JP2002054031A - Carbon fiber and method for producing the same - Google Patents
Carbon fiber and method for producing the sameInfo
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- JP2002054031A JP2002054031A JP2000236646A JP2000236646A JP2002054031A JP 2002054031 A JP2002054031 A JP 2002054031A JP 2000236646 A JP2000236646 A JP 2000236646A JP 2000236646 A JP2000236646 A JP 2000236646A JP 2002054031 A JP2002054031 A JP 2002054031A
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- carbon fiber
- fiber
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- acrylic
- carbon
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、炭素繊維及びその
製造方法に関する。詳しくは、複合材料の大幅な性能向
上に寄与する高度の圧縮強度を有する炭素繊維、及び該
炭素繊維の製造方法に関する。[0001] The present invention relates to a carbon fiber and a method for producing the same. More specifically, the present invention relates to a carbon fiber having a high compressive strength that contributes to a significant improvement in performance of a composite material, and a method for producing the carbon fiber.
【０００２】[0002]
【従来の技術】炭素繊維は、比強度や比弾性率が優れる
ため、スポーツレジャー分野や宇宙航空分野を中心とし
て、用途が拡大している。2. Description of the Related Art Since carbon fibers have excellent specific strength and specific elastic modulus, their applications are expanding mainly in the field of sports and leisure and the field of aerospace.
【０００３】ゴルフシャフトや釣り竿等には、特に軽量
化を目的として引張強度が３．４ＧＰａ以上、引張弾性
率が３４０ＧＰａ以上の高強度、高弾性率炭素繊維が使
用されることが多いが、かかる用途分野では、炭素繊維
の一層の圧縮強度の向上が望まれている。For golf shafts, fishing rods and the like, high-strength, high-modulus carbon fibers having a tensile strength of 3.4 GPa or more and a tensile modulus of 340 GPa or more are often used, particularly for the purpose of weight reduction. In the field of application, it is desired to further improve the compressive strength of carbon fibers.
【０００４】また、炭素繊維を上記した用途の構造材に
適用する場合は、高度の引張弾性率を活かしつつ、構造
材の軽量化を実現するため、構造材の厚みを薄くするこ
とが多いが、この場合、炭素繊維自体の圧縮強度が低下
すると、構造材全体の圧縮強度が低下する傾向が大きく
なる。When carbon fiber is applied to a structural material for the above-mentioned applications, the thickness of the structural material is often reduced in order to realize a reduction in the weight of the structural material while utilizing a high tensile modulus. In this case, when the compressive strength of the carbon fiber itself decreases, the compressive strength of the entire structural material tends to decrease.
【０００５】圧縮強度を向上させる技術としては、例え
ば、特開昭６３−２１１３２６号公報に、アクリル系繊
維の炭化処理に際して、温度を２２００℃以上とし、原
料繊維を積極的に延伸して、その配向緩和を抑制しなが
ら、高引張弾性率、高圧縮強度の炭素繊維を得る技術が
開示されているが、炭素繊維の耐炎化、炭化処理等の熱
処理温度が高いために、炭素繊維の結晶サイズが大きく
なり、圧縮強度の向上度合いは依然として不充分であっ
た。[0005] As a technique for improving the compressive strength, for example, Japanese Patent Application Laid-Open No. 63-213326 discloses a technique in which, during the carbonization treatment of an acrylic fiber, the temperature is raised to 2200 ° C. or more, and the raw fiber is actively drawn. A technique for obtaining carbon fibers having a high tensile modulus and a high compressive strength while suppressing orientation relaxation has been disclosed.However, since the heat treatment temperature such as the flame resistance of the carbon fibers and the carbonization treatment is high, the crystal size of the carbon fibers is high. And the degree of improvement in compressive strength was still insufficient.
【０００６】このように、圧縮強度は一般に熱処理温度
と負の相関関係があり、熱処理温度の上昇に伴い、圧縮
強度は低下する傾向があり、他方、引張弾性率は熱処理
温度と正の相関関係があることから、従来技術によって
は、引張弾性率と圧縮強度が高レベルで両立した炭素繊
維を得るのは困難であった。As described above, the compressive strength generally has a negative correlation with the heat treatment temperature, and the compressive strength tends to decrease with an increase in the heat treatment temperature, while the tensile modulus has a positive correlation with the heat treatment temperature. Therefore, it has been difficult to obtain a carbon fiber having both high tensile modulus and high compressive strength at a high level, depending on the prior art.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、引張弾性率
に優れる一方、得られる複合材料に高レベルの圧縮強度
を発現させる炭素繊維、およびかかる炭素繊維を安定に
製造する方法を提供せんとするものである。DISCLOSURE OF THE INVENTION The present invention is to provide a carbon fiber which is excellent in tensile elastic modulus while exhibiting a high level of compressive strength in the obtained composite material, and a method for stably producing such a carbon fiber. Is what you do.
【０００８】[0008]
【課題を解決するための手段】上記課題を解決するた
め、本発明は次の構成を有する。即ち、引張弾性率が３
４０〜７００ＧＰａ、引張強度が３．４〜５．５ＧＰ
ａ、引張伸度が０．５〜１．４％、広角Ｘ線回折法によ
り求まる炭素網面の(002)面の結晶サイズＬｃが２．５
〜３．２ｎｍ、前記炭素網面の(100)面の結晶サイズＬ
ａが３〜４．５ｎｍ、粉末広角Ｘ線回折法により求まる
平均積層数ｎaveが２〜３．５、かつＡＳＴＭ Ｄ６９
５による圧縮強度が１．４５〜２ＧＰａであるアクリル
系炭素繊維である。In order to solve the above problems, the present invention has the following arrangement. That is, the tensile modulus is 3
40-700 GPa, tensile strength 3.4-5.5 GP
a, the tensile elongation is 0.5 to 1.4%, and the crystal size Lc of the (002) plane of the carbon network plane determined by the wide-angle X-ray diffraction method is 2.5.
