JPS63120741A - Composite composition of carbon fiber high-molecular material - Google Patents
Composite composition of carbon fiber high-molecular materialInfo
- Publication number
- JPS63120741A JPS63120741A JP26564586A JP26564586A JPS63120741A JP S63120741 A JPS63120741 A JP S63120741A JP 26564586 A JP26564586 A JP 26564586A JP 26564586 A JP26564586 A JP 26564586A JP S63120741 A JPS63120741 A JP S63120741A
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- molecular material
- carbon fibers
- polymer
- alkali metal
- 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.)
- Pending
Links
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 61
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 60
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims description 15
- 239000000203 mixture Substances 0.000 title claims description 7
- 239000000463 material Substances 0.000 title abstract description 13
- -1 alkali metal salt Chemical class 0.000 claims abstract description 16
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims description 30
- 230000002378 acidificating effect Effects 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 229920001577 copolymer Polymers 0.000 abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- 239000006229 carbon black Substances 0.000 abstract 1
- 238000011282 treatment Methods 0.000 description 22
- 230000003647 oxidation Effects 0.000 description 16
- 238000007254 oxidation reaction Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000002134 carbon nanofiber Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 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 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000003811 acetone extraction Methods 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- KLFSCDLQXKYZFJ-UHFFFAOYSA-N ethanamine trihydrofluoride Chemical compound F.F.F.C(C)N KLFSCDLQXKYZFJ-UHFFFAOYSA-N 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 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 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
（従来の技術）
炭素繊維で補強された樹脂等の複合材料はスポーツ用品
、レジャー用品、宇宙航空用材料、電磁波シールド用材
料等幅広い分野にわたってその用途開発が進められてい
る。[Detailed description of the invention] (Industrial application field) (Prior art) Composite materials such as resins reinforced with carbon fibers are used in a wide range of fields such as sports goods, leisure goods, aerospace materials, and electromagnetic shielding materials. Development of its use is progressing.
炭素繊維のもつ優れた特性としての比強度、比弾性率を
生かした分野、また優れた電気伝導性を生かした分野等
今後更にその用途は広がっていくことが予想される。It is expected that its applications will further expand in the future, including fields that take advantage of carbon fiber's excellent properties such as specific strength and specific modulus, and fields that take advantage of its excellent electrical conductivity.
しかし複合化時、マトリックスとの接着強度が弱く、素
材のもつ特性を十分に生かしきれ℃いないことは現在こ
の分野におい℃克服すべき最大の問題点であり、この改
善を計るため種々の提案がなされている。However, when compounding, the adhesive strength with the matrix is weak and the characteristics of the material cannot be fully utilized. This is currently the biggest problem to be overcome in this field, and various proposals are being made to improve this. being done.
炭素繊維の改質としては酸化処理が代表的な手法として
挙げられる。酸化処理法としては気相酸化法、薬品によ
る液相酸化法、炭素繊維の電気伝導性を利用した電解酸
化法等があり、商業プラントにおいては効率性、制御性
から電解法が最も広く採用されている。Oxidation treatment is a typical method for modifying carbon fibers. Oxidation treatment methods include gas phase oxidation, liquid phase oxidation using chemicals, and electrolytic oxidation that utilizes the electrical conductivity of carbon fibers.In commercial plants, electrolysis is the most widely adopted method due to its efficiency and controllability. ing.
（発明が解決しようとする問題点）
上記いずれの処理法を採用しても過度の酸化処理は炭素
材料そのものの劣化をもたらすためおのずからその処理
には限度があり、酸化処理後、す子材料と複合化しても
必ずしも高分子材料との良好な接着性を示さない。例え
ばマトリックスとしてポリオンフィンを用いた場合、接
着性が悪く、引張り破断後の断面観察ではマ） ＩＪフ
ックスフィラーの界面でのすっぽ抜は現象が頻繁に見ら
れ、個々のもつ特性から期待されるコンポジット性能を
大きく下回る特性しか得られていない。その他の種々の
、マ） ＩＪフックスなシ得る高分子材料に対しても、
素材に応じ期待されるコンポジット特性の達成度は異な
るがいずれにしても十分満足なものとはいい難い。(Problems to be Solved by the Invention) No matter which treatment method is adopted, excessive oxidation treatment will cause deterioration of the carbon material itself, so there is a limit to the treatment. Even when composited, it does not necessarily show good adhesion with polymeric materials. For example, when polyion fins are used as a matrix, the adhesion is poor, and cross-sectional observation after tensile rupture shows that the phenomenon of IJ hook filler slipping out at the interface is frequently observed, which is expected from the characteristics of each filler. The properties obtained are far below those of composites. For various other polymeric materials such as IJ hooks,
The degree of achievement of the expected composite properties varies depending on the material, but in any case, it is difficult to say that it is fully satisfactory.
