JPH03146720A - Production of pitch-based carbon fiber having high elongation and high strength - Google Patents
Production of pitch-based carbon fiber having high elongation and high strengthInfo
- Publication number
- JPH03146720A JPH03146720A JP28238989A JP28238989A JPH03146720A JP H03146720 A JPH03146720 A JP H03146720A JP 28238989 A JP28238989 A JP 28238989A JP 28238989 A JP28238989 A JP 28238989A JP H03146720 A JPH03146720 A JP H03146720A
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- pitch
- fibers
- elongation
- temperature
- 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 76
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 76
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000000835 fiber Substances 0.000 claims abstract description 93
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001301 oxygen Substances 0.000 claims abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 238000003763 carbonization Methods 0.000 claims abstract description 25
- 238000011282 treatment Methods 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000004927 fusion Effects 0.000 claims description 4
- 239000002344 surface layer Substances 0.000 claims description 3
- 238000009941 weaving Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- 239000012783 reinforcing fiber Substances 0.000 abstract description 5
- 238000009940 knitting Methods 0.000 abstract description 3
- 238000002074 melt spinning Methods 0.000 abstract description 3
- 238000010000 carbonizing Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000005087 graphitization Methods 0.000 abstract 1
- 239000011295 pitch Substances 0.000 description 48
- 238000009987 spinning Methods 0.000 description 20
- 239000007789 gas Substances 0.000 description 17
- 239000010410 layer Substances 0.000 description 16
- 238000003475 lamination Methods 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- 239000013078 crystal Substances 0.000 description 9
- 238000003780 insertion Methods 0.000 description 9
- 230000037431 insertion Effects 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- -1 if necessary Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
先東上土亘且玉１
本発明は、一般には、炭素繊維の製造方法に関するもの
であり、特に、糸扱い性に優れ、編織が容易であって、
宇宙産業、自動車産業、建築産業などにおいて軽量構造
材料用強化繊維として広く使・用することのできる高伸
度、高強度のピッチ系炭素繊維の製造方法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION The present invention generally relates to a method for manufacturing carbon fiber, and in particular, it has excellent yarn handling properties and is easy to knit and weave.
The present invention relates to a method for manufacturing pitch-based carbon fibers with high elongation and high strength, which can be widely used as reinforcing fibers for lightweight structural materials in the space industry, automobile industry, construction industry, etc.
虹え立且１
従来、炭素繊維としては、ＰＡＮ系及びレーヨン系炭素
繊維が広く製造及び使用されているが、ＰＡＮ系及びレ
ーヨン系炭素繊維は原料が高価で炭化収率も悪く、経済
面で良くない。そこで、近年、コストの廉価なピッチを
原料としており、しかも、引張強度及び引張弾性率の点
においても優れているピッチ系炭素繊維が注目を浴びて
いる。1 Conventionally, PAN-based and rayon-based carbon fibers have been widely produced and used as carbon fibers, but PAN-based and rayon-based carbon fibers are economically disadvantageous due to their expensive raw materials and poor carbonization yields. not good. Therefore, in recent years, pitch-based carbon fibers that are made from inexpensive pitch and are excellent in tensile strength and tensile modulus have attracted attention.
現在、ピッチ系炭素繊維は、
（１）石油系ピッチ、石炭系ピッチなどから炭素繊維に
適した炭素質ピッチを調製し、該炭素質ピッチを加熱溶
融して紡糸機にて紡糸し、集束、合糸してピッチ繊維束
を製造し、
（２）前記ピッチ繊維束を不融化炉で酸化性ガス雰囲気
下にて２００〜３５０℃までに加熱して不融化し、
（３）引き続いて、該不融化された繊維束を炭化炉で不
活性ガス雰囲気下にて５００〜２０００℃まで加熱して
炭化して、更には３０００℃まで加熱して黒鉛化するこ
と、
により製造されている。Currently, pitch-based carbon fibers are produced by: (1) preparing carbonaceous pitch suitable for carbon fiber from petroleum-based pitch, coal-based pitch, etc., heating and melting the carbonaceous pitch, spinning it in a spinning machine, converging it, (2) The pitch fiber bundle is heated to 200 to 350°C in an oxidizing gas atmosphere in an infusible furnace to make it infusible; (3) Subsequently, It is manufactured by heating the infusible fiber bundle in a carbonization furnace to 500 to 2000°C in an inert gas atmosphere to carbonize it, and further heating it to 3000°C to graphitize it.
が ゛しようとする
しかしながら、一般に、このようにして得られたピッチ
系炭素繊維は、引張強度は２゜０ＧＰａ （２００Ｋｇ
／ｍｍ” ）以上、引張弾性率は６００ＧＰａ （６０
ｔｏ−ｎ／ｍｍ” ）以上と高いものが得られるが、伸
度（伸び率）は、通常０．５％以下、大きくても１％程
度であった。However, the pitch-based carbon fiber obtained in this way generally has a tensile strength of 2°0 GPa (200 kg
/mm”) or more, the tensile modulus is 600GPa (60
Although a high elongation (elongation rate) of 0.5% or less was obtained, the elongation (rate of elongation) was usually 0.5% or less, and at most about 1%.
このように従来のピッチ系炭素繊維は伸度が小さいため
に取扱いが難しく、編織性に劣り、特に複合材料を製造
する場合に大きな問題となっていた。As described above, conventional pitch-based carbon fibers are difficult to handle due to their low elongation, and have poor weaving and weaving properties, which poses a major problem particularly when manufacturing composite materials.
本発明者らは、ピッチを原料として、引張強度及び引張
弾性率を損なうことなく、高伸度のピッチ系炭素繊維を
得るべく研究開発する過程にて、炭素繊維の結晶構造を
特異なちのとすることで、つまり、Ｘ ｉＩ ｉｌｌ造
パラメーターの配向角（φ）が２５〜３８＠ 積層厚み
（Ｌｃ）が１９〜３５人、層間隔（ｄ、。２）が３．４
５〜３゜５０人である結晶ｔＭ ？ｑを有することによ
り、所定レベル以上の引張強度、引張弾性率を具備し、
良好な編織性を示す１．０％以上の伸度を有した高伸度
、高強度のピッチ系炭素繊維を得ることができることを
見出した。In the process of research and development to obtain pitch-based carbon fibers with high elongation using pitch as a raw material without impairing tensile strength and tensile modulus, the present inventors developed the crystal structure of carbon fibers into a unique structure. In other words, the orientation angle (φ) of the structural parameters is 25 to 38, the lamination thickness (Lc) is 19 to 35, and the layer spacing (d, .2) is 3.4.