~ 3.2 nm, crystal size L of (100) plane of the carbon network plane
a is 3 to 4.5 nm, the average number of layers nave determined by the powder wide-angle X-ray diffraction method is 2 to 3.5, and ASTM D69
5 is an acrylic carbon fiber having a compression strength of 1.45 to 2 GPa.
【０００９】また、上記課題を解決するため、本発明
は、次の構成を有する。即ち、アクリル系前駆体繊維
を、酸化性雰囲気下、温度２００〜３００℃で耐炎化処
理し、続いて不活性雰囲気下、温度４００〜８００℃、
昇温速度２０〜１００℃／分で前炭化処理し、さらに不
活性雰囲気下、温度１８００〜２０００℃で炭化処理す
る炭素繊維の製造方法であって、前記前炭化処理におけ
るアクリル系繊維の延伸倍率を１．０２〜１．１５とす
るアクリル系炭素繊維の製造方法である。Further, in order to solve the above problems, the present invention has the following configuration. That is, the acrylic precursor fiber is subjected to a flame-resistant treatment in an oxidizing atmosphere at a temperature of 200 to 300 ° C., and subsequently in an inert atmosphere at a temperature of 400 to 800 ° C.
A method for producing carbon fibers in which a pre-carbonization treatment is performed at a temperature-raising rate of 20 to 100 ° C./min, and further, a carbonization treatment is performed at a temperature of 1800 to 2000 ° C. in an inert atmosphere. Is 1.02 to 1.15.
【００１０】[0010]
【発明の実施の形態】本発明者等は、炭素繊維の構造と
圧縮強度との相関性に着目し、鋭意検討した結果、炭素
繊維について、結晶の積層状態を制御することにより、
引張弾性率と圧縮強度を高いレベルで両立しうることを
見出し、本発明に至った。BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have paid attention to the correlation between the structure of carbon fiber and compressive strength, and as a result of diligent studies, as a result, by controlling the crystal lamination state of carbon fiber,
The inventors have found that the tensile elastic modulus and the compressive strength can be compatible at a high level, and have reached the present invention.
【００１１】本発明の炭素繊維は、その引張弾性率が３
４０〜７００ＧＰａ、好ましくは３７５〜６４０ＧＰａ
のものである。３４０ＧＰａ未満であると、圧縮強度の
低下は顕在化しないが、適用する用途によっては、引張
弾性率が低下することがあり、７００ＧＰａを越えると
炭素網面の結晶サイズＬｃが拡大し、圧縮強度が低下す
ることがある。The carbon fiber of the present invention has a tensile modulus of 3
40 to 700 GPa, preferably 375 to 640 GPa
belongs to. If it is less than 340 GPa, the decrease in compressive strength does not become apparent, but depending on the application to which it is applied, the tensile modulus may decrease. If it exceeds 700 GPa, the crystal size Lc of the carbon network plane increases, and the compressive strength decreases. May drop.
【００１２】また、本発明の炭素繊維は、その引張強度
が３．４〜５．５ＧＰａ、好ましくは４〜５．５ＧＰａ
のものである。３．４ＧＰａ未満であると、構造材へ適
用しても軽量化効果が小さくなることがあり、５．５Ｇ
Ｐａを越えると、引張弾性率が低下することがある。さ
らに、本発明の炭素繊維は、その引張伸度が０．５〜
１．４％のものである。０．５％未満であると、製造工
程で糸切れが頻発することがあり、１．４％を越えると
優れた弾性率が得られないことがある。The carbon fiber of the present invention has a tensile strength of 3.4 to 5.5 GPa, preferably 4 to 5.5 GPa.
belongs to. If it is less than 3.4 GPa, the effect of reducing the weight may be reduced even when applied to a structural material, and may be less than 5.5 GPa.
If it exceeds Pa, the tensile modulus may decrease. Furthermore, the carbon fiber of the present invention has a tensile elongation of 0.5 to
It is 1.4%. If it is less than 0.5%, yarn breakage may occur frequently in the production process, and if it exceeds 1.4%, an excellent elastic modulus may not be obtained.
【００１３】本発明の炭素繊維は、広角Ｘ線回折法によ
り求まる炭素網面の(002)面の結晶サイズＬｃが２．５
〜３．２ｎｍ、炭素網面の(100)面の結晶サイズＬａが
３．０〜４．５ｎｍのアクリル系炭素繊維である。The carbon fiber of the present invention has a crystal size Lc of the (002) plane of the carbon network plane determined by the wide-angle X-ray diffraction method of 2.5.
It is an acrylic carbon fiber having a crystal size La of 3.0 to 4.5 nm and a (100) plane of a carbon network plane of 3.0 to 4.5 nm.
【００１４】Ｌｃが２．５ｎｍ未満であると引張弾性率
が低下することがあり、Ｌｃが３．２ｎｍを越えると圧
縮強度が低下することがある。また、Ｌａが３．０未満
であると、引張弾性率が低下することがあり、Ｌａが
４．５ｎｍを越えると、圧縮強度が低下することがあ
る。If Lc is less than 2.5 nm, the tensile modulus may decrease, and if Lc exceeds 3.2 nm, the compressive strength may decrease. If La is less than 3.0, the tensile modulus may decrease, and if La exceeds 4.5 nm, the compressive strength may decrease.
