芳香族ポリエーテルケトンがあ
り、市販されている代表的なものにはＶＩＣＴＲＥＸ
ＰＥＫ（商標、ＩＣＩ社製）が挙げられる。[Chemical 5] (In the formula, R is the same as the above.) As the aromatic polyether ketone used in the present invention, there is an aromatic polyether ketone having a repeating unit represented by the formula (2), which is a commercially available representative. VICTREX
PEK (trademark, manufactured by ICI) may be used.

【００１０】[0010]

【化６】 本発明で用いられる樹脂組成物においてポリイミド樹脂
と芳香族ポリエーテルケトンの配合割合は、ポリイミド
樹脂５０〜９９重量％と芳香族ポリエーテルケトン５０
〜１重量％である。[Chemical 6] In the resin composition used in the present invention, the mixing ratio of the polyimide resin and the aromatic polyether ketone is 50 to 99% by weight of the polyimide resin and 50% of the aromatic polyether ketone.
~ 1% by weight.

【００１１】芳香族ポリエーテルケトンの配合割合が５
０重量％を越えると、得られる繊維強化樹脂組成物にお
いて、本発明で用いるポリイミド樹脂の特性が損なわ
れ、又１重量％未満では成形後結晶化時の表面平滑性改
良効果が著しく低下するため、どちらの場合も好ましく
ない。The blending ratio of the aromatic polyether ketone is 5
When it exceeds 0% by weight, the properties of the polyimide resin used in the present invention are impaired in the obtained fiber reinforced resin composition, and when it is less than 1% by weight, the effect of improving the surface smoothness during crystallization after molding is significantly reduced. However, neither case is preferable.

【００１２】本発明の繊維強化樹脂組成物において前記
樹脂組成物と繊維の配合割合は、樹脂組成物９９〜５０
重量部と繊維１〜５０重量部である。In the fiber reinforced resin composition of the present invention, the resin composition and the fibers are mixed in a proportion of 99 to 50.
Parts by weight and 1 to 50 parts by weight of fiber.

【００１３】繊維の配合割合が１重量部未満では繊維強
化組成物とはいえず、また５０重量部を越えると成形後
結晶化時の表面平滑性が著しく悪くなるため、どちらも
好ましくない。If the blending ratio of the fibers is less than 1 part by weight, it cannot be said that the composition is a fiber reinforced composition, and if it exceeds 50 parts by weight, the surface smoothness at the time of crystallization after molding is remarkably deteriorated.

【００１４】一方、本発明で用いられる繊維としては特
に制限はなく、例えばＰＡＮ系、ピッチ系等の炭素繊
維、ガラス繊維、金属繊維、ケブラーに代表されるアラ
ミド繊維、チタン酸カリウム繊維、ホウ酸アルミニウム
繊維、チラノ繊維等が挙げられる。On the other hand, the fiber used in the present invention is not particularly limited, and examples thereof include PAN-based and pitch-based carbon fibers, glass fibers, metal fibers, aramid fibers typified by Kevlar, potassium titanate fibers, and boric acid. Examples include aluminum fibers and tyranno fibers.

【００１５】本発明の繊維強化ポリイミド樹脂組成物
は、通常次のようにして製造することができる。すなわ
ち、ポリイミド樹脂の粉末、芳香族ポリエーテルケトン
樹脂の粉末、及び所定の長さを有する繊維（チョップド
ストランド）をヘシェルミキサー等の混合機で混合した
後、押出機等により混練して成形材料とするか、もしく
は所定の繊維を含有するポリイミド樹脂ペレットと所定
の繊維を有するポリエーテルケトンのペレットをドライ
ブレンドして成形材料とする。The fiber-reinforced polyimide resin composition of the present invention can be usually produced as follows. That is, a polyimide resin powder, an aromatic polyether ketone resin powder, and fibers having a predetermined length (chopped strands) are mixed with a mixer such as a Heschel mixer and then kneaded with an extruder or the like to form a molding material. Alternatively, or a polyimide resin pellet containing a predetermined fiber and a pellet of a polyether ketone having a predetermined fiber are dry blended to obtain a molding material.

【００１６】尚、本発明では必要に応じてタルク、炭酸
カルシウム、マイカ、ガラスビーズ、グラファイト、二
硫化モリブデンなどの充填剤、安定剤、テフロンなど他
の樹脂と本発明の繊維強化ポリイミド系樹脂組成物を混
合して用いることも可能である。In the present invention, if necessary, a filler such as talc, calcium carbonate, mica, glass beads, graphite, molybdenum disulfide, a stabilizer, another resin such as Teflon, and the fiber-reinforced polyimide resin composition of the present invention. It is also possible to use a mixture of substances.

【００１７】[0017]

【実施例】以下、本発明を実施例及び比較例により詳細
に説明する。EXAMPLES The present invention will now be described in detail with reference to Examples and Comparative Examples.

【００１８】尚、実施例及び比較例においての測定は以
下のような手法により実施した。The measurements in Examples and Comparative Examples were carried out by the following methods.