Crystal tM that is 5-3゜50 people? By having q, it has tensile strength and tensile modulus of a predetermined level or higher,
It has been found that it is possible to obtain high-strength, high-strength pitch-based carbon fibers having an elongation of 1.0% or more and exhibiting good weaving properties.
又、本発明者らは、このような炭素繊維を使用して複合
材料を製造する際に最も重要な要素の一つである、繊維
とマトリクス樹脂との接着性が、強化繊維の表面酸素濃
度及び繊維中の全酸素濃度に大きく影響されることを見
出した。つまり、Ｘ線光電子分光法（ＥＳＣＡ）によっ
て検出される繊維表面の原子数比０／Ｃが０．１−０゜
３５であり、繊維中の全酸素濃度が０．Ｏｌ〜０．２重
量％とされる場合に繊維とマトリクス樹脂との間の接着
性は良好であり、この範囲を外れ、繊維表面の原子数比
０／Ｃが０．１未満であり繊維中の全酸素濃度が０．０
１重量％未満であると、接着性が著しく低下することが
分かった。In addition, the present inventors have discovered that the adhesion between the fibers and the matrix resin, which is one of the most important factors when manufacturing composite materials using such carbon fibers, is dependent on the surface oxygen concentration of the reinforcing fibers. It was also found that the total oxygen concentration in the fibers greatly influenced the concentration of oxygen in the fibers. That is, the atomic ratio 0/C on the fiber surface detected by X-ray photoelectron spectroscopy (ESCA) is 0.1-0°35, and the total oxygen concentration in the fiber is 0.35. The adhesion between the fiber and the matrix resin is good when the content of Ol~0.2% by weight is outside this range, and the atomic ratio 0/C on the fiber surface is less than 0.1 and The total oxygen concentration of is 0.0
It has been found that when the amount is less than 1% by weight, the adhesiveness is significantly reduced.
又、繊維表面の原子比０／Ｃが０８３５を越え、繊維中
の全酸素濃度が０．２重量％越えると、炭素繊維の引張
強度、引張弾性率が著しく低下することが分かった。It has also been found that when the atomic ratio 0/C on the fiber surface exceeds 0835 and the total oxygen concentration in the fiber exceeds 0.2% by weight, the tensile strength and tensile modulus of the carbon fiber decrease significantly.
又、本発明者らは、斯る新規な高伸度、高強度のピッチ
系炭素繊維は、不融化繊維の炭化処理工程時に所定のテ
ンションを掛け、更に、繊維が融着しない範囲で迅速に
炭化することにより製造することができ、更に、その後
に酸化処理することによりマトリクスとの接着性が向上
すると共に、繊維の物性も向上することを見出した。In addition, the present inventors have developed such novel high-elongation, high-strength pitch-based carbon fibers by applying a predetermined tension during the carbonization process of infusible fibers, and furthermore, by applying a predetermined tension to the infusible fibers during the carbonization process, and furthermore, by applying a predetermined tension to the carbonization process of the infusible fibers, and then quickly applying the tension within the range that the fibers do not fuse. It has been found that the fibers can be produced by carbonization, and that by subsequent oxidation treatment, the adhesion to the matrix is improved and the physical properties of the fibers are also improved.
本発明は、斯る新規な知見に基づきなされたものである
。The present invention has been made based on this new knowledge.
従って、本発明の目的は、高伸度、高強度を有するピッ
チ系炭素繊維を効率よく製造するための製造方法を提供
することである。Therefore, an object of the present invention is to provide a manufacturing method for efficiently manufacturing pitch-based carbon fibers having high elongation and high strength.
本発明の他の目的は、取扱いが容易であり、編織性に優
れ、又、マトリクス、樹脂との接着性のよい、従って複
合材料を製造するのに適した高伸度、高強度のピッチ系
炭素繊維の製造方法を提供することである。Another object of the present invention is to provide a pitch system with high elongation and high strength that is easy to handle, has excellent knitting and weaving properties, and has good adhesion to matrices and resins, and is therefore suitable for manufacturing composite materials. An object of the present invention is to provide a method for producing carbon fiber.
を ′ るための
上記諸国的は、本発明に係る高伸度、高強度ピッチ系炭
素繊維の製造方法によって達成される。要約すれば本発
明は、１２０〜３５０℃の富酸素雰囲気下で３〜３０分
間にて不融化処理を行い繊維の表層を選択的に強く酸化
した後、不活性ガス雰囲気下で最低温度４００℃、最高
温度１３００℃にて融着しない範囲で昇温しで、フィラ
ンフ１１本当りｏ、ｏｏｔ〜Ｏ１２ｇｒの張力を付与し
ながら、３〜１５分間にて炭化処理を行い、その後酸化
処理を行うことを特徴とする高伸度、高強度ピッチ系炭
素繊維の製造方法である。The above-mentioned methods for producing a pitch-based carbon fiber with high elongation and high strength according to the present invention can be achieved. To summarize, the present invention performs an infusibility treatment in an oxygen-rich atmosphere at 120 to 350°C for 3 to 30 minutes to selectively and strongly oxidize the surface layer of the fibers, and then heats the fibers at a minimum temperature of 400°C in an inert gas atmosphere. , while increasing the temperature to a maximum temperature of 1300°C within a range that does not cause fusion, and applying a tension of o,oot to O12gr per 11 fillets, carbonization treatment is performed for 3 to 15 minutes, and then oxidation treatment is performed. This is a method for producing high-elongation, high-strength pitch-based carbon fiber characterized by the following.
好ましくは、上記炭化処理は、４００〜５５０ ’Ｃま
では昇温温度１０〜９０℃／分で、５５０〜１３００℃
までは昇温温度１００〜５００’Ｃ／分で行なわれる。Preferably, the carbonization treatment is carried out at a temperature of 550-1300°C with a heating temperature of 10-90°C/min until 400-550'C.
Up to this point, heating is performed at a heating temperature of 100 to 500'C/min.