ここにいうコンポジット特性の達成度の指標としては例
えば引張強度については長繊維の場合、体積含有率比に
よる加成性での評価が一般的に使用され、また短繊維の
場合には更に複雑であり、Ｋｅｌｌｙ −Ｔｙｓｏｎの
式等が用いられる。As an indicator of the degree of achievement of the composite properties mentioned here, for example, regarding tensile strength, in the case of long fibers, evaluation of additivity based on volume content ratio is generally used, and in the case of short fibers, it is more complicated. Yes, and the Kelly-Tyson equation is used.
以上に述べたように従来の技術では炭素繊維の表面改質
のみでは十分な接着性を得るに至らないため、マトリッ
クスがポリオレフィンの場合、複合化にあたり変性ポリ
マーを組成の一部として加えることも試みられている。As mentioned above, with conventional techniques, it is not possible to obtain sufficient adhesion only by surface modification of carbon fibers, so when the matrix is polyolefin, attempts have also been made to add modified polymers as part of the composition when making composites. It is being
例えばオレフィンと、ラジカル共重合し得るエポキシ基
を有する不飽和モノマーとの共重合体、又はグラフト重
合体或いはオレフィンと、不飽和ジカルボン酸またはそ
の無水物との共重合体又はグラフト重合体等の変性ポリ
オレフィンである。For example, modification of a copolymer of an olefin and an unsaturated monomer having an epoxy group capable of radical copolymerization, or a graft polymer, or a copolymer or graft polymer of an olefin and an unsaturated dicarboxylic acid or its anhydride. It is a polyolefin.
これらの組み合わせ、即ち酸化処理後サイジング処理或
いはカッブリング剤処理をした市販炭素繊維と変性ポリ
オレフィン及びマトリックスとなるポリオレフィンの単
独或いはコポリマーとの組み合わせによシ得られる複合
材料ではこれらの処理を施さない場合と比較すれば力学
的評価での向上がみられる場合もあるが素材の特性から
期待できるものて対しては低いものであり、破断面観察
結果でも依然としてすっぽ抜は状態が多くみられる等ま
だ改善の余地は大きい。A composite material obtained by a combination of these, that is, a combination of a commercially available carbon fiber that has been subjected to an oxidation treatment, a sizing treatment, or a coupling agent treatment, a modified polyolefin, and a polyolefin as a matrix alone or in combination with a copolymer, does not undergo these treatments. When compared, there may be improvements in mechanical evaluation, but they are still low compared to what can be expected from the characteristics of the material, and even in the fracture surface observation results, there are still many cases where the bottom is pulled out, so there is still improvement. There is a lot of room for this.
１だその他の炭素繊維表面の改質方法としては、各種ポ
リマーのグラフト或いは被覆等種々提案されているもの
の、工程の複雑化等によるコスト面、及びその処理によ
る効果面から広く採用されるまでには至っていない。1. Various other methods for modifying the surface of carbon fibers, such as grafting or coating with various polymers, have been proposed, but they have not been widely adopted due to the cost of complicating the process and the effectiveness of the treatment. has not yet been reached.
本発明者は炭素繊維の特性を低下させることなく、容易
な処理と既存物質との組み合わせにより優れた特性を示
す複合材を得ることを目的として鋭意検討した結果、本
発明に到達したものである。The present inventor has arrived at the present invention as a result of intensive studies aimed at obtaining a composite material that exhibits excellent properties through easy processing and combination with existing materials without degrading the properties of carbon fiber. .
（問題点を解決するための手段）
本発明は炭素繊維と高分子との複合組成物であるが、炭
素繊維としてはその表面に酸性基をつけ、これをアルカ
リ金属塩としたものを用い、高分子としては直鎖中もし
くは分岐鎖中にエポキシ基をもつものを少なくとも１部
含む高分子を用いることを特徴とする。(Means for Solving the Problems) The present invention is a composite composition of carbon fibers and polymers. The polymer used herein is characterized in that it contains at least a portion of the polymer having an epoxy group in its linear or branched chain.
