JPH02269764A - Aromatic polyetherketone resin composition - Google Patents
Aromatic polyetherketone resin compositionInfo
- Publication number
- JPH02269764A JPH02269764A JP1090828A JP9082889A JPH02269764A JP H02269764 A JPH02269764 A JP H02269764A JP 1090828 A JP1090828 A JP 1090828A JP 9082889 A JP9082889 A JP 9082889A JP H02269764 A JPH02269764 A JP H02269764A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- weight
- carbon fiber
- resin composition
- aromatic
- 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
- 229920001643 poly(ether ketone) Polymers 0.000 title claims abstract description 35
- 125000003118 aryl group Chemical group 0.000 title claims description 44
- 239000011342 resin composition Substances 0.000 title claims description 23
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 44
- 239000004917 carbon fiber Substances 0.000 claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 229920001601 polyetherimide Polymers 0.000 claims abstract description 22
- 239000004697 Polyetherimide Substances 0.000 claims abstract description 21
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 28
- 238000002156 mixing Methods 0.000 abstract description 11
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 abstract 1
- 229920004695 VICTREX™ PEEK Polymers 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004695 Polyether sulfone Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920006393 polyether sulfone Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 229920004747 ULTEM® 1000 Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- -1 n-methylbenzene Chemical compound 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 240000008881 Oenanthe javanica Species 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920004738 ULTEM® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は優れた耐熱特性を有する芳香族ポリエーテルケ
トン系樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an aromatic polyetherketone resin composition having excellent heat resistance properties.
［従来の技術１
芳香族ポリエーテルケトン樹脂は機械的、化学的および
熱的性質に優れたエンジニアリングプラスチックである
ことより、電気・電子機器１機械、自動車等の用途への
使用が期待されている６しかし最近の技術進歩に伴い、
芳香族ポリエーテルケトン樹脂が有する特性、特に耐熱
特性を一段と高めたものが要求されるようになったきた
。この為、芳香族ポリエーテルケトン樹脂に繊維状補強
材、特に炭素繊維を配合することにより機械強度を向上
させ耐熱性を改良する方法が実施されている。[Conventional technology 1 Aromatic polyetherketone resin is an engineering plastic with excellent mechanical, chemical, and thermal properties, so it is expected to be used in electrical and electronic equipment 1 machinery, automobiles, etc. 6 However, with recent technological advances,
There has been a growing demand for aromatic polyetherketone resins with even higher properties, particularly heat resistance properties. For this reason, methods have been implemented to improve mechanical strength and heat resistance by blending fibrous reinforcing materials, particularly carbon fibers, with aromatic polyetherketone resins.
炭素繊維はエポキシ樹脂をマトリックスとする炭素繊維
強化プラスチックに多く使用されているため、炭素繊維
の収束剤としては、エポキシ樹脂が使われている。しか
し、エポキシ樹脂収束剤は、エポキシ樹脂等の熱硬化性
樹脂がマトリックスである場合には有効であるが、芳香
族ポリエーテルケトン樹脂等の熱可塑性樹脂に対しては
接着性が悪いため１機械強度の良好な樹脂組成物が得ら
れない、このために、特開昭５３−１０６７５２号公報
に見られるごとく、熱可塑性樹脂に対してはポリアミド
樹脂を収束剤として用いることが試みられている。しか
し芳香族ポリエーテルケトン樹脂の成形には３７０℃以
上の高温が必要であるため、エポキシ樹脂、ポリアミド
樹脂にて収束した炭素繊維を使用した場合には、成形中
に収束剤が熱分解して、ボイドの生成、ウェルド部強度
の低下等の問題を生じていた。Since carbon fiber is often used in carbon fiber reinforced plastics that have epoxy resin as a matrix, epoxy resin is used as a binding agent for carbon fiber. However, although epoxy resin binding agents are effective when the matrix is thermosetting resin such as epoxy resin, they have poor adhesion to thermoplastic resins such as aromatic polyetherketone resin, so For this reason, attempts have been made to use polyamide resin as a binding agent for thermoplastic resins, as seen in JP-A-53-106752, where a resin composition with good strength cannot be obtained. However, since molding of aromatic polyetherketone resin requires high temperatures of 370°C or higher, when carbon fibers bound with epoxy resin or polyamide resin are used, the binding agent may thermally decompose during molding. However, problems such as the formation of voids and a decrease in the strength of the weld portion have occurred.