このように本発明に従って製造された炭素繊維は、Ｘ
Ｉ！構造パラメーターの配向角（φ）が２５〜３８°、
積層厚み（Ｌｃ）が１９〜３５人、層間隔（ｄＯｏ２）
が３．４５〜３゜５０人である結晶構造を有し、Ｘ線光
電子分光法によって検出される繊維表面の原子数比０／
Ｃが０．１〜０．３５であり、繊維中の全酸素濃度が０
．０１〜０．２重量％であり、伸度が１．０％以上であ
る高伸度、高強度ピッチ系炭素繊維とされる。又、通常
、該繊維の引張強度は１５０Ｋｇ／ ｍ ｍ ２以上で
ある。The carbon fiber thus produced according to the present invention is
I! The structural parameter orientation angle (φ) is 25 to 38°,
Lamination thickness (Lc) is 19 to 35 people, layer spacing (dOo2)
It has a crystal structure with a crystalline structure of 3.45 to 3.50 atoms, and the atomic ratio of the fiber surface detected by X-ray photoelectron spectroscopy is 0/
C is 0.1 to 0.35, and the total oxygen concentration in the fiber is 0.
．． 01 to 0.2% by weight, and is considered to be a high elongation, high strength pitch carbon fiber having an elongation of 1.0% or more. Further, the tensile strength of the fiber is usually 150 kg/mm 2 or more.
本発明者らは、上述のように、ピッチを原料として編織
性の良好なピッチ系炭素繊維を得るべく研究開発する過
程にて、先ず、良好な編織性を有するには伸度が少なく
と１．０％以上であることが必要であることが分かった
。又、所定レベル以上の引張強度及び引張弾性率を備え
、しかもこのような高伸度のピッチ系炭素繊維を得るに
は炭素繊維の結晶構造を特異なものとすることが重要で
あることを見出した。As mentioned above, in the process of research and development to obtain pitch-based carbon fibers with good weaving and weaving properties using pitch as a raw material, we first discovered that in order to have good weaving and weaving properties, the elongation must be at least 1. It was found that it is necessary to have a content of .0% or more. We also discovered that in order to obtain pitch-based carbon fibers that have tensile strength and tensile modulus above a predetermined level and also have such high elongation, it is important to make the crystal structure of the carbon fibers unique. Ta.
更に説明すると、本発明者らは、伸度が少な（とも１．
０％以上であり、且つ、１５０Ｋｇ／ｍｍ２以上の引張
強度を有した高伸度のピッチ系炭素繊維を得るには炭素
繊維の結晶構造は、Ｘ線構造パラメーターの配向角（φ
）が２５〜３８°、積層厚み（Ｌｃ）が１９〜３５人、
層間隔（ｄｏ。２）が３．４５〜３．５０入であること
が重要であり、特に、配向角（φ）は、ピッチ系炭素繊
維の伸度を決定する重要なファクターであることを見出
した。又、結晶構造を決定するファクターの１つである
積層厚み（Ｌｃ）及び層間隔（ｄ、、２）は、伸度、引
張強度及び弾性率を適当にバランスさせるために適当範
囲に存在することが又重要であることが分かった。To explain further, the present inventors found that the elongation was small (both 1.
0% or more and has a tensile strength of 150 Kg/mm2 or more, the crystal structure of carbon fiber is determined by the orientation angle (φ
) is 25 to 38 degrees, lamination thickness (Lc) is 19 to 35 people,
It is important that the layer spacing (do. 2) is 3.45 to 3.50, and in particular, the orientation angle (φ) is an important factor that determines the elongation of pitch-based carbon fibers. I found it. In addition, the lamination thickness (Lc) and interlayer spacing (d, 2), which are one of the factors that determine the crystal structure, must be within an appropriate range to appropriately balance elongation, tensile strength, and elastic modulus. was also found to be important.
つまり、配向角（φ）が２０”より小さい場合には十分
な伸度、即ち、良好な編織性を得るに必要な１．０％以
上の伸度が得られず、又、配向角（φ）が３８°を越え
ると引張弾性率が低下し炭素繊維本来の特性である高弾
性率という利点が損なわれてしまう。更に、積層厚み（
Ｌｃ）及び層間隔（ａＯ０２）がそれぞれ１９〜３５人
及び３゜４５〜３．５０人の範囲外である場合には、必
要とされる引張強度及び引張弾性率が得られ難いという
問題が生じる。In other words, if the orientation angle (φ) is smaller than 20", sufficient elongation, that is, the elongation of 1.0% or more necessary to obtain good weaving properties, cannot be obtained; ) exceeds 38°, the tensile modulus decreases and the advantage of high modulus, which is an inherent characteristic of carbon fiber, is lost.Furthermore, if the laminated thickness (
When Lc) and interlayer spacing (aO02) are outside the ranges of 19 to 35 people and 3°45 to 3.50 people, respectively, the problem arises that it is difficult to obtain the required tensile strength and tensile modulus. .
以上のように、高伸度、高強度のピッチ系炭素繊維を得
るには、Ｘ線構造パラメーターである配向角（φ）、積
層厚み（Ｌｃ）、層間隔（ｄｏ。As described above, in order to obtain pitch-based carbon fibers with high elongation and high strength, it is necessary to adjust the X-ray structure parameters such as orientation angle (φ), lamination thickness (Lc), and layer spacing (do).
２）を、掻く狭い範囲の適当範囲にバランスさせること
が重要である。It is important to balance 2) within an appropriate narrow range.
上記特異な結晶構造を有したピッチ系炭素繊維によると
、伸度が少なくと１．０％以上であり、一般に、１．０
〜５．０％とされ、しがち。According to the above-mentioned pitch-based carbon fiber having a unique crystal structure, the elongation is at least 1.0%, and generally 1.0%.
It is said to be ~5.0% and tends to occur.
１５０Ｋｇ／ｍｍ”以上の引張強度を有した高伸度、高
強度のピッチ系炭素繊維を得ることができる。A pitch-based carbon fiber having a tensile strength of 150 Kg/mm" or more, high elongation, and high strength can be obtained.
又、本発明に従って製造されたピッチ系炭素繊維は、Ｘ
線光電子分光法によって検出される繊維表面の原子数比
０７Ｃが０．１〜０．３５であり、繊維中の全酸素濃度
が０．０１〜０．２重量％であり、そのまま複合樹脂の
強化繊維として使用した場合にもマトリクス樹脂との接
着性が良好であり、高強度、高弾性率の炭素繊維強化複
合樹脂を得ることができることが分かった。Furthermore, the pitch-based carbon fiber produced according to the present invention has
The atomic ratio 07C on the fiber surface detected by line photoelectron spectroscopy is 0.1 to 0.35, the total oxygen concentration in the fiber is 0.01 to 0.2% by weight, and the composite resin can be strengthened as it is. It was found that even when used as fibers, the adhesion with the matrix resin was good, and a carbon fiber reinforced composite resin with high strength and high modulus of elasticity could be obtained.
