JPS62238828A - Carbon fiber for composite material - Google Patents
Carbon fiber for composite materialInfo
- Publication number
- JPS62238828A JPS62238828A JP30237886A JP30237886A JPS62238828A JP S62238828 A JPS62238828 A JP S62238828A JP 30237886 A JP30237886 A JP 30237886A JP 30237886 A JP30237886 A JP 30237886A JP S62238828 A JPS62238828 A JP S62238828A
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- carbon fiber
- coefficient
- water
- carbon
- 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
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 31
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 31
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000004513 sizing Methods 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 125000000524 functional group Chemical group 0.000 claims abstract description 9
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims abstract description 3
- 238000003892 spreading Methods 0.000 claims description 7
- 239000000835 fiber Substances 0.000 abstract description 21
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229910017604 nitric acid Inorganic materials 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000012669 compression test Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229920002972 Acrylic fiber Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- OKTJSMMVPCPJKN-BJUDXGSMSA-N carbon-11 Chemical compound [11C] OKTJSMMVPCPJKN-BJUDXGSMSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は機械的特性、特に衝撃後の圧縮強度特性に優れ
た炭素４１維複合材料に有効な炭素ＩＮに関するもので
あり、本発明の炭素繊維を用いた複合材料は航空機をは
じめ、自＠Ｊ東、一般工業用に広く使用しうるちのであ
る。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to carbon IN which is effective for carbon-41 fiber composite materials having excellent mechanical properties, particularly compressive strength properties after impact. Composite materials using fibers are widely used in aircraft, Japan, and general industrial applications.
従来の炭素繊維複合材料に用いる炭素Ｉｌ維は出発繊維
としてポリアクリロニトリル系プレカーサーを用いる場
合、まず酸化雰囲気下２００〜３００℃で耐臭化処理し
、次いで不活性雰囲気下で炭素化して後、一般には気相
もしくは液相酸化してマトリックスとのＩＩＷ性を上げ
、次いで後加工での糸切れや毛羽立ちを抑える為、適当
なサイジング剤で処理したものを用いることが誘過であ
る。When using a polyacrylonitrile precursor as a starting fiber, carbon Il fibers used in conventional carbon fiber composite materials are first treated with odor resistance at 200 to 300°C in an oxidizing atmosphere, then carbonized in an inert atmosphere, and then generally is oxidized in gas phase or liquid phase to improve IIW properties with the matrix, and then treated with an appropriate sizing agent in order to suppress thread breakage and fluffing in post-processing.
しかし、これらの炭素繊維を用いた複合材料は未だに糸
とマトリックスとの接着性が充分でなく、特に衝撃後圧
縮強度（ＣＡ Ｉ ）は、ヨーロッパ公開特許１３３２
８１号公報表■実施例３５にみられる通り、６８．１に
９／ｃｒｔｒ （＝ １５００１ｂ ｉｎ／ｉｎ）の衝
撃後で１９３．２ｘｌＯ３ｋＰａ （＝１９．７に９
／ｒｔｍ２’）のレベルが一般的であり、この実施例３
５に示されるような耐熱性の高いマトリックスを使用し
てのＣＡＩの向上は極めて困難な状況にある。However, composite materials using these carbon fibers still do not have sufficient adhesion between the yarn and the matrix, and in particular, the compressive strength after impact (CA I) is
No. 81 Publication Table■ As seen in Example 35, after an impact of 68.1 to 9/crtr (= 15001b in/in), 193.2xlO3kPa (=19.7 to 9
/rtm2') level is common, and this Example 3
It is extremely difficult to improve CAI using a highly heat-resistant matrix as shown in No. 5.
又、ＣＡ［向上の為にヨーＯツバ公開特許１３３２８０
号公報の実施例６．７．８では平均値として４５．３ｋ
ｓｉ （＝３１． ＥＮＫＦ／ｒＭＡ２）の性能が１
９られているが、この複合材はプリプレグの居間にイン
ターリーフ（１ｎｔｅｒｌｅａｆ）という高靭性の層を
入れたものであり、その層の介在の為にｍ雑容積含有率
が上らず、又プリプレグに面の方向性があり、扱い性に
劣るものであった。Also, CA [Yo O Tsuba Public Patent 133280 to improve
In Example 6.7.8 of the publication, the average value is 45.3k.
The performance of si (=31.ENKF/rMA2) is 1
However, this composite material has a highly tough layer called interleaf in the prepreg, and because of the presence of this layer, the miscellaneous volume content does not increase, and the prepreg The surface had a certain directionality, making it difficult to handle.