本発明によれば炭素繊維の特性を低下させることなく炭
素繊維と高分子材料との接着性を向上させることにより
、優れた特性を示す炭素繊維強化高分子複合材料を得る
ことができる。According to the present invention, a carbon fiber-reinforced polymer composite material exhibiting excellent properties can be obtained by improving the adhesion between carbon fibers and a polymer material without reducing the properties of the carbon fibers.
この複合材料は熱硬化性の場合には層間剪断強度（ＩＬ
ＳＳ ）等によシ接着力を評価することができ、熱可塑
性の場合にはＩＬＳＳ等で直接の評価はできないものの
得られた組成物の機械的特性の向上をみればそれが接着
性向上によることは明らかである。When this composite material is thermosetting, the interlaminar shear strength (IL)
SS) etc. can be used to evaluate the adhesion strength, and in the case of thermoplastics, ILSS etc. cannot be used to directly evaluate the adhesive strength. That is clear.
炭素繊維の表面に生成する酸性基とは−Ｃ０ＯＨ１−Ｏ
Ｈ１＝Ｏ１及びそれらの複合したラクトン型等である。The acidic group generated on the surface of carbon fiber is -C0OH1-O
These include H1=O1 and their combined lactone type.
炭素繊維の表面にこれらの酸性基をつけるには炭素繊維
を気相（例えば空気）酸化、電解酸化、液相酸化等の処
理を行なえばよい。In order to attach these acidic groups to the surface of carbon fibers, carbon fibers may be subjected to treatments such as gas phase (for example, air) oxidation, electrolytic oxidation, liquid phase oxidation, and the like.
炭素繊維の表面には表面処理としての酸化処理を施す前
にも少量ではあるが酸性基が存在していることは文献（
「炭素繊維」犬谷杉部編Ｐ２２２昭和５８年近代編集社
刊）でも報告されている。しかし、自然に生ずる酸性基
はわずかであるので、一般的には前記したような方法で
酸化処理を行なう。そして望ましくは１０ 当量１５’
（ＣＦ）以上の酸性基をつける（ＣＦとは炭素繊維の英
名略称）。It is reported in the literature that a small amount of acidic groups exist on the surface of carbon fibers even before oxidation treatment as a surface treatment.
It is also reported in "Carbon Fiber" edited by Inutani Sugibe, P222 (1981, published by Kindai Editorial Company). However, since there are only a few naturally occurring acidic groups, oxidation treatment is generally performed by the method described above. and preferably 10 equivalents 15'
(CF) or higher acidic groups are attached (CF is the English abbreviation for carbon fiber).
その上限は炭素繊維の種類によって異なるが、繊維の損
傷による機械的強度の低下をもたらさない程度で処理を
停止すべきであシ、例えばＰＡＮ系では５×１０ 当量
／ｇ（ＣＦ）程度である。The upper limit varies depending on the type of carbon fiber, but the treatment should be stopped at a level that does not cause a decrease in mechanical strength due to damage to the fiber, for example, for PAN type, it is about 5 × 10 equivalents/g (CF). .
使用される炭素繊維はＰＡＮ系、ピンチ系、気相成長系
等公知のすべての炭素Ｗｊ、維であり、これらは炭素繊
維、黒鉛化繊維等熱処理条件の如何にかかわらず使用す
ることができる。The carbon fibers used are all known carbon fibers such as PAN type, pinch type, and vapor growth type, and these can be used regardless of heat treatment conditions such as carbon fibers and graphitized fibers.
炭素繊維の表面の酸性基をアルカリ金属塩にするにはこ
の炭素繊維とアルカリ性物質（ＮａＯＨ１ＫＯＨ等）を
接触させればよく、アルカリ性物質を含む雰囲気下に炭
素繊維を存在させて実施する気相法、液中に炭素繊維を
浸漬、あるいは塗布して実施する方法等表面の酸性基の
中和が達成できるならばいずれの方法も用いることがで
きる。液中処理したものはその後水洗、乾燥して使用す
る。In order to convert the acidic groups on the surface of carbon fibers into alkali metal salts, it is sufficient to bring the carbon fibers into contact with an alkaline substance (such as NaOH1KOH), and this method is carried out using a gas phase method in which the carbon fibers are placed in an atmosphere containing an alkaline substance. Any method can be used as long as the acidic groups on the surface can be neutralized, such as by dipping or coating the carbon fibers in a solution. Those treated in liquid are then washed with water and dried before use.