又、斯る炭素繊維は、必要に応じて、更に焼成すること
により、より高強度、高弾性率の炭素繊維及び黒鉛繊維
を得ることができることも分かった。It has also been found that by further firing such carbon fibers, if necessary, carbon fibers and graphite fibers with higher strength and higher modulus of elasticity can be obtained.
次に、本発明に係る炭素繊維の製造方法について説明す
る。Next, a method for manufacturing carbon fiber according to the present invention will be explained.
本発明に係る製造方法を実施するに際しては、先ず、熱
伝導性の良い挿入部材を入れた紡糸ノズルを使用して紡
糸ノズルにおける溶融ピッチの温度変動、特に温度降下
を最低限度に抑えることにより紡糸し炭素質ピッチ繊維
を得る。又、斯かる紡糸法によれば、紡糸時に生じる配
向孔れを適度に制御し得るという利点がある。When carrying out the production method according to the present invention, first, a spinning nozzle containing an insertion member with good thermal conductivity is used to suppress temperature fluctuations in the melt pitch in the spinning nozzle, especially temperature drops, to a minimum, thereby spinning the yarn. to obtain carbonaceous pitch fibers. Further, such a spinning method has the advantage that orientation holes that occur during spinning can be appropriately controlled.
このようにして得られたピッチ繊維を富酸素ガス雰囲気
下（酸素濃度３０−１００％）にて最低ｄ度１２０〜２
００℃から１〜ｂ
速度で最高温度２４０〜３５０℃まで３〜３０分間で加
熱して不融化を行なう。The pitch fibers obtained in this way are heated to a minimum d degree of 120 to 2 in an oxygen-rich gas atmosphere (oxygen concentration 30 to 100%).
The mixture is heated from 00° C. to a maximum temperature of 240° to 350° C. for 3 to 30 minutes at a speed of 1 to 30° C. to infusible.
不融化した繊維は、次に不活性ガス中で、例えば窒素或
はアルゴンガス中で４００〜５５０℃までは昇温速度１
０〜ｂ
１３００℃までは昇温速度１００〜ｂ
で加熱し、短時間にて、例えば３〜１５分間にて炭化処
理を行う。このように、不融化時には、高温の富酸素ガ
ス雰囲気下にて迅速に、かつ繊維の表層を選択的に強く
酸化（内部酸化は少）した後、融着しない範囲で不活性
ガス雰囲気下で迅速に炭化することにより達成される。The infusible fibers are then heated in an inert gas, for example nitrogen or argon gas, at a heating rate of 1 to 400-550°C.
It is heated at a temperature increase rate of 100 to 1300° C., and carbonization is performed in a short time, for example, for 3 to 15 minutes. In this way, during infusibility, the surface layer of the fiber is quickly and selectively strongly oxidized (with little internal oxidation) in a high-temperature oxygen-rich gas atmosphere, and then the fiber is oxidized under an inert gas atmosphere to the extent that it does not fuse. This is achieved by rapid carbonization.
更に、このとき、本発明によれば、炭素繊維の配向角を
改良するだめに、１フイラメント当たり０．００１〜０
．２ｇｒのテンションが付与され、強制配向がなされる
。Furthermore, at this time, according to the present invention, in order to improve the orientation angle of carbon fibers, 0.001 to 0.
．． A tension of 2gr is applied to force orientation.
これにより、伸度が少なくとも１．０％以上であり、一
般に、１．０〜５．０％とされ、しかも、１５０Ｋｇ／
ｍｍ”以上の引張強度を有した高伸度のピッチ系炭素繊
維を得ることができる。As a result, the elongation is at least 1.0% or more, generally 1.0 to 5.0%, and 150 kg/
It is possible to obtain high elongation pitch-based carbon fibers having a tensile strength of 10 mm or more.
このようにして得られた高伸度、高強度のピッチ系炭素
繊維は、引き続いて、酸化処理され、繊維の表面酸素濃
度及び繊維中の全酸素濃度が上記所定範囲内になるよう
に調整される。酸化処理は、気相法、液相法等、特に限
定することはないが例えば酸素含有雰囲気下で短時間の
気相酸化を行うことにより１つの実施例としては、繊維
を酸素濃度６０％の富酸素雰囲気中にて７００℃、３０
秒間加熱することにより好適に行うことができる。又、
このような高温、短時間の酸化処理により、マトリクス
との接着性が向上すると共に、繊維の物性も向上するこ
とが分かった。The pitch-based carbon fibers with high elongation and high strength thus obtained are subsequently oxidized and adjusted so that the surface oxygen concentration of the fibers and the total oxygen concentration in the fibers are within the above-mentioned predetermined ranges. Ru. The oxidation treatment may be carried out by a gas phase method, a liquid phase method, etc., but is not particularly limited. For example, by performing a short time gas phase oxidation in an oxygen-containing atmosphere, the fibers may be oxidized to an oxygen concentration of 60%. 700℃, 30℃ in oxygen-rich atmosphere
This can be suitably carried out by heating for a second. or,
It has been found that such high-temperature, short-time oxidation treatment improves the adhesion to the matrix and also improves the physical properties of the fiber.
該炭素繊維は、その後、必要に応じて、不活性ガス雰囲
気下にて２０００℃まで加熱して炭化するか、更に３０
００℃まで加熱して黒鉛化される。その結果、引張強度
が３００ Ｋ ｇ ／ ｍ ｍ ”以上、及び引張弾性
率が６０ ｔ ｏ ｎ ／ ｍ ｍ ”以上の高強度、
高弾性率のピッチ系炭素繊維が得られる。The carbon fibers are then carbonized by heating to 2000°C in an inert gas atmosphere, or further heated to 300°C, as necessary.
Graphitized by heating to 00°C. As a result, it has high strength with a tensile strength of 300 Kg/mm" or more and a tensile modulus of 60 ton/mm" or more,
A pitch-based carbon fiber with a high modulus of elasticity is obtained.
本明細書において、炭素繊維の特性は下記の如き測定方
法を採用した。In this specification, the following measurement method was used to measure the characteristics of carbon fiber.
・Ｘ線構造パラメータ
配向角（φ）、積層厚さ（Ｌｃ） 層間隔（ｄ、。２
）は広角Ｘ線回折より求められる炭素繊維の微細構造を
表わすパラメータである。・X-ray structural parameters Orientation angle (φ), Lamination thickness (Lc) Layer spacing (d, .2
) is a parameter representing the fine structure of carbon fiber determined by wide-angle X-ray diffraction.