一方、航空機業界では機体等の軽量化の目的からＣＡＩ
を２７Ｋｇ／ｃｍ２以上とする要求があり、これを満足
させるために特別の層を含まぬ複合材の開発が望まれて
いる。On the other hand, in the aircraft industry, CAI is used for the purpose of reducing the weight of aircraft, etc.
There is a demand for 27 kg/cm2 or more, and in order to satisfy this demand, it is desired to develop a composite material that does not include a special layer.
本発明者らは上述の如き問題点に鑑み、鋭意検討した結
果、後述の如旦特定条件を満足する酸化処理された炭素
繊維を用いることにより同一のマトリックス樹脂を用い
るにも拘らず、その衝撃後の圧縮強度を著しく向上しう
ろことを見出゛し、本発明を完成した。In view of the above-mentioned problems, the inventors of the present invention have made extensive studies and found that by using carbon fibers that have been oxidized and satisfies the specific conditions described below, even though the same matrix resin is used, the impact The present invention was completed by discovering a scale that significantly improves the subsequent compressive strength.
（問題点を解決するための手段〕
本発明の要旨とするところは、複合材料用炭素ｍｇとし
て、Ｘ線光電子分光法によって測定される表面の酸素含
有官能基量（Ｏ１Ｓ／Ｃ１５）が０．０５〜０．３０で
あり、水抽出物係数が２．０以下より好ましくは０．５
以下であり、トウの拡がり係数がｌＸ１０’以上であっ
て、好適にはサイジング剤付１１ｉが０．１ｗｔ％以下
である炭素ｖ＆維を用いることにより、同一のマトリッ
クス樹脂を用いるにも拘らず、その衝撃後圧縮強度を著
しく向上せしめることにある。(Means for Solving the Problems) The gist of the present invention is that the amount of oxygen-containing functional groups (O1S/C15) on the surface measured by X-ray photoelectron spectroscopy is 0.5 mg as carbon for composite materials. 05 to 0.30, and the water extractable coefficient is 2.0 or less, preferably 0.5
By using carbon v&fiber with a tow spreading coefficient of 1X10' or more and preferably 0.1wt% or less of 11i with a sizing agent, even though the same matrix resin is used, The object is to significantly improve the compressive strength after impact.
本発明で言う水油出物係数は、炭素繊維１〜５９を内径
８〜１６αのビーカーに入れ、蒸留水を炭素繊維の１１
倍（重量比）投入してこれを種内容１ｆｔ２９８ （幅
）Ｘ１５５（奥行）Ｘ１５２（深さ＃１Ｉ１１＞、槽内
水温５０ｔｈ５℃の超音波洗浄礪（発振周波数４３に１
１ｚ、高周波出力９０−）に入れて１０分間洗浄し、次
いで上澄み液を回収して１ ｃｒｒｒのセル長の石英’
ＦＪｔＪＶセルに入゛れ、対照液に蒸留水を入れてＵＶ
分光光度計により１８７〜４００ｒｖを走査し、２００
ｎｍの吸光度（アプソーバンス）を求め、この吸光度を
ここでは水抽出物係数と呼ぶ。The water-oil extrusion coefficient referred to in the present invention is calculated by placing carbon fibers 1 to 59 in a beaker with an inner diameter of 8 to 16α, and adding distilled water to the carbon fibers 11 to 59.
(weight ratio) and put it into an ultrasonic cleaning tank (oscillation frequency 43 to 1
1z, high frequency power 90-) for 10 minutes, then the supernatant was collected and a 1 crrr cell length quartz cell was washed for 10 minutes.
Put it in the FJtJV cell, add distilled water as a control solution and apply UV light.
Scan from 187 to 400 rv with a spectrophotometer, and
The absorbance in nm is determined, and this absorbance is referred to herein as the water extract coefficient.
本発明の拡がり係数は第１図に示す通り撚りを戻したト
ウをデニール当り７５Ｉｑの張力をかけ５０φのバー（
表面加工硬質クロムメッキ＃２００梨地加工）に対し入
角３０’出角４５°で線速度ＩＴｒＬ／ｗｉｎで通した
時のパース上の拡がり巾を測定（＃ＩＩＩ＋）シ、それ
をトウデニールで割った値として求めるものである。又
、バー１．２の距離は３０ ｃｍ、バー２．３の距離は
５０ｃＩ１１である。The spreading coefficient of the present invention is determined by applying a tension of 75 Iq per denier to the untwisted tow as shown in Fig. 1 with a 50φ bar (
Surface treatment Hard chrome plating #200 (matte finish) was passed through at an entry angle of 30° and an exit angle of 45° at a linear speed of ITrL/win, and the width on the perspective was measured (#III+) and divided by the toe denier. It is determined as a value. Also, the distance between bar 1.2 is 30 cm, and the distance between bar 2.3 is 50 cI11.