本発明はこのように表面処理した炭素繊維と高分子との
複合材であるが、高分子として少なくともその中の１部
にエポキシ基をもつ高分子を含める必要がある。エポキ
シ基は直鎖中にあってもよく、分岐鎖中にあってもよい
。高分子はエポキシ基をもつものが１００％でおっても
よいが、他の高分子中に一部加えても効果を発揮する。The present invention is a composite material of carbon fibers and polymers that have been surface-treated in this way, but it is necessary to include a polymer having an epoxy group in at least a portion thereof. The epoxy group may be in a straight chain or in a branched chain. Although 100% of the polymer may have epoxy groups, the effect can be exerted even if a portion is added to other polymers.
この場合エポキシ基の作用を十分に発現するためにはエ
ポキシを有する高分子が１チ以上存在すれば良い。In this case, in order to fully exhibit the effect of the epoxy group, it is sufficient that one or more epoxy-containing polymers are present.
エポキシ基を有する高分子としてはこれを単独で使用さ
れる場合ビスフェノールＡ系の他エポキシ樹脂とじ粗製
造、市販されているものは好適に用いられ、垣内弘編「
エポキシ樹脂」（昭晃堂昭和５４年６月発行）第５１頁
ないし第１０５頁に製造方法、用途などが示されている
。他の高分子と併用して用いる場合はそれとのなじみを
考えて、他の高分子と類似の構造をもつものが好ましく
、特に他の高分子を改質してエポキシ基を含有する構造
にしたものが好適である。例えば他の高分子がポリエチ
レンの場合、エポキシ基をもつ高分子としてはポリエチ
レンとラジカル共重合又はグラフト重合し得る不飽和モ
ノマーとの共重合体が適しており、市販され工いる商品
とし℃は商漂名ピントファースト（注文化学（株）製）
を挙げることができる。When used alone as a polymer having an epoxy group, those based on bisphenol A and other epoxy resins that are crudely manufactured and commercially available are preferably used.
Manufacturing methods, uses, etc. are shown on pages 51 to 105 of "Epoxy Resin" (published by Shokodo in June 1974). When used in combination with other polymers, it is preferable to use one with a structure similar to that of the other polymer in consideration of compatibility with the other polymer, especially those with a structure containing an epoxy group by modifying the other polymer. Preferably. For example, when the other polymer is polyethylene, a copolymer of polyethylene and an unsaturated monomer capable of radical copolymerization or graft polymerization is suitable as the polymer with epoxy groups. Zenai Pinto First (manufactured by Custom Chemical Co., Ltd.)
can be mentioned.
エポキシ基を有する高分子と併用される他の高分子とし
てはポリオレフィン、その共重合体、例えばエチレン−
酢ビ共重合体（ＥＶＡ ）などが挙げられる。Other polymers used in combination with polymers having epoxy groups include polyolefins and copolymers thereof, such as ethylene-
Examples include vinyl acetate copolymer (EVA).
これらの炭素繊維、高分子から複合組成物をつくるには
熱可塑性高分子の場合、炭素繊維、エポキシ基を有する
高分子、他の高分子をトライブレンド後混練押出機を用
いて複合化し、Ｋノット化又は射出成型するのが一般的
であるが、エポキシ含有不飽和上ツマ−と他の高分子を
重合し得る条件で混練しつつ、同時に又は重合に引き続
き連続的に複合化することもできる。To make a composite composition from these carbon fibers and polymers, in the case of thermoplastic polymers, carbon fibers, polymers with epoxy groups, and other polymers are triblended and then composited using a kneading extruder. Generally, knotting or injection molding is performed, but it is also possible to knead the epoxy-containing unsaturated polymer and other polymers under conditions that allow polymerization, and to compound them simultaneously or continuously after polymerization. .
また熱硬化性高分子の場合、トライブレンド後熱硬化す
る方法の他に、−旦グリプレグとした後望まれる形状と
なし熱硬化することもできる。In addition, in the case of thermosetting polymers, in addition to the method of triblending and then thermosetting, it is also possible to form the glypreg into a desired shape and then thermosetting.