配向角（φ）は結晶の繊維軸方向に対する選択的配向の
程度を示すもので、この角度が小さい程配向が良いこと
を意味する。積層厚さ（Ｌｃ）は炭素微結晶中の（００
２）面の見掛けの積層の厚さを表わし、一般に積層厚さ
（Ｌｃ）が大きい程結晶性が良いと見なされる。又、層
間隔（ｄｏ。The orientation angle (φ) indicates the degree of selective orientation of the crystal with respect to the fiber axis direction, and the smaller this angle, the better the orientation. The lamination thickness (Lc) is (00
2) It represents the apparent thickness of the laminated layers on the surface, and it is generally considered that the larger the laminated thickness (Lc), the better the crystallinity. Also, the layer spacing (do.
２）は微結晶の（００２）面の層間隔を表わし、層間隔
（ｄｏ。２）が小さい程結晶性が良いと見なされる。2) represents the layer spacing of the (002) plane of the microcrystal, and it is considered that the smaller the layer spacing (do. 2), the better the crystallinity.
配向角（φ）の測定は繊維試料台を使用し、繊維束が計
数管の走査面に垂直になっている状態で、計数管を走査
して（００２）回折帯の強度が最大となる回折角２θ（
約２６°）を予め求める。次に計数管をこの位置に保持
した状態で、繊維試料台を３６０°回転することにより
（００２）回折環の強度分布を測定し、強度最大値のｌ
／２の点における半価幅を配向角（φ）とする。To measure the orientation angle (φ), use a fiber sample stage, scan the counter with the fiber bundle perpendicular to the scanning plane of the counter, and find the time at which the intensity of the diffraction band reaches its maximum (002). 2θ(
approximately 26°). Next, with the counter held in this position, the fiber sample stage was rotated 360° to measure the intensity distribution of the (002) diffraction ring, and the intensity distribution of the (002) diffraction ring was measured.
The half width at the point /2 is defined as the orientation angle (φ).
積層厚さ（Ｌｃ）、層間隔（ｄ、、、）は繊維を乳鉢で
粉末状にし、字種法「人造黒鉛の格子定数および結晶子
の大きさ測定法」に準拠して測定・解析を行ない、以下
の式から求めた。Lamination thickness (Lc) and interlayer spacing (d,,,) are measured and analyzed by powdering the fibers in a mortar and following the ``method for measuring the lattice constant and crystallite size of artificial graphite'' method. It was calculated using the following formula.
Ｌｃ＝ＫＬ／βｃｏｓθ
ｄｏｏｉ＝尤／ ２ ｓ ｉ ｎθ
ここで、Ｋ＝１．０． λ＝ １．５４１８入θ：
（００２１回折角２θより求めるβ：補正により求め
た（ ００２）回折帯の半価幅
・Ｘ線光電子分光法（ＥＳＣＡ）による繊維の表面酸素
濃度（Ｏ＋Ｓ／ Ｃ、ｓ）の測定測定装置としては、ク
ラトス製ＸＳＡＭ−８００を使用した。Lc=KL/βcosθ dooi=yield/2s i nθ where K=1.0. λ = 1.5418 in θ:
(β determined from 0021 diffraction angle 2θ: (002) determined by correction Half width of diffraction band / X-ray photoelectron spectroscopy (ESCA) to measure fiber surface oxygen concentration (O + S / C, s) As a measuring device , XSAM-800 manufactured by Kratos was used.
測定すべき繊維をカットし、金製の試料支持台上に拡げ
て並べた後、試料チャンバ内を１×１０−’Ｔ ｏ ｒ
ｒ以下に保った。Ｘ ！ｊｌ ａとしてＭｇＫα１，
２を用いた。そして、運動エネルギが７２２ｅＶのＯ，
ピーク面積、及び９７０ｅＶのＣＩｌ＋ｌ−ピー積の比
から、表面酸素濃度を求めた。After cutting the fibers to be measured and arranging them spread out on a gold sample support stand, the inside of the sample chamber was heated to 1 x 10-'T or
It was kept below r. X! MgKα1 as jl a,
2 was used. And O, whose kinetic energy is 722 eV,
The surface oxygen concentration was determined from the peak area and the ratio of CIl+l-p product at 970 eV.
本発明でいう繊維表面とは、繊維表面から繊維中心に向
って約０．０１μｍ以下の超薄層を意味する。The fiber surface as used in the present invention means an ultra-thin layer of about 0.01 μm or less from the fiber surface toward the fiber center.
次に、本発明を実施例について説明する。Next, the present invention will be described with reference to examples.
実施例１
光学的異方性相（ＡＰ）を約５０％含有する炭素質ピッ
チを前駆体ピッチとして使用し、こ゛れをローター内有
効容積２００ｍＪ２の円筒型連続遠心分離装置でロータ
ー温度３５０℃に制御しつつ遠心力１００００ＧでＡＰ
排出口よりピッチを抜き出した。得られたピッチは光学
的異方性相を９８％含み、軟化点が２７６℃であった。Example 1 A carbonaceous pitch containing approximately 50% optically anisotropic phase (AP) was used as a precursor pitch, and the pitch was heated to a rotor temperature of 350°C in a cylindrical continuous centrifugal separator with an effective internal volume of 200 mJ2. AP with centrifugal force of 10,000G while controlling
I pulled out the pitch from the outlet. The obtained pitch contained 98% of the optically anisotropic phase and had a softening point of 276°C.
次に、得られた光学的異方性相ピッチをノズル径０．３
ｍｍの溶融紡糸装置で３３０℃で紡糸した。このとき使
用した紡糸装置及び紡糸口金の構造が第１図〜第３図に
図示される。Next, the obtained optically anisotropic phase pitch was adjusted to a nozzle diameter of 0.3
The fibers were spun at 330° C. using a 1.0 mm melt spinning device. The structures of the spinning device and spinneret used at this time are illustrated in FIGS. 1 to 3.
紡糸装置１０はピッチ配管より溶融したピッチ１１が注
入された加熱シリンダー１２と、該シリンダー１２内の
ピッチを加圧するプランジャー１３と、加熱シリンダー
１２の底面側に取付けられた紡糸口金１４とを具備し、
紡糸口金１４は、紡糸ノズル１５が１個穿設されており
、ボルト１７及び口金押え１８によって加熱シリンダー
１２の低面側に着脱自在に固着することによって構成さ
れた。紡糸されたピッチ繊維は紡糸筒１９を通過した後
巻き取りボビーン２０に巻き取られた。The spinning device 10 includes a heating cylinder 12 into which molten pitch 11 is injected from a pitch pipe, a plunger 13 that pressurizes the pitch within the cylinder 12, and a spinneret 14 attached to the bottom side of the heating cylinder 12. death,
The spinneret 14 has one spinning nozzle 15 drilled therein, and is constructed by being removably fixed to the lower side of the heating cylinder 12 with a bolt 17 and a spinneret holder 18. After passing through the spinning tube 19, the spun pitch fibers were wound up onto a winding bobean 20.