対象とする炭素ｍ維は、ポリアクリロニトリル系プレカ
ーサー、ピッチ系プレカーサーいずれから得られるもの
であってもよく、その引張り弾性率ハ１つｔＯｎ／ｍｍ
ｌ＃＋２以上、引張す強度ｔ、ｔ ２５ ＯＫ！ｊ／Ｍ
２以上、引張り伸度１．５％以上のものである。The targeted carbon fibers may be obtained from either a polyacrylonitrile precursor or a pitch precursor, and their tensile modulus is 1tOn/mm.
l#+2 or more, tensile strength t, t 25 OK! j/M
2 or more, and the tensile elongation is 1.5% or more.
本発明の炭素ａｍは、Ｘ線光電子分光法によって求めら
れる炭素繊維表面の酸素含有官能基量（０１，／Ｃ１，
）が０．０５〜０．３０のものであることが必要である
。The carbon am of the present invention has an oxygen-containing functional group amount (01, /C1,
) is required to be 0.05 to 0.30.
０．０５未満ではマトリックス樹脂と炭素繊維との接着
性が不足し０．３０を越えると繊維強度が低下する為望
ましくない。酸素含有官能基量が０．０５〜０．３０の
炭素繊維を得るためには、液相処理の場合は、例えば硝
酸水溶液中で処理槽の直前に配置した金属性ガイドロー
ラーを介して炭素ｔｄＡＨに＋ＩｊＪ電圧を印加し処理
液中に配した白金製陰穫板との間に炭素繊維１ｇ当り６
０〜６００クーロンの電気ｍを負荷する方法、あるいは
気相処理の場合は、例えば１００〜２００℃のオゾン１
〜５ ｖｏ１％を含む空気雰囲気中で１〜５分処理する
方法等が挙げられる。If it is less than 0.05, the adhesion between the matrix resin and carbon fibers will be insufficient, and if it exceeds 0.30, the fiber strength will decrease, which is not desirable. In order to obtain carbon fibers having an oxygen-containing functional group content of 0.05 to 0.30, in the case of liquid phase treatment, carbon tdAH 6 per gram of carbon fiber between a platinum shield plate placed in the treatment solution and a +IjJ voltage applied to the
In the case of a method of loading electricity m of 0 to 600 coulombs, or in the case of gas phase treatment, for example, ozone 1 of 100 to 200 °C
Examples include a method of processing for 1 to 5 minutes in an air atmosphere containing 1 to 5 vol%.
これらの表面処理を施した炭素繊維は一般に直ちにサイ
ジング剤で処理されるが、その拡がり係数が１ Ｘ １
０−３に上となるようにサイジング剤と量の関係が満足
されれば、特にサイジング剤の種類は特定されない。い
ずれにしてもマトリックスとの相溶性の高いものが望ま
しい。拡がり係数が１×１０−３未満のときは、トウ内
繊維の開繊が不充分となりマトリックス樹脂との接着性
を阻害するので好ましくない。These surface-treated carbon fibers are generally immediately treated with a sizing agent, but the spreading coefficient is 1 x 1
The type of sizing agent is not particularly specified as long as the relationship between the sizing agent and the amount is satisfied such that it is above 0-3. In any case, it is desirable that the material has high compatibility with the matrix. When the spreading coefficient is less than 1×10 −3 , the fibers within the tow are not sufficiently opened, which impairs the adhesion with the matrix resin, which is not preferable.
上記の条件を満足するサイジング剤の付＠陽はＱ、１ｗ
ｔ％以下より好ましくは０．０１’ｌｌｔ％以下である
。With sizing agent that satisfies the above conditions @Yang is Q, 1w
It is less than t%, preferably less than 0.01'llt%.
サイジング剤付着量はＪＩＳ Ｒ７６０１６８，２Ｖ
ｔ酸洗浄法を用いて測定する。Sizing agent adhesion amount is JIS R760168, 2V
Measure using the acid washing method.