（作用）
本発明によって接着性が向上する要因は明らかではない
が炭素繊維表面の酸性基をアルカリ処理によってアルカ
リ金属塩とすることによシ、エポキシ環を開環して反応
し易くなシ、これを介し炭素繊維と高分子材料が化学的
に結合した効果であると推測される。従って例えば有機
酸のアルカリ金属塩を別につくり、これを炭素繊維の表
面に付着させても本発明のような効果は得られない。(Function) The reason why the adhesiveness is improved by the present invention is not clear, but by converting the acidic group on the surface of the carbon fiber into an alkali metal salt by alkali treatment, the epoxy ring does not easily open and react. It is presumed that this is the effect of chemical bonding between the carbon fiber and the polymer material. Therefore, for example, even if an alkali metal salt of an organic acid is prepared separately and attached to the surface of carbon fibers, the effects of the present invention cannot be obtained.
（効果）
本発明によれば炭素繊維の特性を低下させることなく、
簡単な処理及び特定高分子の組合せにより、後に実施例
に示すように曲げ強さ、曲げ弾性率等の機械的特性を向
上することができる。(Effect) According to the present invention, without deteriorating the characteristics of carbon fiber,
By simple processing and combination of specific polymers, mechanical properties such as flexural strength and flexural modulus can be improved as shown in Examples later.
以下実施例を示す。Examples are shown below.
炭素繊維（Ａ）
市販のＰＡＮ系炭素繊維（東邦ベスロン製： ＨＴＡ−
Ｃ６）を５５℃で６ｈｒアセトン抽出しサイソング剤を
除去した。（この時点での表面状態は炭化後酸化処理を
施した状態である。）
乾燥後過剰の濃度１１５０規定ＮａＯＨ水溶液を投入後
１１５０規定ＨＣ１水溶液で逆滴定し、炭素繊維表面の
全酸性基を定量したところ４×１０ 当量／ｇ（ＣＦ＞
であった。Carbon fiber (A) Commercially available PAN carbon fiber (manufactured by Toho Bethlon: HTA-
C6) was extracted with acetone at 55°C for 6 hours to remove the Cysong agent. (The surface condition at this point is a state in which oxidation treatment has been performed after carbonization.) After drying, add an excess concentration of 1150N NaOH aqueous solution and perform back titration with 1150N HC1 aqueous solution to quantify the total acidic groups on the carbon fiber surface. As a result, 4×10 equivalents/g (CF>
Met.
サイジング剤除去後乾燥した炭素繊維を１０倍当量のＫ
ＯＨ水溶液中に浸漬し、８０℃で４ｈｒ処理した後水洗
した。水洗終了後１００℃で真空乾燥し、表面の酸性基
をアルカリ金属塩とした炭素繊維（Ａ）を得た。After removing the sizing agent, the dried carbon fiber was treated with 10 times the equivalent of K.
It was immersed in an OH aqueous solution, treated at 80° C. for 4 hours, and then washed with water. After washing with water, the fibers were vacuum dried at 100° C. to obtain carbon fibers (A) in which the acidic groups on the surface were made with alkali metal salts.
炭素繊維（Ｂ）
水素ガスをキャリアーとして、鉄の超微粉末をエチルア
ルコール中に分散させた液を反応管内に噴射する方法で
得た気相成長炭素繊維（特開昭５８−１８０６１５）を
６０％ＨＮＯ，，１００℃の条件で、４８ ｈｒ酸化処
理を施した。Carbon fiber (B) Vapor-grown carbon fiber (Japanese Unexamined Patent Publication No. 180615/1983) obtained by injecting a liquid in which ultrafine iron powder is dispersed in ethyl alcohol using hydrogen gas as a carrier into a reaction tube was %HNO, 48 hr oxidation treatment at 100°C.
処理後−７になるまで水洗した。After treatment, it was washed with water until it reached -7.
この状態で前記［株］）と同様の手法で定量した表面の
全酸性量は５ Ｘ １０−’当量／Ｅｌ （ＣＦ ）で
あった。In this state, the total acidity on the surface was determined by the same method as in the above-mentioned [Co., Ltd.], and was 5 x 10-' equivalent/El (CF).
水洗に引き続き１０倍当量のＫＯＨ水溶液中に浸漬し８
０℃で２ｈｒ処理した後水洗した。After washing with water, immerse in a 10-fold equivalent KOH aqueous solution.