また特開昭５６−１２０７３０号公報には芳香族ポリス
ルホン樹脂にて収束した炭素繊維の使用が開示されてお
り、ボイドの生成、ウェルド部強度の低下等の問題をな
くしているが、機械強度の向上が少なく、より一層の機
械強度向上が要求されている。更に芳香族ポリスルホン
樹脂にて収束された炭素繊維を使用した芳香族ポリエー
テルケトン樹脂組成物は、炭素繊維と芳香族ポリエーテ
ルケトン樹脂との界面に芳香族ポリスルホン樹脂が存在
するため、この樹脂組成物は芳香族ポリスルホン樹脂が
侵される薬液に浸漬した場合、機械強度が低下すること
が指摘されている。Furthermore, JP-A No. 56-120730 discloses the use of carbon fibers bound with aromatic polysulfone resin, which eliminates problems such as the generation of voids and a decrease in the strength of the weld part, but it does not reduce the mechanical strength. There is little improvement in mechanical strength, and further improvement in mechanical strength is required. Furthermore, aromatic polyetherketone resin compositions using carbon fibers condensed with aromatic polysulfone resin are difficult to use because the aromatic polysulfone resin is present at the interface between the carbon fibers and the aromatic polyetherketone resin. It has been pointed out that when an object is immersed in a chemical solution that attacks aromatic polysulfone resin, its mechanical strength decreases.
さらにまた上記芳香族ポリエーテルケトン樹脂に炭素繊
維を配合した場合機械強度は向上するが、マトリックス
のガラス転移温度を越えた温度範囲での強度低下は改善
されないという欠点があった。Furthermore, when carbon fiber is blended with the aromatic polyetherketone resin, the mechanical strength is improved, but there is a drawback that the decrease in strength cannot be improved in a temperature range exceeding the glass transition temperature of the matrix.
［発明が解決しようとする課題］
本発明の目的は、マトリックス自体の耐熱性を改良し、
高温時機械強度に優れた炭素繊維配合芳香族ポリエーテ
ルケトン系樹脂組成物を提供することにある。[Problem to be solved by the invention] The purpose of the present invention is to improve the heat resistance of the matrix itself,
An object of the present invention is to provide a carbon fiber-containing aromatic polyetherketone resin composition that has excellent mechanical strength at high temperatures.
［課題を解決するための手段］
本発明者らは前記目的を達成するために種々検討した結
果、芳香族ポリエーテルケトン樹脂に特定量のポリエー
テルイミドを配合することにより得られる樹脂組成物を
マトリックスとして用いることが有効であることを見い
出し１本発明を完成するに至った。[Means for Solving the Problems] As a result of various studies to achieve the above object, the present inventors have developed a resin composition obtained by blending a specific amount of polyetherimide with an aromatic polyetherketone resin. The present invention was completed based on the discovery that it is effective to use it as a matrix.
すなわち本発明は。That is, the present invention.
ｆａｔ下記（１）式で表される繰り返し単位を有する芳
香族ポリエーテルケトン９５〜６０重量％と、下記（２
）式で表される繰り返し単位を有するポリエーテルイミ
ド５〜４０重量％とからなる樹脂組成物の７５〜５５重
量％と、
（ｂｌ芳香族ポリスルホン樹脂で表面を被覆した後、３
００〜４００℃で加熱された炭素繊維の２５〜４５ｆｆ
ｉｆ１％とからなる芳香族ポリエーテルケトン系樹脂組
成物である。fat: 95 to 60% by weight of an aromatic polyetherketone having a repeating unit represented by the following formula (1), and the following (2)
75 to 55% by weight of a resin composition consisting of 5 to 40% by weight of a polyetherimide having a repeating unit represented by the formula (3) after coating the surface with (bl aromatic polysulfone resin).
25-45ff of carbon fiber heated at 00-400℃
This is an aromatic polyetherketone resin composition consisting of 1% if.