【００１９】・Ｒａ ：ＪＩＳ−Ｂ０６０１の中心線平
均粗さ測定に準じた。Ra: According to JIS-B0601 center line average roughness measurement.

【００２０】・ＨＤＴ：ＡＳＴＭ Ｄ−６４８に準じ
た。HDT: According to ASTM D-648.

【００２１】＜実施例１〜６、比較例１〜３＞４，４’
−ビス（３−アミノフェノキシ）ビフェニルとピロメリ
ット酸二無水物を原料として得られたポリイミド樹脂粉
末、芳香族ポリエーテルケトン（ＩＣＩ社製、ＶＩＣＴ
ＲＥＸ ＰＥＫ ナチュラル）、及び第１表に示す長さ
３ｍｍの繊維束を各々第１表に記載の組成でドライブレ
ンドした後、４０ｍｍ径押出機にて押出温度３８０〜４
００℃で溶融混練しながら押出す操作を行って均一配合
ペレットを得た。<Examples 1 to 6 and Comparative Examples 1 to 3> 4, 4 '
-Polyimide resin powder obtained from bis (3-aminophenoxy) biphenyl and pyromellitic dianhydride as raw materials, aromatic polyether ketone (ICT, VICT)
REX PEK natural) and a fiber bundle having a length of 3 mm shown in Table 1 are dry-blended with the composition shown in Table 1, respectively, and then extruded at an extrusion temperature of 380 to 4 with a 40 mm diameter extruder.
An extrusion operation was carried out while melt-kneading at 00 ° C. to obtain uniformly mixed pellets.

【００２２】次に上記の均一配合ペレットを通常の射出
成形機を用いてダンベル試験片を作製し、平均表面粗さ
を測定した。次いで上記ダンベル試験片を２６０℃／２
０時間、更に３２０℃／２時間加熱して結晶化し再度平
均表面粗さを測定した。結果を第１表に示す。Then, dumbbell test pieces were prepared from the above-mentioned uniformly compounded pellets using an ordinary injection molding machine, and the average surface roughness was measured. Then, the dumbbell test piece was subjected to 260 ° C / 2.
Crystallization was carried out by heating for 0 hour and further at 320 ° C./2 hours, and the average surface roughness was measured again. The results are shown in Table 1.

【００２３】[0023]

【表１】 ＜実施例７＞実施例１で得たペレットを用いて試験片
（６mm×７０mm×３mm）を成形後、実施例１と同様に結
晶化してＨＤＴを測定した結果、３４５℃であった。[Table 1] <Example 7> A test piece (6 mm x 70 mm x 3 mm) was molded using the pellet obtained in Example 1 and then crystallized in the same manner as in Example 1 to measure the HDT. The result was 345 ° C.

【００２４】＜比較例４＞樹脂組成をポリイミド樹脂４
０重量部とＰＥＫ６０重量部に変えた以外は実施例７と
同様に処理してＨＤＴを測定した結果、３１７℃であっ
た。すなわち、実施例７と比較してポリイミド樹脂の持
つ耐熱性が損なわれる結果となった。Comparative Example 4 Polyimide resin 4 was used as the resin composition.
HDT was measured in the same manner as in Example 7 except that the amount was changed to 0 parts by weight and 60 parts by weight of PEK, and the result was 317 ° C. That is, the heat resistance of the polyimide resin was impaired as compared with Example 7.

【００２５】＜実施例８〜９、比較例５＞ビス［４−
（３−アミノフェノキシ）フェニル］スルフィドとピロ
メリット酸二無水物を原料として得られたポリイミド樹
脂粉末、芳香族ポリエーテルケトンおよび第２表に示す
繊維をドライブレンド後、実施例１と同様に処理してＲ
ａを測定した。結果を第２表に示す。<Examples 8 to 9 and Comparative Example 5> Bis [4-
(3-Aminophenoxy) phenyl] sulfide and pyromellitic dianhydride were used as raw materials, and the polyimide resin powder, aromatic polyether ketone and the fibers shown in Table 2 were dry blended and treated in the same manner as in Example 1. Then R
a was measured. The results are shown in Table 2.

【００２６】＜実施例１０〜１１、比較例６＞２，２−
ビス［４−（３−アミノフェノキシ）フェニル］プロパ
ンと３，３’，４，４’−ベンゾフェノンテトラカルボ
ン酸二無水物を原料として得られたポリイミド樹脂粉
末、芳香族ポリエーテルケトンおよび第２表に示す繊維
をドライブレンド後、実施例１と同様に処理してＲａを
測定した。その結果を第２表に示す。<Examples 10 to 11, Comparative Example 6> 2,2-
Polyimide resin powder obtained from bis [4- (3-aminophenoxy) phenyl] propane and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride as raw materials, aromatic polyetherketone and Table 2 The fiber shown in 1 was dry blended and then treated in the same manner as in Example 1 to measure Ra. The results are shown in Table 2.