After being treated at 0°C for 2 hours, it was washed with water.
水洗終了後ｌＯＯ℃で真空乾燥し、表面の酸性基をアル
カリ金属塩とした炭素繊維の）を得た。After washing with water, it was vacuum dried at 100° C. to obtain a carbon fiber whose surface acidic groups were alkali metal salts.
エポキシ変性ポリプロピレン
ポリプロピレン（商標名ニジヨウアロマ−１銘柄：ＭＡ
５１０） １５０ ｇ、メタクリル酸グリシジル（和光
紬薬（株）製）１５（１、過酸化ベンゾイル（東京化成
（株）製）１．０９を溶媒としたキシレン３１に入れ１
１０℃で３ｈｒ反応させた。反応終了後アセトンを加え
ポリマー析出後、再溶解、再沈殿により未反応モノマー
を洗い出しエポキシ基を含有する変性ポリプロピレンを
得た。Epoxy modified polypropylene polypropylene (trade name Nijiyo Aroma-1 brand: MA
510) 150 g, glycidyl methacrylate (manufactured by Wako Tsumugi Co., Ltd.) 15 (1, benzoyl peroxide (manufactured by Tokyo Kasei Co., Ltd.) 1.09 in xylene 31 as a solvent, and 1
The reaction was carried out at 10°C for 3 hours. After the reaction was completed, acetone was added to precipitate the polymer, and unreacted monomers were washed out by redissolution and reprecipitation to obtain modified polypropylene containing epoxy groups.
グラフト量は赤外吸収ス４クトルにより検量した。グラ
フト量は０．３重量％であった。The graft amount was calibrated using an infrared absorption spectrum. The amount of grafting was 0.3% by weight.
比較炭素繊維（Ｃ）
市販の炭素繊維（東邦ペスロン（株）製ＨＴＡ −Ｃ６
）をそのまま用いた。なおこの繊維はメーカー側にて酸
化処理及びサイジング剤付与がなされ℃いる。Comparison carbon fiber (C) Commercially available carbon fiber (HTA-C6 manufactured by Toho Peslon Co., Ltd.)
) was used as is. This fiber has been oxidized and given a sizing agent by the manufacturer.
比較炭素繊維０）
上記の炭素繊維を前記（４）に示す、アセトン抽出によ
るサイジング剤除去処理までを施したもの。Comparative carbon fiber 0) The above carbon fiber was subjected to the sizing agent removal treatment by acetone extraction as shown in (4) above.
即ち炭素繊維て酸化処理のみを施した表面状態に相当す
る。In other words, it corresponds to the surface condition of carbon fibers subjected to only oxidation treatment.
比較炭素繊維＠）
前記（Ｂ）に示す、気相成長炭素繊維を酸化処理まで施
したもの。Comparative carbon fiber @) The vapor-grown carbon fiber shown in (B) above, which has been subjected to oxidation treatment.
比較炭素繊維Ｖ）
０３）に示したような処理を何ら施すことなく気相中で
生成したままの炭素繊維。Comparative Carbon Fiber V) Carbon fiber as produced in the gas phase without any treatment as shown in 03).
実施例１〜４、比較例１〜１２
炭素繊維Ａ、Ｂ、比較炭素繊維Ｃ，Ｄ、Ｅ、Ｆ、前記エ
ポキシ変性ポリプロピレン及びポリプロピレン（商標名
；ショウアロマ−銘柄： ＭＡ５１０ ）を表１に示す
配合割合にてう？ゲラストミル（東洋精器製作新製：形
式２８−１２５、ローラミキサー型式Ｒ−６０）を用い
混練した。炭素繊維は長さ６ｍのものを用いたが、混練
後は平均３００＃Ｉとなった。Examples 1 to 4, Comparative Examples 1 to 12 Carbon fibers A, B, comparative carbon fibers C, D, E, F, the epoxy-modified polypropylene and polypropylene (trade name: Show Aroma brand: MA510) are shown in Table 1. What about the blending ratio? The mixture was kneaded using a gelasto mill (manufactured by Toyo Seiki Seisakusho, model 28-125, roller mixer model R-60). The carbon fibers used had a length of 6 m, and after kneading, the average length was 300 #I.