サイジング剤付着聞が０．１ｗｔ％を越えると、トウの
拡がり性が悪くなり局部的に繊維と繊維が接着している
為にその部分へのマトリックス樹脂の浸透が阻害される
傾向を示すが、トウを熱風で一度解繊したり、バーを通
して解繊したり又張力下の繊維を叩いて解繊する方法等
を単一もしくは組合せることにより解繊して、拡がり係
数を１×１０−３のレベルに上げられるものであれば０
．１ｗｔ％より多量のサイジング剤の付着があっても差
支えない。ここで使用するサイジング剤は、マトリック
ス樹脂と馴染み易いという点からビスフェノールＡジグ
リシジルエーテル又はそのビスフェノール八との反応物
、あるいはそのグリシジル基をエチレンオキシドから得
られるポリエーテルアルコールと反応させた下記一般式
のような化合物が望ましい。If the amount of sizing agent attached exceeds 0.1 wt%, the spreadability of the tow deteriorates and fibers locally adhere to each other, which tends to inhibit the penetration of the matrix resin into those areas. The tow is defibrated once with hot air, defibrated through a bar, or defibrated by hitting the fibers under tension, either singly or in combination, to achieve a spreading coefficient of 1 x 10-3. 0 if it can be raised to the level of
．． There is no problem even if more than 1 wt% of the sizing agent is attached. The sizing agent used here is bisphenol A diglycidyl ether or its reaction product with bisphenol 8, or the following general formula in which the glycidyl group is reacted with a polyether alcohol obtained from ethylene oxide, because it is easily compatible with the matrix resin. Such compounds are desirable.
上Ｃ
巴−δ
よ−一
己
巳
本発明の水抽出物係数が２．０より大である場合には、
炭素繊維の表面に比較的弱い結合力の層が生成しており
、この層を介してマトリックス樹脂が結合する為、特に
衝撃力に対してその弱い結合力の層が破壊すると考えら
れる。Upper C Tomoe-δ Yo-Ikkimi When the water extractable coefficient of the present invention is greater than 2.0,
A layer of relatively weak bonding force is formed on the surface of the carbon fiber, and the matrix resin is bonded through this layer, so it is thought that the layer of weak bonding force is destroyed especially by impact force.
従ってこの層をより減少することが好ましく、そのレベ
ルは水抽出物係数として２．０以下であることが必要で
ある。Therefore, it is preferable to further reduce this layer, and its level needs to be 2.0 or less as a water extractable coefficient.
炭素ｍＭｉの水抽出物係数を減少するには、炭素繊維を
製造後、表面酸化処理をした後、例えばｐＨ４〜１２の
水もしくは水湿液で洗浄する方法が有効である。この洗
浄時超音波洗浄を併用したり更に加熱したりすることは
有効であり、又誘電ｈ１１熱を利用することも有効であ
る。In order to reduce the water extractable coefficient of carbon mmi, it is effective to perform a surface oxidation treatment on the carbon fiber after manufacturing it, and then wash it with water or a water wet solution having a pH of 4 to 12, for example. During this cleaning, it is effective to use ultrasonic cleaning in combination or to further heat it, and it is also effective to use dielectric h11 heat.
以下実施例により、本発明を具体的に説明する。 The present invention will be specifically described below with reference to Examples.
衝撃後圧縮強度の測定は次の方法によった。The post-impact compressive strength was measured by the following method.
ＮＡＳＡ ＲＰ １０９２に準拠して、パネル寸法
４″Ｘ６″Ｘ０．２５″の板を３″×５″の穴のあいた
スチール製台上に固定した後、その中心に１／２″Ｒの
ノーズをつけた４、９Ｋｇの分銅を落下せしめ、板厚１
ｉｎｃｈ当り１５００１ｂｉｎの衝撃を加えた後そのパ
ネルを圧縮試験することにより、衝撃後圧縮強度を求め
る。In accordance with NASA RP 1092, a board with panel dimensions of 4" x 6" x 0.25" was fixed on a steel stand with a 3" x 5" hole, and a 1/2" R nose was placed in the center. A weight of 4.9 kg attached was dropped, and the thickness of the plate was 1.
After applying an impact of 15,001 bins per inch, the panel is subjected to a compression test to determine the post-impact compressive strength.