【００１５】また、本発明の炭素繊維は、粉末広角Ｘ線
回折法により求まる平均積層数ｎave（以下、単にｎave
と略記）が２．０〜３．５、好ましくは２．５〜３．
５、ＡＳＴＭ Ｄ６９５による圧縮強度が１．４〜２Ｇ
Ｐａ、好ましくは１．４５〜１．８ＧＰａのものであ
る。ｎaveが２．０未満であると、炭化繊維が構造的に
安定しないことがあり、ｎaveが３．５を越えると、圧
縮強度が著しく低下し、高度の引張弾性率と圧縮強度が
要求される用途に適用できなくなることがある。The carbon fiber of the present invention has an average lamination number nave (hereinafter simply referred to as nave) determined by a powder wide-angle X-ray diffraction method.
Abbreviated as 2.0) to 3.5, preferably 2.5 to 3.
5. Compressive strength according to ASTM D695 is 1.4 to 2G
Pa, preferably 1.45 to 1.8 GPa. If the nave is less than 2.0, the carbonized fiber may not be structurally stable. If the nave exceeds 3.5, the compressive strength is significantly reduced, and a high tensile modulus and compressive strength are required. It may not be applicable to the application.
【００１６】尚、上述したような本発明による炭素繊維
は、例えば、以下に示すような、本発明による炭素繊維
の製造方法によって安定に製造することができる。The carbon fiber according to the present invention as described above can be stably manufactured by, for example, the following method for manufacturing a carbon fiber according to the present invention.
【００１７】炭素繊維の前駆体である、アクリル系繊維
の原料としては、アクリロニトリル９０重量％以上、ア
クリロニトリルと共重合しうる成分が１０重量％以下で
構成されるアクリル系共重合体が使用できる。As a raw material of acrylic fiber, which is a precursor of carbon fiber, an acrylic copolymer composed of 90% by weight or more of acrylonitrile and 10% by weight or less of a component copolymerizable with acrylonitrile can be used.
【００１８】前記共重合体としては、アクリル酸、メタ
アクリル酸、イタコン酸、およびそれらのメチルエステ
ル、エチルエステル、プロピルエステル、ブチルエステ
ル、アルカリ金属塩、アンモニウム塩、アリルスルホン
酸、メタリルスルホン酸、スチレンスルホン酸、及びそ
れらのアルカリ金属塩からなる群から選ばれる少なくと
も１種が使用できる。Examples of the copolymer include acrylic acid, methacrylic acid, itaconic acid, and their methyl esters, ethyl esters, propyl esters, butyl esters, alkali metal salts, ammonium salts, allylsulfonic acid, methallylsulfonic acid. And at least one selected from the group consisting of styrenesulfonic acid, and alkali metal salts thereof.
【００１９】アクリル系重合体は、乳化重合、塊状重
合、溶液重合等従来公知の重合法により合成される。ま
た、溶媒としては、ジメチルアセトアミド、ジメチルス
ルホキシド、ジメチルホルムアミド、硝酸、ロダンソー
ダ水溶液等が用いられ、紡糸原液が調整される。The acrylic polymer is synthesized by a conventionally known polymerization method such as emulsion polymerization, bulk polymerization, and solution polymerization. In addition, as the solvent, dimethylacetamide, dimethylsulfoxide, dimethylformamide, nitric acid, an aqueous solution of rhoda soda, or the like is used, and a spinning stock solution is prepared.
【００２０】ここで、アクリル系重合体は、得られる炭
素繊維の物性をより高める観点から、その極限粘度
［η］が１以上、好ましくは１．３５以上、より好まし
くは１．７以上であるのが良い。ここで極限粘度［η］
の上限値としては、紡糸を安定させる観点から、５以下
とするのが良い。Here, the acrylic polymer has an intrinsic viscosity [η] of 1 or more, preferably 1.35 or more, more preferably 1.7 or more, from the viewpoint of further improving the physical properties of the obtained carbon fiber. Is good. Where the intrinsic viscosity [η]
Is preferably 5 or less from the viewpoint of stabilizing spinning.
【００２１】本発明において、アクリル系繊維は、前記
した紡糸原液を使用し、湿式紡糸方法や乾湿式紡糸方法
によって紡糸して製造することができる。In the present invention, the acrylic fiber can be produced by spinning the above-mentioned stock solution by a wet spinning method or a dry-wet spinning method.
【００２２】ここで、アクリル系繊維は、０．３３〜
１．１１ｄtex、好ましくは０．５５〜０．８９ｄtexで
あるのが良い。０．３３ｄtex未満であると、製糸工程
で、繊維から微細な粉塵が発生し、環境、衛生面での問
題が生じることがあり、１．１１ｄtexを越えると、後
の耐炎化工程、前炭化工程、及び炭化工程で、均一な熱
処理が困難となることがある。Here, the acrylic fiber is 0.33 to
It is good to be 1.11 dtex, preferably 0.55 to 0.89 dtex. If it is less than 0.33 dtex, fine dust may be generated from the fiber in the spinning process, which may cause environmental and sanitary problems. If it exceeds 1.11 dtex, the subsequent flame-resistance step and pre-carbonization step In the carbonization step, uniform heat treatment may be difficult.
【００２３】また、アクリル系繊維束は、１、０００〜
３０、０００フィラメント、好ましくは３、０００〜２
４、０００フィラメントであるのが良い。１、０００フ
ィラメント未満であると、糸切れが増すことがあり、３
０、０００フィラメントを越えると、耐炎化工程で被処
理繊維束中の蓄熱量が増し、繊維が燃焼することがあ
る。Also, the acrylic fiber bundle is preferably 1,000 to
30,000 filaments, preferably 3,000-2
Preferably, it is 4,000 filaments. If the number of filaments is less than 1,000, yarn breakage may increase.