混線条件
温度 １７０℃
時間 樹脂線９ ５分
炭素繊維投入 〃
混練 〃
計 １５分
得られた混線物を一旦冷却後平均２〜４圏立方のサイズ
に切断し熱板プレスを用い２２０℃で成形した。平板か
ら所定のサイズに試験片を打ち抜き、曲げ強度、曲げ弾
性率、引張シ強度、アイゾツト衝撃試験に供した。Mixed wire conditions Temperature: 170°C Time: Resin wire 9 5 minutes Addition of carbon fiber〃 Kneading〃 Total: 15 minutes The obtained mixed wire was once cooled, cut into an average size of 2 to 4 cubes, and molded at 220°C using a hot plate press. . Test pieces were punched out to a predetermined size from a flat plate and subjected to bending strength, bending modulus, tensile strength, and Izot impact tests.
結果をまとめて表１に示す。The results are summarized in Table 1.
ＰＡＮ系炭素繊維、気相成長炭素繊維ともに本発明方法
による組み合わせで得られた複合体の特性は、その組み
合わせの１つ（炭素繊維表面の酸性基のアルカリ金属塩
化或いは変性ポリオレフィンのいずれか）を欠いた場合
に比べ大きく向上することが明らかとなった。The properties of the composite obtained by combining both PAN-based carbon fibers and vapor-grown carbon fibers by the method of the present invention are that one of the combinations (either alkali metal chloride of the acidic group on the carbon fiber surface or modified polyolefin) It became clear that there was a significant improvement compared to the case without it.
、−ｃ、、 ７ｙ１，４＠ ？’Ｌｓ ｌｏ
ｉ＋ ４ イｈ Ｈｚ’ ；Ｊｉｉａ ｚ
−，１３゜実施例５
市販のＰＡＮ系炭素繊維「ベスファイトＨＴＡ３０００
」（東邦ベスロン（株）製）を（８）と全く同様の条件
で処理して得た、表面の酸性基をアルカリ金属塩とした
炭素繊維を「エピコート８２８Ｊ（シェル化学（株）製
エポキシ樹脂）８０重量部、３弗化はう素モノエチルア
ミン４重量部、メチルエチルケトン１６重量部の混合液
に含浸し、金型に充填して２００℃で４０分加熱硬化し
た。得られた硬化物を所定の大きさに調整し、テンシロ
ンＵＴＭ −Ｉ −２５００（東洋？−ルドウィン社製
）にて曲げ試験治具を用い０．５＋ｍ／分の速度でＩＬ
ＳＳを評価したところ１０、５ ｋｇ７ｍ であった。,-c,, 7y1,4@? 'Ls lo
i+ 4 Ih Hz';Jia z
-,13゜Example 5 Commercially available PAN-based carbon fiber "Besphite HTA3000"
'' (manufactured by Toho Bethlon Co., Ltd.) under exactly the same conditions as (8), and the acidic groups on the surface were treated with alkali metal salts. ), 4 parts by weight of boronic monoethylamine trifluoride, and 16 parts by weight of methyl ethyl ketone. IL was adjusted to the size of 0.5 + m/min using a bending test jig using Tensilon UTM-I-2500 (manufactured by Toyo?-Ludwin).
When the SS was evaluated, it was 10.5 kg and 7 m.
比較例１３
実施例５に用いた「ペスファイ）ＨＴＡ３０００Ｊを市
販されている状態のまま、実施例５と同様の手順でき浸
、硬化、ＩＬＳＳ測定を実施した。ＩＬＳＳ値は８．０
ｋｇ７簡であった。Comparative Example 13 Using the commercially available Pesphi HTA3000J used in Example 5, immersion, curing, and ILSS measurement were carried out in the same manner as in Example 5. The ILSS value was 8.0.
It was 7 kg.