実施例１
アクリロニトリル９８ｗｔ％、アクリル酸メチル１ｗｔ
％、メタクリルＭ １ ｗｔ％の組成を有する比粘度［
ηＳｔ）］＝０．２０の重合体をジメチルホルムアミド
を溶媒として湿式紡糸を行ない、引き続き湯浴上５倍に
延伸し、水洗後乾燥して更に乾熱１７０℃で１．３倍に
延伸して１．２デニールの繊度を有するフィラメント数
６０００のアクリル繊維を得た。Example 1 Acrylonitrile 98wt%, methyl acrylate 1wt
%, specific viscosity with a composition of methacrylic M 1 wt% [
ηSt)]=0.20 was wet-spun using dimethylformamide as a solvent, then stretched 5 times on a hot water bath, washed with water, dried, and further stretched 1.3 times with dry heat at 170°C. Acrylic fibers having a fineness of 1.2 denier and having 6000 filaments were obtained.
Ｘ線回析より求められるｔａＩｉの配向度口は９０．３
％であった。The orientation degree of taIi determined by X-ray diffraction is 90.3
%Met.
このアクリル繊維を２２０℃−２４０℃−２６０℃の３
段階の温度ブＯファイルを有する熱風循環型の耐炎化炉
を６００分間通過しめて耐炎化処理を行なうに際し、繊
維の密度が１．２２ｇ／ｃｍ３に達するまでに回転ロー
ルの速度差によって１５％の伸長を与え、その後繊維と
接触する回転ロールの速度を等速に固定することにより
、繊維の局部的収縮を抑制して耐炎化処理を終了した。This acrylic fiber was heated at 220℃-240℃-260℃
During the flame-retardant treatment by passing through a hot-air circulating type flame-retardant furnace with a temperature-controlled O file for 600 minutes, the fibers elongate by 15% due to the speed difference of the rotating rolls until the fiber reaches a density of 1.22 g/cm3. was applied, and then the speed of the rotating roll in contact with the fibers was fixed at a constant speed, thereby suppressing local shrinkage of the fibers and completing the flame-retardant treatment.
次に該耐炎化繊維を純粋なＮ２気流中６００℃の第１炭
素化炉中を３分間通過せしめるに際して１０％の伸長を
加え、さらに同雰囲気中１２００℃の最ｉ０ｉ温度を有
する第２炭素化炉中において４００部ｇ／デニールの張
力下に熱処理を行ない引張り強度５０３Ｋｆｆ／ｍａｒ
、弾性率２４ ｔｏｎ／ ｍｍ ２、密度１．７
９（１／ｃｃ、目イ」０．４ｇ／ＴｒＬの物性を有する
炭素繊維（Ｉ−ａ＞を得た。The flame-retardant fibers are then passed through a first carbonization furnace at 600°C in a pure N2 stream for 3 minutes, elongated by 10%, and then subjected to a second carbonization process in the same atmosphere with a maximum i0i temperature of 1200°C. Heat treated in a furnace under a tension of 400 parts g/denier, resulting in a tensile strength of 503 Kff/mar.
, elastic modulus 24 ton/mm2, density 1.7
A carbon fiber (I-a>) having physical properties of 9 (1/cc, 0.4 g/TrL) was obtained.
上で得られた炭素繊維は次いで２００℃の１．８容量％
０３を含む空気中にトウの状態で３分滞在せしめて後、
外径７０鴫のステンレス製穴明き紙管にｉ ｏｏｏｍ、
巻きとり後、浴比１／２０で清水中に放置し、放置時間
を変えて水抽出物像＠２．５．０．８．０．７．０．５
の各レヘルノ炭素１１維（Ｉ−ｂ）を１ｎた。この時の
炭素繊維の表面酸素含有官能Ｗａｌｋ （０１５／Ｃ１
，） ハ０．１５〜０．２０であった。次いでこの炭素
繊維をエピコート８３４（油化シェル社製ビスフェノー
ルＡ型エポキシ樹脂）をメチルエチルケトンに溶解した
溶液に通すことによりサイジング剤付着患０．０１．０
．０７．０．２．０．５各Ｗ（％の炭素繊維（Ｉ−ｃ）
を得た。The carbon fibers obtained above were then heated to 1.8% by volume at 200°C.
After being allowed to stay in the tow state for 3 minutes in air containing 03,
iooom in a stainless steel perforated paper tube with an outer diameter of 70 mm.
After winding, it was left in clean water at a bath ratio of 1/20, and the water extract image @2.5.0.8.0.7.0.5 was obtained by changing the standing time.