本発明において用いられる芳香族ポリエーテルケトンは
下記（１）式で表される繰り返し単位を有する熱可塑性
結晶性樹脂である。The aromatic polyetherketone used in the present invention is a thermoplastic crystalline resin having a repeating unit represented by the following formula (1).
本発明においては、＾ＳＴＭ Ｏ＋２３８に準じ、３８
０℃、２．１６ｋｇ荷償条件下でｄ（す定したメルトフ
ローインデックスか５〜５０ｇ／ｌ０ｍ１ｎ 、望まし
くは１０〜２５ｇ／１０ｍ１ｎの範囲内のポリエーテル
ケトンが好ましく用いられる。In the present invention, according to ^STM O+238, 38
A polyetherketone having a predetermined melt flow index of 5 to 50 g/10 m1n, preferably 10 to 25 g/10 m1n is preferably used under conditions of 0 DEG C. and 2.16 kg unloading.
市販されているものとして、英国インペリアル・ケミカ
ル・インダストリーズ社の「ピクトレックス ポリエー
テルケトンＰＥＫ ２２０Ｐ （商標）」があげられる
。A commercially available product is "Pictrex Polyetherketone PEK 220P (trademark)" manufactured by Imperial Chemical Industries Ltd. in the UK.
本発明において用いられるポリエーテルイミドは下記（
２）式で表される繰り返し単位を有する。市販されてい
るものとしては、米国ゼネラル・エレクトリック社製の
商品名「ウルテム」が広く知られており、例えば特開昭
５６−８２６号公報に記載された方法によって容易に製
造することができる。The polyetherimide used in the present invention is as follows (
2) It has a repeating unit represented by the formula. As a commercially available product, the product name "Ultem" manufactured by General Electric Company of the United States is widely known, and it can be easily produced, for example, by the method described in JP-A-56-826.
本発明においては、３２０℃、 ２．１６ｋｇ荷重条件
下で測定したメルトフローインデックスが０．３〜５ｇ
／１０ｍ１ｎ 、望ましくは０．５〜３ ｇ／１０ｍ１
ｎの範囲のポリエーテルイミドが好ましく用いられる。In the present invention, the melt flow index measured at 320°C and a load of 2.16 kg is 0.3 to 5 g.
/10m1n, preferably 0.5-3 g/10m1
Polyetherimides in the range n are preferably used.
芳香族ポリエーテルケトンとポリエーテルイミドの配合
割合は、芳香族ポリエーテルケトン９５〜７０重量％、
望ましくは９０〜７０重量％、ポリエーテルイミド５〜
３０重量％、望ましくは１０〜３０重量％が適当である
。芳香族ポリエーテルケトンが９５重量％を越え、ポリ
エーテルイミドが５重量％未満の場合には目的とする樹
脂組成物の高温での機械強度の向上効果が不十分であり
、また芳香族ポリエーテルケトンが７０重量％未満、ポ
リエーテルイミドが３０重量％を越えた場合には得られ
る樹脂組成物は、芳香族ポリエーテルケトンが有してい
る優れた化学的特性を失ってくる。The blending ratio of aromatic polyetherketone and polyetherimide is 95 to 70% by weight of aromatic polyetherketone,
Desirably 90-70% by weight, 5-5% polyetherimide
A suitable amount is 30% by weight, preferably 10-30% by weight. If the amount of aromatic polyetherketone exceeds 95% by weight and the amount of polyetherimide is less than 5% by weight, the desired effect of improving the mechanical strength of the resin composition at high temperatures will be insufficient; When the ketone content is less than 70% by weight and the polyetherimide content exceeds 30% by weight, the resulting resin composition loses the excellent chemical properties possessed by aromatic polyetherketones.
本発明において、収束剤として炭素繊維の表面を被覆す
るのに用いられる芳香族ポリスルホン樹脂は、アリーレ
ン結合、エーテル結合及びスルホン結合を結合単位とす
る線状重合体であり、例えば１次式のような繰り返し単
位からなるものが知られている。In the present invention, the aromatic polysulfone resin used as a sizing agent to coat the surface of carbon fibers is a linear polymer having arylene bonds, ether bonds, and sulfone bonds as bonding units, for example, as shown in the linear formula. It is known to consist of repeating units.