本実施例で使用された紡糸口金１４に形成された紡糸ノ
ズル１５は、大径のノズル導入部１５ａと、該ノズル導
入部１５ａに連通して形成された小径のノズル部１５ｂ
とを有し、大径のノズル導入部１５ａと小径のノズル部
１５ｂとの間には切頭円錐形状のノズル遷移部１５ｃが
形成された。紡糸口金１４はステンレス鋼（ＳＵＳ３０
４）にて作製され、紡糸ノズル１５部の厚さ（Ｔ）は５
ｍｍとされ、大径のノズル導入部１５ａ及び小径のノズ
ル部１５ｂの長さ（Ｔ、）及び（Ｔ２）はそれぞれ４ｍ
ｍ及び０゜６５ｍｍとされた。又、大径のノズル導入部
１５ａ及び小径のノズル部１５ｂの直径（Ｄｌ）及び（
Ｄ２）はそれぞれ１ｍｍ及び０．３ｍｍとされた。The spinning nozzle 15 formed in the spinneret 14 used in this example includes a large diameter nozzle introduction part 15a and a small diameter nozzle part 15b formed in communication with the nozzle introduction part 15a.
A truncated conical nozzle transition section 15c was formed between the large diameter nozzle introduction section 15a and the small diameter nozzle section 15b. The spinneret 14 is made of stainless steel (SUS30
4), the thickness (T) of 15 parts of the spinning nozzle is 5
mm, and the lengths (T, ) and (T2) of the large diameter nozzle introduction part 15a and the small diameter nozzle part 15b are each 4 m.
m and 0°65 mm. Moreover, the diameter (Dl) and (
D2) were set to 1 mm and 0.3 mm, respectively.
又、紡糸ノズル１５の大径ノズル導入部１５ａには前記
紡糸口金１４より大きい熱伝導度を有した、本実施例で
は銅製の挿入部材１６が配置された。該挿入部材１６は
、一端１６ａが小径ノズル部１５ｂの入口に近接し、他
端１６ｂは大径ノズル導入部１５ａの入口より外方へと
延在する細長の棒状体とされ、全長（Ｌ）は２０ｍｍで
あり、直径（ｄ）は、挿入部材が大径ノズル導入部１５
ａに円滑に挿入され、且つ確実に保持されるように、大
径ノズル導入部１５ａと挿入部材１６との間の空隙が１
／ １００〜５ ／ １００ ｍ ｍとなるように形
成された。Further, in the present embodiment, an insertion member 16 made of copper, which has a higher thermal conductivity than the spinneret 14, was arranged in the large-diameter nozzle introduction part 15a of the spinning nozzle 15. The insertion member 16 has an elongated rod-like body with one end 16a close to the inlet of the small-diameter nozzle section 15b and the other end 16b extending outward from the inlet of the large-diameter nozzle introducing section 15a, and has an overall length (L). is 20 mm, and the diameter (d) is that the insertion member is the large diameter nozzle introduction part 15.
The gap between the large-diameter nozzle introduction part 15a and the insertion member 16 is set to 1 so that the large-diameter nozzle introduction part 15a and the insertion member 16 can be smoothly inserted into
/100 to 5/100 mm.
又、挿入部材１６の該表面には溶融ピッチをノズル部１
５ｂへと流動案内するべく、該挿入部材の軸線方向に沿
って半径（ｒ）が０．１５ｍｍの円弧状をした４個の溝
１８が形成された。Further, the surface of the insertion member 16 is coated with molten pitch at the nozzle portion 1.
5b, four arcuate grooves 18 with a radius (r) of 0.15 mm were formed along the axial direction of the insertion member.
上記構成の紡糸装置にて溶融ピッチを紡糸した場合には
、紡糸ノズルを通過する際の温度降下を３℃以下に抑え
ることができた。When the molten pitch was spun using the spinning apparatus having the above configuration, the temperature drop during passing through the spinning nozzle could be suppressed to 3° C. or less.
このようにして得られたピッチ繊維を酸素６０％の富酸
素ガス雰囲気で開始温度１８０’Ｃ１最終温度３１０℃
、昇温速度１３℃／分で昇温して１０分間で不融化した
。The pitch fiber thus obtained was heated in an oxygen-rich gas atmosphere containing 60% oxygen at a starting temperature of 180'C and a final temperature of 310'C.
The temperature was increased at a rate of 13° C./min, and the mixture became infusible in 10 minutes.
不融化処理の終了後、窒素ガス雰囲気中で、４００℃か
ら５５０℃まで５０℃／分で昇温し、５５０℃から１１
００℃まで２５０’Ｃ／分昇温して炭化を行った。この
とき、１１００℃での保持時間は零であった。総炭化時
間は５．２分であった。After the infusibility treatment was completed, the temperature was raised from 400°C to 550°C at a rate of 50°C/min in a nitrogen gas atmosphere, and the temperature was increased from 550°C to 11°C.
Carbonization was carried out by increasing the temperature to 00°C at 250'C/min. At this time, the holding time at 1100°C was zero. Total carbonization time was 5.2 minutes.
又、この炭化処理時には繊維の配向角を改良する目的で
、フィラメント１本当たり０゜０１７ｇｒのテンション
を掛けた。Further, during this carbonization treatment, a tension of 0°017 gr was applied to each filament in order to improve the orientation angle of the fibers.
この炭化処理した炭素繊維を更に、７００℃に維持され
た、酸素濃度６０％の富酸素ガス雰囲気中（ｏｘ ／Ｎ
２＝６０／４０）を、３０秒間通して、気相酸化処理し
た。The carbonized carbon fibers were further placed in an oxygen-rich gas atmosphere (ox/N) maintained at 700°C with an oxygen concentration of 60%.
2=60/40) for 30 seconds.
この炭素繊維は、Ｘ線回折の結果、配向角（φ）が３２
° 積層厚さ（Ｌｃ）が１９゜４人、層間隔（ｄｏ、）
が３．４８４人であった。As a result of X-ray diffraction, this carbon fiber has an orientation angle (φ) of 32
° Lamination thickness (Lc) is 19° 4 people, layer spacing (do,)
There were 3,484 people.