If it exceeds 000 filaments, the amount of heat stored in the fiber bundle to be treated increases in the flame-proofing step, and the fibers may burn.
【００２４】次に、上述した方法によって得られたアク
リル系繊維から、耐炎化処理、前炭化処理、炭化処理の
各処理を経て、炭素繊維が製造される。Next, carbon fibers are produced from the acrylic fibers obtained by the above-described method, through respective treatments such as anti-oxidation treatment, pre-carbonization treatment and carbonization treatment.
【００２５】耐炎化処理では、アクリル系繊維を、空気
等の酸化性雰囲気下、２００〜３００℃として処理する
必要があり、好ましくは２２０〜２８０℃で処理するの
が良い。２００℃未満であると、ニトリル基の閉環反応
が進行しなくなり、耐炎化の程度が不足することがあ
り、３００℃を越えると耐炎化が完了する前に繊維が燃
焼することがある。In the oxidation treatment, it is necessary to treat the acrylic fiber at 200 to 300 ° C. in an oxidizing atmosphere such as air, preferably at 220 to 280 ° C. When the temperature is lower than 200 ° C., the ring-closing reaction of the nitrile group does not proceed, and the degree of flame resistance may be insufficient. When the temperature exceeds 300 ° C., the fiber may burn before the flame resistance is completed.
【００２６】また、耐炎化処理時の延伸倍率は、いわゆ
る配向緩和を抑制するために、０．９５〜１．１好まし
くは１〜１．１とするのが良い。０．９５未満であると
引張弾性率、引張強度が不足することがあり、１．１を
越えると毛羽が増すことがある。The draw ratio at the time of the oxidation treatment is preferably 0.95 to 1.1, more preferably 1 to 1.1, in order to suppress so-called relaxation of orientation. If it is less than 0.95, the tensile modulus and tensile strength may be insufficient, and if it exceeds 1.1, fluff may increase.
【００２７】耐炎化処理では、被処理繊維の比重が１．
２５〜１．６ｇ／ｃｍ3、好ましくは１．３〜１．５ｇ
／ｃｍ3になるまで処理するのが良い。１．２５ｇ／ｃ
ｍ3未満であると、前炭化処理工程で糸切れが発生する
ことがあり、１．６ｇ／ｃｍ3を越えると、得られる炭
素繊維の比重が下がり、引張弾性率が低下することがあ
る。In the oxidation treatment, the specific gravity of the fiber to be treated is 1.
25 to 1.6 g / cm 3 , preferably 1.3 to 1.5 g
/ Cm 3 . 1.25 g / c
If it is less than m 3 , yarn breakage may occur in the pre-carbonization step, and if it exceeds 1.6 g / cm 3 , the specific gravity of the obtained carbon fiber may decrease, and the tensile modulus may decrease.
【００２８】耐炎化処理後、前炭化処理する。ここで
は、被処理繊維を、窒素等の不活性雰囲気下、温度４０
０〜８００℃で処理する必要があり、好ましくは４００
〜７００℃で処理するのが良い。また、昇温速度は２０
〜１００℃／分で処理する必要があり、好ましくは４０
〜１００℃／分で処理するのが良い。After the oxidation treatment, a pre-carbonization treatment is performed. Here, the fiber to be treated is heated at a temperature of 40 under an inert atmosphere such as nitrogen.
It is necessary to process at 0 to 800 ° C., preferably 400
It is better to process at ~ 700 ° C. The heating rate is 20
処理 100 ° C./min, preferably 40
It is good to process at -100 ° C / min.
【００２９】昇温速度が２０℃／分未満であると、熱履
歴を均等化するため、糸速を低くする必要が生じ、これ
により製造コストが上昇することがあり、１００℃／分
を越えると糸切れが生じることがある。If the heating rate is less than 20 ° C./min, it is necessary to lower the yarn speed in order to equalize the heat history, which may increase the production cost and exceed 100 ° C./min. And thread breakage may occur.
【００３０】また、前炭化処理時の延伸倍率は１．０２
〜１．１５とする必要があり、好ましくは１．０４〜
１．１２とするのが良い。１．０２未満であると、得ら
れる炭素繊維において、引張弾性率が低下することがあ
り、１．１５を越えると糸切れが生じることがある。The stretching ratio during the pre-carbonization treatment is 1.02
１．１1.15, preferably 1.04〜
1.12. If it is less than 1.02, the tensile modulus of the obtained carbon fiber may decrease, and if it exceeds 1.15, thread breakage may occur.
【００３１】前炭化処理後、炭化処理する。ここでは、
被処理繊維を、窒素等の不活性雰囲気下、温度１８００
〜２０００℃で処理する必要があり、好ましくは１８５
０〜１９５０℃で処理するのが良い。１８００℃未満で
あると、得られる炭素繊維において、引張弾性率が低下
することがあり、２０００℃を越えると結晶サイズが大
きくなり、圧縮強度が低下することがある。After the pre-carbonization, carbonization is performed. here,
The fiber to be treated is heated under an inert atmosphere such as nitrogen at a temperature of 1800.
~ 2000 ° C, preferably 185 ° C
The treatment is preferably performed at 0 to 1950 ° C. If the temperature is lower than 1800 ° C., the tensile modulus of the obtained carbon fiber may decrease. If the temperature exceeds 2000 ° C., the crystal size may increase and the compressive strength may decrease.
【００３２】炭化処理時の延伸倍率は０．９５〜１．
１、好ましくは０．９６〜１．０５とするのが良い。
０．９５未満であると、得られる炭素繊維において、引
張弾性率が低下することがあり、１．１を越えると糸切
れが生じることがある。The stretching ratio during the carbonization treatment is 0.95 to 1.