（３） −［−０舎ｓｏｉφ→ （５） ＋ｏ（■ｓｏ□（シ０舎０（）モＣＩ。(3) −[−0sha soiφ→ (5) +o(■so□(shi0sha0()moCI.
（７）＋ ｏ−＠ｒ−ｓｏ 、−＠）−ｏｇ（ｓ ）−
ｔ−０（）ＳＯ，ｉＳＯ，（）０（芹（９）千ｏ＋ｓｏ
、舎ｏ−＠７ｃｎ、知ＦＣＩ＋３
Ｃ１０゜
これらの芳香族ポリスルホン樹脂は１例えば特公昭４０
−１００６７号公報、特公昭４２−７７９９号公報、・
及び特公昭４１−６２７号公報等に記載された方法によ
って製造することができ、少なくともこれらの一種また
は二種以上の混合物が用いられる。市販されているもの
としては１式（３）で示される代表例として、英国イン
ペリアル・ケミカル・インダストリーズ社の［ピクトレ
ックス ポリエーテルスルホン（商Ｐ４）」が挙げられ
５式（４）で示される代表例として、米国アモコ・ケミ
カル社のｒニーデル・ポリスルホン（商Ｐ４）」等があ
る。(7) + o-@r-so, -@)-og(s)-
t-0()SO,iSO,()0(seri(9)1000+so
, Shao-@7cn, ChiFCI+3 C10゜These aromatic polysulfone resins are 1, e.g.
-10067 Publication, Special Publication No. 1977-7799,・
It can be produced by the method described in Japanese Patent Publication No. 41-627, etc., and at least one kind or a mixture of two or more of these can be used. Commercially available products include ``Pictrex Polyethersulfone (Commercial P4)'' manufactured by Imperial Chemical Industries Ltd. in the UK, as a representative example shown by formula 1 (3), and representative example shown by formula 5 (4). An example is "Needel Polysulfone (Commercial P4)" manufactured by Amoco Chemical Company, USA.
また本発明で使用される炭素繊維はアクリル系、レーヨ
ン系、リグニン系、ピッチ系等が挙げられ、いずれも使
用される０本発明では繊維強度の最も高いアクリル系が
最も好ましく使用される。炭素繊維の形態は、チョップ
トストランド、ロービング、織物等いずれでも良い、こ
れらの炭素繊維は予めその表面を酸化処理してお（と更
に好ましい、これら炭素繊維への芳香族ポリスルホン樹
脂への被覆方法としては、芳香族ポリスルホン樹脂をジ
クロルメタン、クロロホルム、１．２ジクロルエタン、
１．１．１．２．２−テトラクロルエタン、ジメチルス
ルホオキシド、ノルマルメチルベンクン、メチルエチル
ケトン、１．１．２−トリクロルエタンなどの溶剤に溶
解した溶液に、炭素繊維を浸し、その後乾燥し溶剤を除
去して、芳香族ポリスルホン樹脂を被覆した炭素繊維を
得る。Further, the carbon fibers used in the present invention include acrylic, rayon, lignin, and pitch type carbon fibers, and although any of them may be used, in the present invention, acrylic fibers having the highest fiber strength are most preferably used. The carbon fibers may be in the form of chopped strands, rovings, textiles, etc. These carbon fibers may have their surfaces oxidized in advance (and more preferably, the method of coating these carbon fibers with aromatic polysulfone resin) As aromatic polysulfone resin, dichloromethane, chloroform, 1.2 dichloroethane,
1.1.1.2.2-Tetrachloroethane, dimethyl sulfoxide, n-methylbenzene, methyl ethyl ketone, 1.1.2-Trichloroethane, etc. are dissolved in a solution of the carbon fibers by soaking them in a solution and then drying them. The solvent is removed to obtain carbon fibers coated with aromatic polysulfone resin.