又、該繊維の糸径は９．９μｍであり、引張強度は２．
８ＧＰａ （２８０Ｋｇ／ｍｍ２）、引張弾性率は１１
０ＧＰａ （ｌ １．０ｔｏｎ／ｍｍ” ）、伸度は２
．５％であって、伸びの大きいしなやかな糸であった。The fiber has a thread diameter of 9.9 μm and a tensile strength of 2.9 μm.
8GPa (280Kg/mm2), tensile modulus is 11
0GPa (l 1.0ton/mm”), elongation is 2
．． 5%, and was a flexible yarn with great elongation.
この繊維をＸ線光電子分光法により繊維の表面酸素濃度
を測定したところ、繊維表面の原子数比０／Ｃの値は０
．１５１であった。又、元素分析で求めた系中の全酸素
濃度は０．１重量％であった。When the surface oxygen concentration of this fiber was measured using X-ray photoelectron spectroscopy, the value of the atomic ratio 0/C on the fiber surface was 0.
．． It was 151. Further, the total oxygen concentration in the system determined by elemental analysis was 0.1% by weight.
更に、このようにして得られた繊維を使用して層間剪断
強度（Ｉ ＬＳＳ）を測定したところ１３．２Ｋｇ／ｍ
ｍ”であり、高い値を示した。Furthermore, when the interlaminar shear strength (ILSS) of the fiber thus obtained was measured, it was 13.2 Kg/m.
m” and showed a high value.
又、この炭素繊維を２５００℃まで昇温しで得た黒鉛繊
維は、糸径が９，８μｍであり、引張強度は４．１ＧＰ
ａ （４１０Ｋｇ／ｍｍ２）、引張弾性率は７００ＧＰ
ａ （７０ｔｏｎ／ｍｍ” ）と、高い物性を示した。In addition, graphite fiber obtained by heating this carbon fiber to 2500°C has a thread diameter of 9.8 μm and a tensile strength of 4.1 GP.
a (410Kg/mm2), tensile modulus is 700GP
a (70 ton/mm"), showing high physical properties.
比較例１
実施例１と同じ材料を使用し、同じ方法にて不融化繊維
及び炭素繊維を得た。実施例１と異なり、この炭素繊維
に対し気相酸化は行わなかった。Comparative Example 1 Infusible fibers and carbon fibers were obtained using the same materials and the same method as in Example 1. Unlike Example 1, this carbon fiber was not subjected to gas phase oxidation.
この炭素繊維のＸ線回折の結果、配向角（φ）は３２°
、積層厚さ（Ｌｃ）が１９．５人、層間隔（ｄ、、、）
が３．４８５人であった。As a result of X-ray diffraction of this carbon fiber, the orientation angle (φ) is 32°
, lamination thickness (Lc) is 19.5 people, layer spacing (d, , )
There were 3,485 people.
又、該繊維の糸径はｌｏＩｉｍであり、引張強度は２．
５ＧＰａ （２５０Ｋｇ／ｍｍ２）、引張弾性率は１１
０ＧＰａ （１１ｔｏｎ／ｍｍ” ）、伸度は２．３％
であった。Further, the yarn diameter of the fiber is loIim, and the tensile strength is 2.
5GPa (250Kg/mm2), tensile modulus is 11
0GPa (11ton/mm”), elongation is 2.3%
Met.
この繊維をＸ線光電子分光法により繊維の表面酸素濃度
を測定したところ、原子数比Ｏ／Ｃの値は０．０３であ
り、又、元素分析で求めた系中の全酸素濃度は０．０１
重量％以下であった。When the surface oxygen concentration of this fiber was measured using X-ray photoelectron spectroscopy, the value of the atomic ratio O/C was 0.03, and the total oxygen concentration in the system determined by elemental analysis was 0.03. 01
It was less than % by weight.
更に、このようにして得られた繊維を使用して層間剪断
強度（ＩＬＳＳ）を測定したところ９゜５Ｋｇ／ｍｍ”
であった。Furthermore, when the interlaminar shear strength (ILSS) of the fiber thus obtained was measured, it was 9.5 kg/mm.
Met.
又、この炭素繊維を２５００℃まで昇温して得た黒鉛繊
維は、糸径が９．８μｍであり、引張強度は３．５ＧＰ
ａ （３５０Ｋｇ／ｍｍ” ）、引張弾性率は７００Ｇ
Ｐａ （７０ｔｏｎ／ｍｍ” ）であった。Furthermore, the graphite fiber obtained by heating this carbon fiber to 2500°C has a thread diameter of 9.8 μm and a tensile strength of 3.5 GP.
a (350Kg/mm”), tensile modulus is 700G
Pa (70 ton/mm").
比較例２
実施例１と同じ材料を使用し、同じ方法にて不融化繊維
を得た。Comparative Example 2 Infusible fibers were obtained using the same materials and the same method as in Example 1.
該不融化繊維を、テンションを掛けなかった以外は実施
例１と同様に炭化して炭素繊維を作製した。炭化後の炭
素繊維の気相酸化は行わなかった。The infusible fibers were carbonized to produce carbon fibers in the same manner as in Example 1, except that no tension was applied. Gas phase oxidation of the carbon fibers after carbonization was not performed.
この炭素繊維は、Ｘ線回折の結果、配向角（φ）が４１
“ 積層厚さ（Ｌｃ）が１９゜５人、層間隔（ｄ、。２
）が３．４９７人であった。As a result of X-ray diffraction, this carbon fiber has an orientation angle (φ) of 41
“Lamination thickness (Lc) is 19°5, layer spacing (d, .2
) was 3.497 people.
又、該繊維の糸径はｌｏＬＬｍであり、引張強度は０
、７ Ｇ Ｐ ａ （７０Ｋ ｇ ／ ｍ ｒｄ ）
、引張弾性率は８０ＧＰａ（８，０ｔｏｎ／ｍｔ＆）、
伸度は０．９％であった。Moreover, the thread diameter of the fiber is loLLm, and the tensile strength is 0.
, 7 GPa (70Kg/mrd)
, tensile modulus is 80GPa (8,0ton/mt&),
The elongation was 0.9%.
この炭素繊維を２５００℃まで昇温して得た黒鉛繊維は
、糸径が９．８μｍであり、引張強度は２．８ＧＰａ
（２８０Ｋｇ／ｍｍ” ）、引張弾性率は６５０ＧＰａ
（６５ｔｏｎ／ｍｍ” ）であった。The graphite fiber obtained by heating this carbon fiber to 2500°C has a thread diameter of 9.8 μm and a tensile strength of 2.8 GPa.