1, preferably 0.96 to 1.05.
If it is less than 0.95, the tensile modulus of the obtained carbon fiber may decrease, and if it exceeds 1.1, thread breakage may occur.
【００３３】[0033]
【実施例】以下、実施例により、本発明をさらに具体的
に説明する。各実施例、比較例においては、各物性値
は、以下に示す方法により測定した。 ＜引張弾性率＞測定する炭素繊維に、ユニオンカーバイ
ド（株）製、ベークライト（登録商標）ＥＲＬ−４２２
１を１０００ｇ（９３０重量％）、三フッ化ホウ素モノ
エチルアミン（ＢＦ3・ＭＥＡ）を３０ｇ（３重量％）
及びアセトンを４０ｇ（４重量％）混合したエポキシ樹
脂組成物を含浸させ、次に１３０℃で、３０分間加熱
し、硬化させ、樹脂含浸ストランドとする。ＪＩＳ Ｒ
７６０１の樹脂含浸ストランド試験法に従い、引張強度
と引張弾性率を求める。 ＜結晶サイズＬｃ、Ｌａ、平均積層数ｎave＞ Ａ．測定試料の作製 測定する炭素繊維から、長さ４ｃｍの試験片を切り出
し、金型とコロジオン・アルコール溶液を用いて固め、
角柱形状として結晶サイズ用の測定試料とする。The present invention will be described more specifically with reference to the following examples. In each of Examples and Comparative Examples, each property value was measured by the following method. <Tensile modulus> Bakelite (registered trademark) ERL-422 manufactured by Union Carbide Co., Ltd. was applied to the carbon fiber to be measured.
1000 g (930% by weight) and 30 g (3% by weight) of boron trifluoride monoethylamine (BF 3 .MEA)
And an epoxy resin composition in which 40 g (4% by weight) of acetone and acetone are mixed, and then heated at 130 ° C. for 30 minutes to be cured to obtain a resin-impregnated strand. JIS R
According to the resin impregnated strand test method of 7601, the tensile strength and the tensile modulus are determined. <Crystal size Lc, La, average number of layers nave> Preparation of measurement sample From the carbon fiber to be measured, a 4 cm long test piece was cut out and hardened using a mold and a collodion-alcohol solution.
It is a prism-shaped measurement sample for crystal size.
【００３４】一方、積層構造の解析用試料は、測定に供
する炭素繊維を凍結粉砕して粉末とし、粉砕後の試料を
アルミ製標準試料枠に収納して作製する。 Ｂ．測定装置 （ａ）広角Ｘ線回折法（透過法） 上述した方法により作成した結晶サイズ用の測定試料
を、次の構成、条件で測定する。ここでは、測定装置と
して、（株）理学電機社製、４０３６Ａ型(管球型)を使
用した場合について示す。 （構成） Ｘ線源：ＣｕＫα線（Ｎｉフィルター使用） 出力 ：４０ｋＶ、２０ｍＡ ゴニオメータ （株）理学電機社製 スリット：２ｍｍφ−１゜−１゜ 検出器 ：シンチレーションカウンター 計数記録装置：（株）理学電機社製 ＲＡＤ−Ｃ型 （測定条件） ２θ/θ ：ステップスキャン（赤道線方向、子午線
方向） 測定範囲 ：２θ＝５〜９０゜ サンプリング：０．０５゜ 積算時間 ：２秒 尚、赤道線方向は繊維径方向、子午線方向は繊維軸方向
に相当する。 （ｂ）広角Ｘ線回折法（反射法） 上述した方法により作成した積層構造の解析用の測定試
料を、次の構成、条件で測定する。ここでは、測定装置
として、（株）理学電機社製、ＲＵ−２００(回転対陰
極型)を使用した場合について示す。 （構成） Ｘ線源：ＣｕＫα線（湾曲結晶モノクロメータ使用） 出力 ：５０ｋＶ、２００ｍＡ ゴニオメータ （株）理学電機社製 ２１５５Ｄ型 スリット：１゜−０．１５ｍｍφ−１゜−０．４５ｍｍ 検出器 ：シンチレーションカウンター 計数記録装置：（株）理学電機社製 ＲＡＤ−Ｂ型 （測定条件） ２θ/θ ：ステップスキャン 測定範囲 ：２θ＝５〜４０゜ サンプリング：０．０５゜ 積算時間 ：２秒 Ｃ．結晶サイズＬｃ、Ｌａの測定 上述した透過法により得られた(002)、(100)面のピーク
の半値幅から、次のScherrerの式により求める。ここで
は、(002)面から求めた値がＬｃ、(100)面から求めた値
がＬａとなる。On the other hand, a sample for analysis of the laminated structure is prepared by freeze-grinding carbon fibers to be used for measurement into powder, and storing the ground sample in an aluminum standard sample frame. B. Measurement device (a) Wide-angle X-ray diffraction method (transmission method) A measurement sample for a crystal size prepared by the above-described method is measured under the following configuration and conditions. Here, a case where a 4036A type (tube type) manufactured by Rigaku Corporation is used as a measuring device will be described. (Configuration) X-ray source: CuKα ray (using Ni filter) Output: 40 kV, 20 mA Goniometer Slit: 2 mm φ-1 {-1} Detector: Scintillation counter Counting and recording device: Rigaku Corporation Model RAD-C (Measurement conditions) 2θ / θ: Step scan (Equatorial line direction, Meridian direction) Measurement range: 2θ = 5-90 ° Sampling: 0.05 ° Integration time: 2 seconds Note that the equatorial line direction is The fiber diameter direction and the meridian direction correspond to the fiber axis direction. (B) Wide-angle X-ray diffraction method (reflection method) A measurement sample for analysis of a laminated structure created by the method described above is measured under the following configuration and conditions. Here, a case where RU-200 (rotating anti-cathode type) manufactured by Rigaku Corporation is used as a measuring device will be described. (Constitution) X-ray source: CuKα ray (using a curved crystal monochromator) Output: 50 kV, 200 mA Goniometer 2155D type manufactured by Rigaku Corporation Slit: 1 ゜ -0.15 mmφ-1 ゜ -0.45 mm Detector: Scintillation Counter Count recording device: RAD-B type manufactured by Rigaku Corporation (Measurement conditions) 2θ / θ: Step scan Measurement range: 2θ = 5 to 40 ° Sampling: 0.05 ° Integration time: 2 seconds Measurement of Crystal Sizes Lc and La From the half-value width of the peaks of the (002) and (100) planes obtained by the transmission method described above, it is determined by the following Scherrer equation. Here, the value obtained from the (002) plane is Lc, and the value obtained from the (100) plane is La.