Claims (1)
からなる組成物であって、該高分子中に直鎖中もしくは
分岐鎖中にエポキシ基をもつ高分子を少なくとも１部含
むことを特徴とする炭素繊維複合高分子組成物。A composition consisting of a polymer and a carbon fiber whose surface acidic groups are alkali metal salts, characterized in that the polymer contains at least one portion of a polymer having an epoxy group in its linear or branched chain. Carbon fiber composite polymer composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26564586A JPS63120741A (en) | 1986-11-10 | 1986-11-10 | Composite composition of carbon fiber high-molecular material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26564586A JPS63120741A (en) | 1986-11-10 | 1986-11-10 | Composite composition of carbon fiber high-molecular material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63120741A true JPS63120741A (en) | 1988-05-25 |
Family
ID=17420012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26564586A Pending JPS63120741A (en) | 1986-11-10 | 1986-11-10 | Composite composition of carbon fiber high-molecular material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63120741A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04209656A (en) * | 1990-12-07 | 1992-07-31 | Osaka Gas Co Ltd | Carbon fiber-reinforced resin composition |
| US5462799A (en) * | 1993-08-25 | 1995-10-31 | Toray Industries, Inc. | Carbon fibers and process for preparing same |
| WO2005073291A1 (en) * | 2004-02-02 | 2005-08-11 | Idemitsu Kosan Co., Ltd. | Carbon fiber-reinforced polyolefin resin composition and formed article made therefrom |
| JP2008106109A (en) * | 2006-10-24 | 2008-05-08 | Nagase Chemtex Corp | Method for producing carbon fiber-reinforced composite material |
| JP2010150371A (en) * | 2008-12-25 | 2010-07-08 | Toyobo Co Ltd | Carbon filament-reinforced polypropylene composite material |
| JP2011178914A (en) * | 2010-03-02 | 2011-09-15 | Teijin Chem Ltd | Carbon fiber reinforced polypropylene-based resin composition |
| JP2018159015A (en) * | 2017-03-23 | 2018-10-11 | 新日鉄住金化学株式会社 | Carbon fiber-reinforced resin composition and molded product |
| JP2019172802A (en) * | 2018-03-28 | 2019-10-10 | 日鉄ケミカル＆マテリアル株式会社 | Polyolefin-based resin composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61119772A (en) * | 1984-11-13 | 1986-06-06 | 三菱レイヨン株式会社 | Surface treatment of carbon fiber |
| JPS62149968A (en) * | 1985-12-23 | 1987-07-03 | 東レ株式会社 | Treatment of carbon fiber |
-
1986
- 1986-11-10 JP JP26564586A patent/JPS63120741A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61119772A (en) * | 1984-11-13 | 1986-06-06 | 三菱レイヨン株式会社 | Surface treatment of carbon fiber |
| JPS62149968A (en) * | 1985-12-23 | 1987-07-03 | 東レ株式会社 | Treatment of carbon fiber |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04209656A (en) * | 1990-12-07 | 1992-07-31 | Osaka Gas Co Ltd | Carbon fiber-reinforced resin composition |
| US5462799A (en) * | 1993-08-25 | 1995-10-31 | Toray Industries, Inc. | Carbon fibers and process for preparing same |
| US5587240A (en) * | 1993-08-25 | 1996-12-24 | Toray Industries, Inc. | Carbon fibers and process for preparing same |
| US5589055A (en) * | 1993-08-25 | 1996-12-31 | Toray Industries, Inc. | Method for preparing carbon fibers |
| US5691055A (en) * | 1993-08-25 | 1997-11-25 | Toray Industries, Inc. | Carbon fibers and process for preparing same |
| JP2005213479A (en) * | 2004-02-02 | 2005-08-11 | Idemitsu Kosan Co Ltd | Carbon fiber-reinforced, polyolefin-based resin composition and formed article consisting of the same |
| WO2005073291A1 (en) * | 2004-02-02 | 2005-08-11 | Idemitsu Kosan Co., Ltd. | Carbon fiber-reinforced polyolefin resin composition and formed article made therefrom |
| JP4586372B2 (en) * | 2004-02-02 | 2010-11-24 | 株式会社プライムポリマー | Polyolefin-based carbon fiber reinforced resin composition and molded article comprising the same |
| JP2008106109A (en) * | 2006-10-24 | 2008-05-08 | Nagase Chemtex Corp | Method for producing carbon fiber-reinforced composite material |
| JP2010150371A (en) * | 2008-12-25 | 2010-07-08 | Toyobo Co Ltd | Carbon filament-reinforced polypropylene composite material |
| JP2011178914A (en) * | 2010-03-02 | 2011-09-15 | Teijin Chem Ltd | Carbon fiber reinforced polypropylene-based resin composition |
| JP2018159015A (en) * | 2017-03-23 | 2018-10-11 | 新日鉄住金化学株式会社 | Carbon fiber-reinforced resin composition and molded product |
| JP2019172802A (en) * | 2018-03-28 | 2019-10-10 | 日鉄ケミカル＆マテリアル株式会社 | Polyolefin-based resin composition |
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