1 n of each Leherno carbon 11 fiber (I-b) was prepared. Surface oxygen-containing functional walk of carbon fiber at this time (015/C1
,) was 0.15 to 0.20. Next, this carbon fiber was passed through a solution of Epicoat 834 (bisphenol A type epoxy resin manufactured by Yuka Shell Co., Ltd.) dissolved in methyl ethyl ketone to reduce the chance of sizing agent adhesion.
．． 07.0.2.0.5 each W (% carbon fiber (I-c)
I got it.
得られた表１に示す各種炭素Ｉｌ雑に特公昭６０−１７
２８９号公報の実施例１に記載されたマトリックス樹脂
のメチルエチルケトン溶液（エポキシ樹脂（ハ）（エピ
コート８２８、シェル化学製）１００部に４．４′ジア
ミノジフ工ニルスルホン９部を加え、隈伴器つき加熱容
器に入れて内温１５０℃で攪拌下４時間重合せしめ、重
合後水冷したパネル上へ薄膜上に吐出し、重合停止し、
得られた予１ｉｉ綜合物＠１００部に対し、Ｎ−（３・
４−ジクロロフェニル）−Ｎ’−Ｎ’ −ジメチル尿素
３部を加え、５０℃で攪拌混合してペースト状物を１ｑ
、このペースト状物６０部をメチルエチルケトン４０部
と混合し、均一溶液としたもの）を含浸しつつ、ドラム
に巻きつけた後、乾燥し、次いで切り開くことにより、
一方向プリプレグ（糸目付１４５ｓ／ｍ 、樹脂含有
率３３ｗｔ％）を得た。The obtained various carbon materials shown in Table 1 were
To 100 parts of the matrix resin methyl ethyl ketone solution (epoxy resin (III) (Epicote 828, manufactured by Shell Chemical Co., Ltd.) described in Example 1 of Publication No. 289, 9 parts of 4.4'diaminodiphenyl sulfone was added, and the mixture was heated with a shank. The mixture was placed in a container and polymerized for 4 hours with stirring at an internal temperature of 150°C. After polymerization, the mixture was discharged onto a thin film onto a water-cooled panel to stop the polymerization.
N-(3.
Add 3 parts of 4-dichlorophenyl)-N'-N'-dimethylurea and stir and mix at 50°C to make 1q of paste.
, 60 parts of this paste-like material was mixed with 40 parts of methyl ethyl ketone to form a homogeneous solution) and wound around a drum, dried, and then cut open.
A unidirectional prepreg (thickness: 145 s/m 2 , resin content: 33 wt%) was obtained.
このプリプレグを
［＋４５１０／−４５／９０］ ４ｓの受環方性に積層
し、１８０℃で２ｖＦ間硬化させ複合材パネルを得た。This prepreg was laminated in an annular orientation of [+4510/-45/90] 4s and cured for 2vF at 180°C to obtain a composite panel.
そのコンポジットの繊維容積含有率は表１の通りであっ
た。その後、衝撃後圧縮強度を求めた。結果を併せて表
１に示した。本結果より水抽出物係数が低いこと、拡が
り係数の大きいこと、又、サイジング剤付着量が低い炭
素繊維が高い衝撃後圧縮強度を与えることが明らかであ
る。The fiber volume content of the composite was as shown in Table 1. Thereafter, the compressive strength after impact was determined. The results are also shown in Table 1. From these results, it is clear that carbon fibers with a low water extractable coefficient, a large spreading coefficient, and a low amount of sizing agent attached provide high compressive strength after impact.
実施例１、比較例１のＩＩ後圧縮試験の試験片の破断面
の電子類ｔａ鏡写真（各９００倍）を第２及び第３図に
示す。この写真より糸とマトリックスの）Ｂ Ｗ性が水
ｈｂ出物係数の違いにより大きく変わり、水抽出物係数
の大きいものの接着性が低いことが明らかである。FIGS. 2 and 3 show electronic mirror photographs (each magnified at 900 times) of the fracture surfaces of the test pieces of the II post-compression test of Example 1 and Comparative Example 1. It is clear from this photograph that the BW properties (of the yarn and the matrix) vary greatly depending on the water-HBB extraction coefficient, and that those with a high water-extractable coefficient have low adhesion.