通常、炭素繊維に対する芳香族ポリスルホン樹脂の被覆
量は炭素繊維１００重量部に対し０．１−１０市量部が
良く、０．１重量部以下では本発明の効果はえられず、
またＩＯ重量部以上波被覆せても１機械強度の向上は期
待できず意味がない。Usually, the coating amount of the aromatic polysulfone resin on the carbon fiber is preferably 0.1-10 parts by weight per 100 parts by weight of the carbon fiber, and if it is less than 0.1 part by weight, the effect of the present invention cannot be obtained.
Further, even if the wave coating exceeds IO parts by weight, no improvement in mechanical strength can be expected and it is meaningless.
以上のようにして芳香族ポリスルホン樹脂を被覆した炭
素繊維の熱処理は、空気中３００〜４００℃、特に好ま
しくは３４０〜３８０℃の温度下に曝すことにより行わ
れる。加熱処理時間は３〜２０時間、特に好ましくは５
〜１５時間である。The carbon fiber coated with the aromatic polysulfone resin as described above is heat-treated by exposing it in air to a temperature of 300 to 400°C, particularly preferably 340 to 380°C. The heat treatment time is 3 to 20 hours, particularly preferably 5 hours.
~15 hours.
このようにして得られる芳香族ポリスルホン樹脂を被覆
した炭素繊維と芳香族ポリエーテルケトンとポリエーテ
ルイミドの樹脂組成物との混合には種々の手法が採用で
きる。例えば被覆、加熱処理した炭素繊維を３〜６ｍｍ
長さに切断し、これと芳香族ポリエーテルケトンとポリ
エーテルイミドの樹脂組成物を個々別々に溶融押出機に
供給して混合することもできるし、あらかじめヘンシェ
ルミキサー、スーパーミキサー、リボンブレンダーなど
の混合機で予備ブレンドした後、溶融押出機に供給する
こともできる。更に被層、加熱処理した炭素繊維ロービ
ングを直接溶融押出機に供給し、芳香族ポリエーテルケ
トンとポリエーテルイミドの樹脂組成物と混合すること
もできる。すなわち、炭素繊維、ポリエーテルケトン、
ポリエーテルイミドの３成分は最終的に本発明の組成比
になるのであればその混合順序、混合方法に制限は無い
。Various methods can be adopted for mixing the carbon fiber coated with the aromatic polysulfone resin thus obtained and the resin composition of aromatic polyetherketone and polyetherimide. For example, 3 to 6 mm of coated and heat-treated carbon fiber
It is also possible to cut it into lengths and feed it and the resin composition of aromatic polyetherketone and polyetherimide individually into a melt extruder for mixing. It can also be preblended in a mixer and then fed to a melt extruder. Furthermore, the coated and heat-treated carbon fiber roving can be directly fed to a melt extruder and mixed with a resin composition of aromatic polyetherketone and polyetherimide. i.e. carbon fiber, polyetherketone,
There are no restrictions on the mixing order or mixing method of the three components of polyetherimide, as long as they finally have the composition ratio of the present invention.
本発明において芳香族ポリスルホン樹脂を被覆した炭素
繊維と芳香族ポリエーテルケトンとポリエーテルイミド
の樹脂組成物との配合割合は、炭素繊維２５〜４５重量
％、芳香族ポリエーテルケトンとポリエーテルイミドの
混合物７５〜５５重量％である。炭素繊維の電が２５重
量％未満の場合には、得られる樹脂組成物の機械強度が
低（好ましくない。また炭素繊維を４５重厘％越えて配
合した場合には、得られた樹脂組成物の均一な溶融混合
が難しくなり、溶融流動性も著しく低下して射出成形な
どの加工性を損なう結果となる。本発明の樹脂組成物に
は、必要に応じ、タルク、炭酸力ルシュウム、マイカ、
ガラスピーズ等の充填材、ガラス繊維、チタン酸カリ繊
維、アラミド繊維、セラミック質繊維等の繊維状補強材
、安定剤、着色剤を樹脂組成物の品質、性能を損なわな
い範囲で混和してもよい。In the present invention, the blending ratio of carbon fiber coated with aromatic polysulfone resin, aromatic polyetherketone, and polyetherimide resin composition is 25 to 45% by weight of carbon fiber, aromatic polyetherketone, and polyetherimide. The mixture is 75-55% by weight. If the carbon fiber content is less than 25% by weight, the mechanical strength of the resulting resin composition will be low (unfavorable).If the carbon fiber content exceeds 45% by weight, the resulting resin composition will have a low mechanical strength (unfavorable). It becomes difficult to uniformly melt and mix the materials, and the melt flowability is also significantly reduced, impairing processability in injection molding, etc.The resin composition of the present invention may contain talc, lucium carbonate, mica,
Fillers such as glass peas, fibrous reinforcing materials such as glass fibers, potassium titanate fibers, aramid fibers, and ceramic fibers, stabilizers, and colorants may be mixed as long as they do not impair the quality and performance of the resin composition. good.