【００３５】Ｌ（ｈｋｌ）＝Ｋλ／β0ｃｏｓθB 但し、 Ｌ（ｈｋｌ）：微結晶の（ｈｋｌ）面に垂直な方向の平
均の大きさ Ｋ：１．０、λ：０．１５４１８ｎｍ（Ｘ線の波長）、 β0：（βE 2−β1 2）1/2 βE：見かけの半値幅（測定値）、β12：１．０４６×
１０-2ｒａｄ θB：Braggの回折角 Ｄ．平均積層数ｎave 上述した反射法により得られた回折プロファイルに、各
種光学補正を施した補正プロファイルをフーリエ変換し
得られたパターソン関数の各ピーク面積から積層数分布
f(n)を求め、次式より平均積層数ｎaveを求める。[0035] L (hkl) = Kλ / β 0 cosθ B where, L (hkl): average direction perpendicular to the (hkl) plane of the crystallite size K: 1.0, λ: 0.15418nm ( X line wavelength), β 0: (β E 2 -β 1 2) 1/2 β E: half width (measured apparent), β 12: 1.046 ×
10 -2 rad θ B : Bragg diffraction angle Average stacking number nave Stacking number distribution from each peak area of Patterson function obtained by performing Fourier transform of a correction profile obtained by applying various optical corrections to the diffraction profile obtained by the above-mentioned reflection method.
f (n) is obtained, and the average number of layers nave is obtained from the following equation.
【００３６】ｎave＝Σf(n)/Σ[f(n)/n] ＜積層板の圧縮強度＞ Ａ．樹脂組成物の調整 次に示す原料樹脂を混合し、３０分間攪拌して樹脂組成
物を得る。 ・ビスフェノールＡジグリシジルエーテル樹脂、エピコ
ート１００１（油化シェルエポキシ社製、登録商標）、
３０重量％ ・ビスフェノールＡジグリシジルエーテル樹脂、エピコ
ート８２８（油化シェルエポキシ社製、登録商標）、３
０重量％ ・フェノールノボラックポリグリシジルエーテル樹脂、
エピクロン−Ｎ７４０（大日本インキ化学工業社製、登
録商標）、４０重量％ ・ポリビニルホルマール樹脂、ビニレックスＫ（チッソ
社製、登録商標）、５重量％ ・ジシアンジアミド、ＤＩＣＹ７（大日本インキ化学工
業社製、登録商標）、４重量％ ・３，４−ジクロロフェニル−１，１−ジメチルウレ
ア、ＤＣＭＵ９９（保土谷化学社製、硬化剤）、４重量
％ 次に、前記樹脂組成物をシリコン塗布ペーパ上に離型紙
にコーティングして得た樹脂フィルムを、円周約２．７
ｍの、６０〜７０℃に温調した鋼製ドラムに巻き付け
る。Nave = Σf (n) / Σ [f (n) / n] <Compressive strength of laminate> Preparation of Resin Composition The following starting resins are mixed and stirred for 30 minutes to obtain a resin composition. Bisphenol A diglycidyl ether resin, Epicoat 1001 (registered trademark, manufactured by Yuka Shell Epoxy),
30% by weight Bisphenol A diglycidyl ether resin, Epikote 828 (registered trademark, manufactured by Yuka Shell Epoxy), 3
0% by weight ・ Phenol novolak polyglycidyl ether resin,
Epicron-N740 (registered trademark, manufactured by Dainippon Ink and Chemicals, Inc.), 40% by weight ・ Polyvinyl formal resin, vinylex K (registered trademark, manufactured by Chisso Corporation), 5% by weight ・ Dicyandiamide, DICY7 (Dainippon Ink and Chemicals, Inc.) , 4% by weight), 3,4-dichlorophenyl-1,1-dimethylurea, DCMU99 (manufactured by Hodogaya Chemical Co., Ltd., curing agent), 4% by weight Next, the resin composition was coated on silicon-coated paper. The resin film obtained by coating the release paper on the circumference is about 2.7 circumference.
m of a steel drum temperature-controlled to 60-70 ° C.
【００３７】この上に、炭素繊維を、クリールから巻き
出し、トラバースを介して配列する。さらにその上か
ら、前記樹脂フィルムで再度覆い、ロールで回転しなが
ら、加圧し樹脂を繊維内に含浸せしめ、幅３００ｍｍ、
長さ２．７ｍの一方向プリプレグを作成する。ここで、
プリプレグの繊維目付はドラムの回転数とトラバースの
送り速度を変化させ、１９０ｇ／ｍ2に調整する。ま
た、プリプレグの樹脂量は約３５重量％とする。On this, carbon fibers are unwound from the creel and arranged via traverses. Furthermore, from above, the resin film is covered again, and while rotating with a roll, pressure is applied to impregnate the resin into the fiber, and the width is 300 mm.