実施例５〜８、比較例５〜８
実施例１において、使用する炭素繊維として２％ｌｉｌ
’１Ｍ水溶液中で糸１ｇ当り２００クーロンの電気量を
流すことにより、陽極酸化してその後湯洗して表面酸素
含有官能基ｆｆｌ （０１，／Ｃ１，）が０．１８〜０
．２２のものを用いて、又使用するマトリックス樹脂と
して、特開昭５９−２１５３１４号公報の実施例４の組
成物を用いる他は実施例１と同様にして表２の結果を得
た。Examples 5 to 8, Comparative Examples 5 to 8 In Example 1, 2% lil was used as the carbon fiber.
'By passing 200 coulombs of electricity per gram of thread in a 1M aqueous solution, it is anodized and then washed with hot water to reduce the surface oxygen-containing functional group ffl (01,/C1,) from 0.18 to 0.
．． The results shown in Table 2 were obtained in the same manner as in Example 1, except that the composition of Example 4 of JP-A-59-215314 was used as the matrix resin.
実施例９〜１２、比較例９〜１２
実施例１において使用するマトリックス樹脂としてヨー
ロッパ公開特許１３３２８１号公報の実施例２の組成物
を用いる他は同様にして表３の結果を得た。Examples 9 to 12, Comparative Examples 9 to 12 The results shown in Table 3 were obtained in the same manner as in Example 1, except that the composition of Example 2 of European Patent Publication No. 133281 was used as the matrix resin.
比較例１３
実施例１で得た炭素繊維（Ｉ−ａ）を２００℃の１．８
容１％０３を含む空気中にトウの状態で０．５分、８分
滞在させることにより酸化処理をした復、実施例１の通
り清水処理して水抽出物係数０．５とした。この時の表
面酸素含有官能基量（０、、／ Ｃ１ｓ）はそれぞれ０
．０３．０．４であった。次いで、実施例１のサイジン
グ剤を０．０１ｗｔ％付着せしめた炭素繊維を得た後、
実施例１と同様にしてコンポジットを作成し、衝ｗＪ後
圧縮強度を求めたところ、それぞれ１８に９／１ｎｓ２
（ＶＦ６１ ％） 、２５に９／ａ＋” （Ｖｆ６０％
） Ｔ：あり、表面酸素含有官能基量が低い時は充分な
性能の得られないことは明らかである。又、高過ぎる場
合にも性能が低下することが伺える。Comparative Example 13 The carbon fiber (I-a) obtained in Example 1 was heated to 1.8
The tow was oxidized by being left in air containing 1% 03 by volume for 0.5 and 8 minutes, and then treated with clean water as in Example 1 to give a water extractable coefficient of 0.5. At this time, the amount of surface oxygen-containing functional groups (0, , / C1s) is 0, respectively.
．． It was 03.0.4. Next, after obtaining carbon fibers to which 0.01 wt% of the sizing agent of Example 1 was attached,
A composite was prepared in the same manner as in Example 1, and the compressive strength after impact wJ was determined.
(VF61%), 25 to 9/a+” (Vf60%
) T: Yes, and it is clear that sufficient performance cannot be obtained when the amount of surface oxygen-containing functional groups is low. It can also be seen that performance deteriorates when the temperature is too high.
実施例１３〜１６、比較例１４〜１７
実施例１において炭素繊維（Ｉ−ａ）を得るに当り、焼
成条件を第２炭素化炉の雰囲気最高ｍ度を１８００℃と
することにより引張り強度４５８Ｋｇ／ｒＩｔＩＲ２、
弾性率３０．２ ｔｏｎ／ｍ２、密度１．７７０９／ｃ
ｍ３、目付０．３９ｓ／ｍの物性の炭素繊維を得た。こ
れを５％重炭酸アンモニウムの水溶液中で糸１ｇ当り２
５０クーロンの電気伍を流すことにより陽極酸化してそ
の湯洗後の表面ＨＭ含有官能塁身０１３／ＣＩｓが０．
２−０．２１のものを得た。又、使用するマトリックス
樹脂として特開昭６０−５８４２４号公報の実施例２の
組成物を用いる他は実施例１と同様にして表４の結果を
得た。Examples 13 to 16, Comparative Examples 14 to 17 In obtaining the carbon fiber (I-a) in Example 1, the tensile strength was 458 kg by setting the firing conditions to a maximum temperature of 1800°C in the atmosphere of the second carbonization furnace. /rItIR2,
Elastic modulus 30.2 ton/m2, density 1.7709/c
A carbon fiber having physical properties of 0.39 s/m and a basis weight of 0.39 s/m was obtained. This was mixed in an aqueous solution of 5% ammonium bicarbonate at 2 ml per gram of yarn.