上記した本発明の改良された炭素繊維と芳香族ポリエー
テルケトンとポリエーテルイミドとの樹脂組成物は、射
出成形法、押出成形法、トランスファー成形法、圧縮成
形性等公知の成形法により所定の成形品に成形すること
ができる。The resin composition of the improved carbon fiber, aromatic polyetherketone, and polyetherimide of the present invention described above can be manufactured by known molding methods such as injection molding, extrusion molding, transfer molding, and compression molding. Can be formed into molded products.
このようにして成形された本発明の樹脂組成物は、機械
強度、特に高温時の機械強度に優れているため、高温に
おいて高い機械強度を必要とされる機械部品、自動車部
品等に特に好適にもちいることができる。The resin composition of the present invention molded in this manner has excellent mechanical strength, particularly mechanical strength at high temperatures, and is therefore particularly suitable for mechanical parts, automobile parts, etc. that require high mechanical strength at high temperatures. It can be used.
［実施例〕 以下、実施例により本発明を説明する。[Example〕 The present invention will be explained below with reference to Examples.
実施例１〜３
インペリアル・ケミカル・インダストリーズ社の「ピク
トレックス ポリエーテルスルホンＰＥ５５００３Ｐ
（商標）」を２０重量％、ジクロルメタン４０重量％、
１．１．２ トリクロルエタン４０重量％を使用してポ
リエーテルスルホン溶液を調製した。表面を酸処理した
アクリル系炭素繊維（東邦レーヨン社製、商品名ＨＴＡ
。以下の実施例、比較例において、炭素繊維は特記した
以外はこの製品を使用した）のロービングをポリエーテ
ルスルホン溶液に６０ Ｍ ／ ｌ（Ｒの速度で連続的
に浸漬し、乾燥し脱溶剤を行った後３ｎｕａ長さに切断
し、チョップトストランドとした。Examples 1 to 3 Pictrex polyether sulfone PE55003P manufactured by Imperial Chemical Industries
(Trademark)” 20% by weight, dichloromethane 40% by weight,
1.1.2 A polyethersulfone solution was prepared using 40% by weight trichloroethane. Acrylic carbon fiber with acid-treated surface (manufactured by Toho Rayon Co., Ltd., product name: HTA)
. In the following Examples and Comparative Examples, a roving of carbon fiber (this product was used except as specified) was continuously immersed in a polyethersulfone solution at a rate of 60 M/l (R), dried, and desolventized. After that, it was cut into a length of 3nua to obtain chopped strands.
このチョップトストランドをステンレス製のバットに入
れ、３７０℃に昇温した電気炉に入れ、空気雰囲気下で
１０時間加熱処理を行った。The chopped strands were placed in a stainless steel vat, placed in an electric furnace heated to 370°C, and heat-treated in an air atmosphere for 10 hours.
このようにして得られた炭素繊維チョップトストランド
と、芳香族ポリエーテルケトン（ＰＥＫ＋としてインペ
リアル・ケミカル・インダストリーズ社％ＰＥＫ ２２
叶と、ポリエーテルイミド（ＰＥＩＩとしてゼネラル・
エレクトリック社製のウルテム１０００とを表−１に示
した割合でトライブレンドした後６５ｍｎ＋径押出機に
て押出温度３８０℃で溶融混練しながら押出す操作を行
って均一配合ベレットを得た。The carbon fiber chopped strands thus obtained and aromatic polyetherketone (PEK+, manufactured by Imperial Chemical Industries Co., Ltd.% PEK 22
Polyetherimide (PEII)
After tri-blending with Ultem 1000 manufactured by Electric Co., Ltd. in the proportions shown in Table 1, extrusion was performed using a 65 mm+ diameter extruder while melt-kneading at an extrusion temperature of 380°C to obtain a uniformly blended pellet.