【００２７】[0027]

【表２】 ＜実施例１２＞実施例１で得たポリイミド樹脂粉末７０
重量部と長さ３ｍｍの炭素繊維３０重量部をドライブレ
ンド後、押出温度４００℃で溶融混練しながら押し出す
操作を行ってペレットを得た。一方、芳香族ポリエーテ
ルケトン７０重量部と長さ３ｍｍの炭素繊維３０重量部
をドライブレンド後、押出温度３８０℃で溶融混練しな
がら押し出してペレットを得た。この様にして得た繊維
強化ポリイミド樹脂ペレット７０重量部と繊維強化ポリ
エーテルケトンのペレット３０重量部をドライブレンド
後、射出成形してダンベル試験片を作製し、このダンベ
ル試験片を２７０℃／５時間加熱して結晶化し、ついで
実施例１と同様にＲａを測定した。その結果、結晶化前
のＲａが０．７８μｍであるのに対し結晶化後のＲａは
１．７２μｍと実施例１とほぼ同様の結果が得られた。[Table 2] <Example 12> Polyimide resin powder 70 obtained in Example 1
After 30 parts by weight of 30 parts by weight of carbon fibers having a length of 3 mm were dry blended, extrusion was performed at an extrusion temperature of 400 ° C. while melt kneading to obtain pellets. On the other hand, 70 parts by weight of aromatic polyether ketone and 30 parts by weight of carbon fiber having a length of 3 mm were dry-blended and then extruded while melt-kneading at an extrusion temperature of 380 ° C. to obtain pellets. 70 parts by weight of the fiber-reinforced polyimide resin pellets thus obtained and 30 parts by weight of the fiber-reinforced polyetherketone pellets were dry-blended and injection-molded to produce a dumbbell test piece. It was heated for crystallization to crystallize, and Ra was measured in the same manner as in Example 1. As a result, Ra before crystallization was 0.78 μm, while Ra after crystallization was 1.72 μm, which was almost the same as in Example 1.

【００２８】[0028]

【発明の効果】本発明の繊維強化ポリイミド系樹脂組成
物は、表面平滑性を損なうことなく結晶化により耐熱性
を大幅に向上でき、工業的意義は大きい。Industrial Applicability The fiber-reinforced polyimide resin composition of the present invention can greatly improve the heat resistance by crystallization without impairing the surface smoothness, and has great industrial significance.

フロントページの続き (72)発明者 滝沢 信宏 神奈川県横浜市栄区笠間町1190番地 三井 東圧化学株式会社内 (72)発明者 冨本 裕昭 神奈川県横浜市栄区笠間町1190番地 三井 東圧化学株式会社内(72) Inventor Nobuhiro Takizawa 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Hiroaki Tomimoto 1190, Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】 式（１）で表わされる繰り返し単位を有
するポリイミド樹脂５０〜９９重量％と芳香族ポリエー
テルケトン５０〜１重量％で構成される樹脂組成物９９
〜５０重量部と繊維１〜５０重量部とからなることを特
徴とする繊維強化ポリイミド系樹脂組成物。 【化１】 （式中、Ｘは直接結合、炭素数１ないし１０の２価の炭
化水素基、六フッ素化されたイソプロピリデン基、カル
ボニル基、チオ基、およびスルホニル基からなる群より
選ばれた基を表わす。又、Ｒは炭素数２以上の脂肪族
基、環式脂肪族基、単環式芳香族基、縮合多環式芳香族
基、および、芳香族基が直接または架橋員により相互に
連結された非縮合多環式芳香族基からなる群より選ばれ
た４価の基を表わす。）1. A resin composition 99 comprising 50 to 99% by weight of a polyimide resin having a repeating unit represented by the formula (1) and 50 to 1% by weight of an aromatic polyether ketone.
˜50 parts by weight and 1 to 50 parts by weight of fibers, a fiber-reinforced polyimide resin composition. [Chemical 1] (In the formula, X represents a group selected from the group consisting of a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, and a sulfonyl group. Further, R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group directly or by a cross-linking member. Represents a tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups.) 【請求項２】 芳香族ポリエーテルケトンが式（２）で
表わされる繰返し単位を有する請求項１記載の繊維強化
ポリイミド系樹脂組成物。 【化２】 2. The fiber-reinforced polyimide resin composition according to claim 1, wherein the aromatic polyether ketone has a repeating unit represented by the formula (2). [Chemical 2] 【請求項３】 繊維が炭素繊維、ガラス繊維、金属繊
維、アラミド繊維、チタン酸カリウム繊維、ホウ酸アル
ミニウム繊維およびチラノ繊維からなる群より選ばれた
少なくとも１種である請求項１記載の繊維強化ポリイミ
ド系樹脂組成物。3. The fiber reinforced according to claim 1, wherein the fiber is at least one selected from the group consisting of carbon fiber, glass fiber, metal fiber, aramid fiber, potassium titanate fiber, aluminum borate fiber and tyrano fiber. Polyimide resin composition.