Create a 2.7 m long unidirectional prepreg. here,
The basis weight of the prepreg is adjusted to 190 g / m 2 by changing the rotation speed of the drum and the feed speed of the traverse. The resin content of the prepreg is about 35% by weight.
【００３８】このプリプレグを繊維方向を引き揃えて積
層し、温度１３０℃、圧力０．３ＭＰａで、２時間硬化
させ、厚さが１ｍｍの積層板を成形する。The prepregs are laminated in the same fiber direction and cured at a temperature of 130 ° C. and a pressure of 0.3 MPa for 2 hours to form a laminated plate having a thickness of 1 mm.
【００３９】次に、この積層板に、試験片の被破壊部分
以外を補強する板を接着層の厚さが均一となるよう接着
剤等で固着させ、一方向積層板を作製する。Next, a plate for reinforcing the test piece other than the portion to be destroyed is fixed to the laminate with an adhesive or the like so that the thickness of the adhesive layer is uniform, thereby producing a one-way laminate.
【００４０】この積層板から、被破壊部分が中心になる
ように、厚さ約１±０．１ｍｍ、幅１２．７±０．１３
ｍｍ、長さ８０±０．０１３ｍｍ、ゲージ部の長さ５±
０．１３ｍｍの試験片を切り出す。From this laminated plate, the thickness is about 1 ± 0.1 mm and the width is 12.7 ± 0.13 so that the portion to be destroyed is centered.
mm, length 80 ± 0.013mm, gauge part length 5 ±
A test piece of 0.13 mm is cut out.
【００４１】この試験片より、ＡＳＴＭ Ｄ６９５に示
される圧縮治具を使用し、歪み速度１．２７ｍｍ／分の
条件で測定し、繊維体積分率６０％に換算して積層板の
圧縮強度を得る。 （実施例１〜５、比較例１〜６）アクリロニトリル９
９．５モル％、イタコン酸０．５モル％からなる極限粘
度［η］が１．８０のアクリル共重合体を２０重量％含
むジメチルスルホキシド（以下、ＤＭＳＯと略記）の溶
液を調整し、紡糸原液とした。The test piece was measured using a compression jig shown in ASTM D695 under the condition of a strain rate of 1.27 mm / min, and converted to a fiber volume fraction of 60% to obtain the compressive strength of the laminate. . (Examples 1 to 5, Comparative Examples 1 to 6) Acrylonitrile 9
A solution of dimethylsulfoxide (hereinafter abbreviated as DMSO) containing 20% by weight of an acrylic copolymer having an intrinsic viscosity [η] of 1.80 and consisting of 9.5% by mole and itaconic acid 0.5% by mole was prepared and spun. The stock solution was used.
【００４２】次に、この紡糸原液を６０℃に温調し、孔
数３０００の口金から、温度６０℃、ＤＭＳＯ濃度６０
重量％の水溶液からなる凝固浴中に紡出し、フィラメン
ト数３０００の凝固糸条とした。Next, the temperature of the spinning solution was adjusted to 60 ° C., and the temperature was 60 ° C. and the DMSO concentration was 60
It was spun into a coagulation bath composed of a weight% aqueous solution to obtain a coagulated yarn having 3000 filaments.
【００４３】次いで、凝固糸条を水洗後、９０℃の熱水
中で３倍に延伸し、さらに糸条を、アミノ変性シリコ−
ンを含む、油剤濃度が２重量％のシリコ−ン系油剤浴中
を通過させ、油剤を糸条重量に対して０．７重量％付与
した。Next, after washing the coagulated yarn with water, the coagulated yarn was stretched three times in hot water at 90 ° C.
The oil was passed through a silicone oil bath having an oil agent concentration of 2% by weight, and the oil agent was applied at 0.7% by weight based on the weight of the yarn.
【００４４】次に、１５０℃に温調した加熱ロ−ラで乾
燥緻密化し、加圧スチ−ム延伸装置で倍率４で延伸した
後、１８０℃に温調した加熱ロ−ラで乾燥処理し、単糸
繊度０．８１dtex、総繊度２４３０dtexのアクリル系繊
維を得た。Next, the film was dried and densified by a heating roller adjusted to 150 ° C., stretched at a magnification of 4 by a pressure steam stretching device, and dried by a heating roller adjusted to 180 ° C. Thus, an acrylic fiber having a single yarn fineness of 0.81 dtex and a total fineness of 2,430 dtex was obtained.
【００４５】このアクリル系繊維を、空気雰囲気中、温
度２２０〜２８０℃、倍率１で耐炎化処理し、耐炎化繊
維とした。The acrylic fiber was subjected to a flameproofing treatment in an air atmosphere at a temperature of 220 to 280 ° C. at a magnification of 1 to obtain a flameproofed fiber.
【００４６】この耐炎化繊維を、窒素雰囲気中、最高雰
囲気温度が８００℃の前炭化炉で、温度４００〜５００
℃での昇温速度を１００℃／分とし、延伸倍率を適宜変
更して前炭化処理し、さらに窒素雰囲気中、温度を適宜
変更し、、延伸倍率を０．９６として炭化処理して、フ
ィラメント数３０００の炭素繊維を得た。The oxidized fiber was placed in a nitrogen atmosphere in a pre-carbonization furnace having a maximum atmosphere temperature of 800 ° C. and a temperature of 400 to 500.
The heating rate at 100 ° C. is 100 ° C./min, the drawing ratio is appropriately changed, the pre-carbonization treatment is performed, and the temperature is appropriately changed in a nitrogen atmosphere, the drawing ratio is set to 0.96, and the carbonization treatment is performed. Several thousand carbon fibers were obtained.