次に上記の均一配合ペレットを日精樹脂工業社製８０Ｔ
ＯＮ （型締力）の射出成形機を用い、シリンダー温度
３８０℃、金型温度１８０℃の温度条件下でＡＳＴＭ
１号ダンベル試験片を成形した。室温下（２３℃）と、
高温下（１６５℃）で引張試験、曲げ試験を、それぞれ
ＡＳＴＭ−Ｄ６３８． Ｄ７９０に準じ実施した。その
結果を表−１に示した。Next, the above uniformly mixed pellets were mixed into 80T manufactured by Nissei Resin Industries Co., Ltd.
Using an ON (mold clamping force) injection molding machine, ASTM was carried out under the temperature conditions of cylinder temperature 380℃ and mold temperature 180℃.
A No. 1 dumbbell test piece was molded. At room temperature (23℃),
Tensile test and bending test were conducted at high temperature (165°C) according to ASTM-D638. It was carried out according to D790. The results are shown in Table-1.
比較例１
実施例１においてマトリックス樹脂としてインペリアル
・ケミカル・インダストリーズ社製ＰＥＫ２２０Ｐだけ
を用いたほかは実施例１と同様の操作で炭素繊維配合Ｐ
ＥＫ ＰＩ３脂の試験片を作成し、引張強度、曲げ強度
を測定しその結果を表−１に示した。Comparative Example 1 Carbon fiber compound P was produced in the same manner as in Example 1 except that only PEK220P manufactured by Imperial Chemical Industries was used as the matrix resin in Example 1.
A test piece of EK PI3 resin was prepared, and its tensile strength and bending strength were measured, and the results are shown in Table 1.
比較例２
実施例１においてマトリックス樹脂としてゼネラル・エ
レクトリック社製のウルテムｌ０００だけを用いたほか
は実施例１と同様の操作で炭素繊維配合ＰＥＩ樹脂の試
験片を作成し、引張強度、曲げ強度を測定しその結果を
表−１に示した。Comparative Example 2 A test piece of carbon fiber-containing PEI resin was prepared in the same manner as in Example 1, except that only Ultem 1000 manufactured by General Electric Co. was used as the matrix resin in Example 1, and the tensile strength and bending strength were measured. The results are shown in Table 1.
比較例３
実施例１においてＰＥＫ ２２０Ｐとウルテム１０００
の配合比率を６０対４０（重量％）としたほかは実施例
１と同様の操作で炭素繊維配合ＰＥＩ ＄＃を脂の試験
片を作成し、引張強度、曲げ強度を測定しその結果を表
−１に示した。Comparative Example 3 PEK 220P and Ultem 1000 in Example 1
A test piece of carbon fiber compounded PEI $# was prepared in the same manner as in Example 1, except that the blending ratio was 60:40 (wt%), and the tensile strength and bending strength were measured and the results are shown. -1.
実施例４
実施例２において炭素繊維の添加量を４０重１％とじた
ほかは、実施例２と同様の操作で炭素繊維配合樹脂の試
験片を作成し、引張強度、曲げ強度を測定しその結果を
表−１に示した。Example 4 A test piece of carbon fiber-containing resin was prepared in the same manner as in Example 2, except that the amount of carbon fiber added was reduced to 40% by weight, and the tensile strength and bending strength were measured. The results are shown in Table-1.
比較例４〜５
実施例２において炭素繊維の添加量を２０重量％または
５０重量％としたほかは、実施例２と同様の操作で炭素
繊維配合樹脂の試験片を作成し、引張強度、曲げ強度を
測定しその結果を表−１に示した。Comparative Examples 4 to 5 Test specimens of carbon fiber-containing resin were prepared in the same manner as in Example 2, except that the amount of carbon fiber added in Example 2 was changed to 20% or 50% by weight. The strength was measured and the results are shown in Table 1.