After being anodized by flowing 50 coulombs of electricity, the surface after washing with hot water has a HM-containing functional base material 013/CIs of 0.
2-0.21 was obtained. The results shown in Table 4 were obtained in the same manner as in Example 1, except that the composition of Example 2 of JP-A-60-58424 was used as the matrix resin.
実施例１７、比較例１８
実施例１及び比較例１で用いた炭素繊維を用いてヨーロ
ッパ公開特許１３３２８１号公報の実施例８のマトリッ
クス樹脂を含浸させる他は実施例１、比較例１と同様に
してコンポジットを作成し衝撃後の圧縮試験を実施した
。結果は表５の通りであった。Example 17, Comparative Example 18 The same procedure as Example 1 and Comparative Example 1 was carried out except that the carbon fiber used in Example 1 and Comparative Example 1 was impregnated with the matrix resin of Example 8 of European Patent Publication No. 133281. A composite was prepared and a compression test was conducted after impact. The results are shown in Table 5.
第１図は拡がり係数測定の方法を示したものである。矢
印はトウの移動方向を示す。
１：分銅
２．３，４：５０Φロール
５：炭素繊維トウ
第２図、及び第６図は、それぞれ実施例１および比較例
１で得られた試験片の破断面の粒子構造の電子顕微鏡写
真（各９００倍）である。
各図面の左下端の白色部分は長さ１０μを示す。FIG. 1 shows the method of measuring the spread coefficient. Arrows indicate the direction of tow movement. 1: weight 2.3, 4: 50Φ roll 5: carbon fiber tow Figures 2 and 6 are electron micrographs of the particle structure of the fractured surface of the test pieces obtained in Example 1 and Comparative Example 1, respectively. (900 times each). The white portion at the lower left corner of each drawing indicates a length of 10μ.
Claims (3)
含有官能基量（Ｏ＿１＿Ｓ／Ｃ＿１＿Ｓ）が０．０５〜
０．３、水抽出物係数が２．０以下、 トウの拡がり係数が１×１０＾−＾３以上 であることを特徴とする耐衝撃性に優れた複合材料用炭
素繊維。(1) The amount of oxygen-containing functional groups on the surface (O_1_S/C_1_S) measured by X-ray photoelectron spectroscopy is 0.05 to
0.3, a water extractable coefficient of 2.0 or less, and a tow spreading coefficient of 1×10^-^3 or more. Carbon fiber for composite materials having excellent impact resistance.
とを特徴とする特許請求の範囲第１項記載の炭素繊維。(2) The carbon fiber according to claim 1, wherein the amount of sizing agent deposited is 0.1 wt% or less.
弾性率が１９ｔｏｎ／ｍｍ＾２以上、引張り伸度が１．
５％以上であることを特徴とする特許請求の範囲第１項
記載の炭素繊維。(3) Tensile strength is 250 kg/mm^2 or more, tensile modulus is 19 ton/mm^2 or more, and tensile elongation is 1.
The carbon fiber according to claim 1, characterized in that the carbon fiber content is 5% or more.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28670685 | 1985-12-19 | ||
| JP60-286706 | 1985-12-19 | ||
| JP60-287498 | 1985-12-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62238828A true JPS62238828A (en) | 1987-10-19 |
| JPH0444016B2 JPH0444016B2 (en) | 1992-07-20 |
Family
ID=17707936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30237886A Granted JPS62238828A (en) | 1985-12-19 | 1986-12-18 | Carbon fiber for composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62238828A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0457973A (en) * | 1990-06-25 | 1992-02-25 | Idemitsu Kosan Co Ltd | Carbon fiber composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5711216A (en) * | 1980-06-18 | 1982-01-20 | Mitsubishi Rayon Co Ltd | Production of carbon fiber |
| JPS58136838A (en) * | 1982-02-08 | 1983-08-15 | Mitsubishi Rayon Co Ltd | Production of high-performance carbon fiber |
-
1986
- 1986-12-18 JP JP30237886A patent/JPS62238828A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5711216A (en) * | 1980-06-18 | 1982-01-20 | Mitsubishi Rayon Co Ltd | Production of carbon fiber |
| JPS58136838A (en) * | 1982-02-08 | 1983-08-15 | Mitsubishi Rayon Co Ltd | Production of high-performance carbon fiber |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0457973A (en) * | 1990-06-25 | 1992-02-25 | Idemitsu Kosan Co Ltd | Carbon fiber composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0444016B2 (en) | 1992-07-20 |
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