【００４７】さらに、得られた炭素繊維に５０ク−ロン
／ｇの電荷を与え、硫酸水溶液中で陽極酸化処理を施
し、水洗し、乾燥した後、エポキシを成分とする表面処
理剤を付与した。Further, the obtained carbon fiber was given a charge of 50-colon / g, anodized in an aqueous sulfuric acid solution, washed with water and dried, and then a surface treating agent containing epoxy as a component was applied. .
【００４８】各実施例、比較例の製造条件、得られた炭
素繊維について、各物性値をそれぞれ表１に示す。 （実施例６、７）実施例１で調整した紡糸原液を４５℃
に温調し、孔数３０００の口金から、４ｍｍのエア−ギ
ャップを通過させて、ＤＭＳＯ濃度６０重量％の水溶液
からなる凝固浴中に紡出し、さらに折返ガイドで方向を
転換し、水切りガイドを通過させながら、凝固浴から引
き取ってフィラメント数３０００の凝固繊維とした以外
は実施例１と同様にして、単糸繊度０．８１dtex、総繊
度２４３０dtexのアクリル系繊維を得た。Table 1 shows the physical properties of the carbon fibers obtained in each of the examples and comparative examples. (Examples 6 and 7) The spinning solution prepared in Example 1 was heated at 45 ° C.
The mixture is spun into a coagulation bath composed of an aqueous solution having a DMSO concentration of 60% by weight through a 4 mm air gap from a base having 3,000 holes, and the direction is changed by a folding guide. An acrylic fiber having a single yarn fineness of 0.81 dtex and a total fineness of 2,430 dtex was obtained in the same manner as in Example 1 except that the fiber was taken out of the coagulation bath while passing through to obtain a coagulated fiber having 3000 filaments.
【００４９】この凝固糸条から、実施例１と同様にし
て、耐炎化処理、前炭化処理、炭化処理、表面処理の各
処理工程を経て炭素繊維を得た。[0049] From this coagulated yarn, carbon fibers were obtained in the same manner as in Example 1 through the respective steps of oxidization, pre-carbonization, carbonization, and surface treatment.
【００５０】各実施例、比較例の製造条件、得られた炭
素繊維について、各物性値をそれぞれ表１に示す。Table 1 shows the physical properties of the carbon fibers obtained in each of the examples and comparative examples.
【００５１】[0051]
【表１】 [Table 1]
【００５２】[0052]
【発明の効果】本発明によれば、引張弾性率に優れる一
方、得られる複合材料に高度の圧縮強度を発現させる炭
素繊維、およびかかる炭素繊維を安定に製造する方法が
提供できる。According to the present invention, it is possible to provide a carbon fiber which is excellent in tensile elastic modulus and which exhibits a high compressive strength in the obtained composite material, and a method for stably producing such a carbon fiber.
Claims (2)
強度が３．４〜５．５ＧＰａ、引張伸度が０．５〜１．
４％、広角Ｘ線回折法により求まる炭素網面の(002)面
の結晶サイズＬｃが２．５〜３．２ｎｍ、前記炭素網面
の(100)面の結晶サイズＬａが３〜４．５ｎｍ、粉末広
角Ｘ線回折法により求まる平均積層数ｎaveが２〜３．
５、かつＡＳＴＭ Ｄ６９５による圧縮強度が１．４５
〜２ＧＰａであるアクリル系炭素繊維。1. A tensile modulus of 340 to 700 GPa, a tensile strength of 3.4 to 5.5 GPa, and a tensile elongation of 0.5 to 1.
4%, the crystal size Lc of the (002) plane of the carbon network plane determined by the wide-angle X-ray diffraction method is 2.5 to 3.2 nm, and the crystal size La of the (100) plane of the carbon network plane is 3 to 4.5 nm. The average number of layers nave determined by the powder wide-angle X-ray diffraction method is 2-3.
5, and the compression strength according to ASTM D695 is 1.45.
Acrylic carbon fiber of up to 2 GPa.
下、温度２００〜３００℃で耐炎化処理し、続いて不活
性雰囲気下、温度４００〜８００℃、昇温速度２０〜１
００℃／分で前炭化処理し、さらに不活性雰囲気下、温
度１８００〜２０００℃で炭化処理する炭素繊維の製造
方法であって、前記前炭化処理におけるアクリル系繊維
の延伸倍率を１．０２〜１．１５とするアクリル系炭素
繊維の製造方法。2. An acrylic precursor fiber is subjected to a flameproofing treatment in an oxidizing atmosphere at a temperature of 200 to 300.degree. C., followed by an inert atmosphere at a temperature of 400 to 800.degree.
A method for producing carbon fibers which is pre-carbonized at 00 ° C./min and further carbonized at a temperature of 1800 to 2000 ° C. in an inert atmosphere, wherein the draw ratio of the acrylic fiber in the pre-carbonizing is 1.02 to 1.02. 1. A method for producing an acrylic carbon fiber to be 1.15.
Priority Applications (1)
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|---|---|---|---|
| JP2000236646A JP2002054031A (en) | 2000-08-04 | 2000-08-04 | Carbon fiber and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000236646A JP2002054031A (en) | 2000-08-04 | 2000-08-04 | Carbon fiber and method for producing the same |
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| Publication Number | Publication Date |
|---|---|
| JP2002054031A true JP2002054031A (en) | 2002-02-19 |
Family
ID=18728656
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000236646A Pending JP2002054031A (en) | 2000-08-04 | 2000-08-04 | Carbon fiber and method for producing the same |
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| Country | Link |
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| JP (1) | JP2002054031A (en) |
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