／
／
／
／
／
［発明の効果１
本発明の芳香族ポリエーテルケトン系樹脂組成物は、マ
トリックス自体の高温時耐熱性が改良された由に、これ
が炭素繊維による補強効果と相乗し、総合的に優れた耐
熱性を示す。/ / / / / [Effect of the invention 1 The aromatic polyetherketone resin composition of the present invention has improved heat resistance at high temperatures of the matrix itself, and this synergizes with the reinforcing effect of carbon fibers, resulting in comprehensive improvement. Shows excellent heat resistance.
代 理 人 若 林 巾teenager Reason Man young Hayashi Width
Claims (1)
香族ポリエーテルケトン９５〜６０重量％と、下記（２
）式で表される繰り返し単位を有するポリエーテルイミ
ド５〜４０重量％とからなる樹脂組成物の７５〜５５重
量％と、 （１）▲数式、化学式、表等があります▼ （２）▲数式、化学式、表等があります▼ （ｂ）芳香族ポリスルホン樹脂で表面を被覆した後、３
００〜４００℃で加熱された炭素繊維の２５〜４５重量
％とからなる芳香族ポリエーテルケトン系樹脂組成物。[Scope of Claims] (a) 95 to 60% by weight of an aromatic polyetherketone having a repeating unit represented by the following formula (1), and the following (2)
) 75 to 55% by weight of a resin composition consisting of 5 to 40% by weight of polyetherimide having a repeating unit represented by the formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) ▲ Mathematical formula , chemical formulas, tables, etc. ▼ (b) After coating the surface with aromatic polysulfone resin, 3
An aromatic polyetherketone resin composition comprising 25 to 45% by weight of carbon fibers heated at 00 to 400°C.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1090828A JP2667246B2 (en) | 1989-04-12 | 1989-04-12 | Aromatic polyetherketone resin composition |
| EP90106734A EP0392408B1 (en) | 1989-04-12 | 1990-04-08 | Aromatic polyetherketone resin compositions |
| DE69032302T DE69032302T2 (en) | 1989-04-12 | 1990-04-08 | Compositions based on aromatic polyether ketones |
| KR1019900005064A KR930010236B1 (en) | 1989-04-12 | 1990-04-12 | Aromatic polyether keton resin composition |
| US07/948,413 US5223556A (en) | 1989-04-12 | 1992-09-22 | Aromatic polyetherketone resin compositions containing polyetherimide, polysulfone-coated carbon fibers and mechanical component formed therefrom |
| KR1019930015927A KR930010237B1 (en) | 1989-04-12 | 1993-08-17 | Aromatic polyether keton resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1090828A JP2667246B2 (en) | 1989-04-12 | 1989-04-12 | Aromatic polyetherketone resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02269764A true JPH02269764A (en) | 1990-11-05 |
| JP2667246B2 JP2667246B2 (en) | 1997-10-27 |
Family
ID=14009450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1090828A Expired - Lifetime JP2667246B2 (en) | 1989-04-12 | 1989-04-12 | Aromatic polyetherketone resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2667246B2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59184254A (en) * | 1983-04-04 | 1984-10-19 | Toray Ind Inc | Polyaryl ketone resin composition |
| JPS61225247A (en) * | 1985-03-27 | 1986-10-07 | アモコ、コ−ポレ−ション | Abrasion resistant poly(aryl ether ketone)/polyimide mixture |
| JPS6424856A (en) * | 1987-07-20 | 1989-01-26 | Mitsui Toatsu Chemicals | Aromatic polysulfone resin composition |
-
1989
- 1989-04-12 JP JP1090828A patent/JP2667246B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59184254A (en) * | 1983-04-04 | 1984-10-19 | Toray Ind Inc | Polyaryl ketone resin composition |
| JPS61225247A (en) * | 1985-03-27 | 1986-10-07 | アモコ、コ−ポレ−ション | Abrasion resistant poly(aryl ether ketone)/polyimide mixture |
| JPS6424856A (en) * | 1987-07-20 | 1989-01-26 | Mitsui Toatsu Chemicals | Aromatic polysulfone resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2667246B2 (en) | 1997-10-27 |
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