(280Kg/mm”), tensile modulus is 650GPa
(65 ton/mm”).
比較例３
実施例１と同じ材料を使用し、同じ方法にて不融化繊維
を得た。Comparative Example 3 Infusible fibers were obtained using the same materials and the same method as in Example 1.
該不融化繊維に、フィラメント１本当たり０゜３３ｇｒ
のテンションを掛けて炭化した以外は実施例１と同様に
処理した。但し、炭化後の炭素繊維の気相酸化は、行わ
なかった。The infusible fiber contains 0°33gr per filament.
The treatment was carried out in the same manner as in Example 1, except that the tension was applied to carbonize. However, gas phase oxidation of the carbonized carbon fibers was not performed.
この炭素繊維は、Ｘ線回折の結果、配向角（φ）が２４
° 積層厚み（Ｌｃ）が１９゜５人、層間隔（ｄｏｏ２
）が３．４８２人であった。As a result of X-ray diffraction, this carbon fiber has an orientation angle (φ) of 24
° Lamination thickness (Lc) is 19° 5 people, layer spacing (doo2
) was 3.482 people.
又、該繊維の糸径はｌ１０１Ｌであり、引張強度は１．
３ＧＰａ （１４０Ｋｇ／ｍｍ” ）、引張弾性率は１
４０ＧＰａ （１４ｔｏｎ／ｍｍ” ）、伸度は０．９
％であった。The fiber has a thread diameter of 1101L and a tensile strength of 1.
3GPa (140Kg/mm”), tensile modulus is 1
40GPa (14ton/mm”), elongation is 0.9
%Met.
この炭素繊維を２５００℃まで昇温して得た黒鉛繊維は
、糸径が９．８μｍであり、引張強度は２．８ＧＰａ
（２８０Ｋｇ／ｍｍ” ）、引張弾性率は７５０ＧＰａ
（７５ｔｏｎ／ｍｍ’ ）であった。The graphite fiber obtained by heating this carbon fiber to 2500°C has a thread diameter of 9.8 μm and a tensile strength of 2.8 GPa.
(280Kg/mm”), tensile modulus is 750GPa
(75 ton/mm').
比較例４
実施例１と同じ材料を使用し、同じ方法にて不融化繊維
を得た。Comparative Example 4 Infusible fibers were obtained using the same materials and the same method as in Example 1.
該不融化繊維を、４００℃から１１００℃まで５℃／分
で昇温し、１４０分間かけて炭化した以外は実施例１と
同様に処理して炭素繊維を作製した。但し、炭化後の炭
素繊維の気相酸化は行わなかった。Carbon fibers were produced in the same manner as in Example 1, except that the infusible fibers were heated from 400°C to 1100°C at a rate of 5°C/min and carbonized for 140 minutes. However, the carbon fibers were not subjected to gas phase oxidation after carbonization.
この炭素繊維は、Ｘ ！１回折の結果、配向角（φ）が
４１° 積層厚み（Ｌｃ）が１９゜６人、層間隔（ｄｏ
。２）が３．４９５人であった。This carbon fiber is X! As a result of one diffraction, the orientation angle (φ) is 41°, the laminated thickness (Lc) is 19°, 6 people, and the layer spacing (do
. 2) was 3.495 people.
又、該繊維の糸径は１０ｕｍであり、引張強度は０．８
ＧＰａ （８０Ｋｇ／ｍｍ” ）、引張弾性率は９０Ｇ
Ｐａ （９，０ｔｏｎ／ｍｍ” ） 、伸度は０．９％
であった。Moreover, the thread diameter of the fiber is 10 um, and the tensile strength is 0.8
GPa (80Kg/mm”), tensile modulus is 90G
Pa (9.0ton/mm”), elongation is 0.9%
Met.
この炭素繊維を２５００℃まで昇温して得た黒鉛繊維は
、糸径が９．８ｕｍであり、引張強度は２．８ＧＰａ
（２８０Ｋｇ／ｍｍ” ）、引張弾性率は６５０ＧＰａ
（６５ｔｏｎ／ｍｍ” ）であった。The graphite fiber obtained by heating this carbon fiber to 2500°C has a thread diameter of 9.8 um and a tensile strength of 2.8 GPa.
(280Kg/mm”), tensile modulus is 650GPa
(65 ton/mm”).
比較例５
実施例１と同じ材料を使用し、同じ方法にて不融化繊維
を得た。Comparative Example 5 Infusible fibers were obtained using the same materials and the same method as in Example 1.
該不融化繊維を、４００℃から１１００℃まで２５０℃
／分で昇温し、約３分間で炭化した以外は実施例１と同
様に処理して炭素繊維を作製した。The infusible fiber was heated at 250°C from 400°C to 1100°C.
Carbon fibers were produced in the same manner as in Example 1, except that the temperature was raised at a rate of 1/min and carbonized for about 3 minutes.
この場合には、炭化時１部融着を起こし、正常な糸が得
られなかった。In this case, some fusion occurred during carbonization, and a normal thread could not be obtained.
比較例６
実施例１と同一のピッチを用いて、挿入部材なしの紡糸
口金を用いて紡糸温度３３０℃で紡糸し、得られたピッ
チ繊維を空気雰囲気において１８０℃から０．３℃／分
の速度で２５５℃まで昇温て不融化した。Comparative Example 6 Using the same pitch as in Example 1, spinning was carried out at a spinning temperature of 330°C using a spinneret without an insert member, and the obtained pitch fiber was spun at 0.3°C/min from 180°C in an air atmosphere. The temperature was raised to 255°C at a rapid rate to make it infusible.
該不融化繊維を、テンションなしで窒素ガス雰囲気中に
て４００℃から１１００℃まで５℃／分で昇温し、１４
０分間かけて炭化した。The temperature of the infusible fiber was raised from 400°C to 1100°C at a rate of 5°C/min in a nitrogen gas atmosphere without tension.
Carbonization took 0 minutes.
１１００℃までの保持時間はゼロであった。炭化後の炭
素繊維の気相酸化は実施しなかった。The holding time up to 1100°C was zero. Gas phase oxidation of the carbon fibers after carbonization was not performed.
この炭素繊維は、Ｘ線回折の結果、配向角（φ）が４３
° 積層厚み（Ｌｃ）が１９゜５人、層間隔（ｄｏ０２
）が３．４９７人であった。As a result of X-ray diffraction, this carbon fiber has an orientation angle (φ) of 43
° Lamination thickness (Lc) is 19° 5 people, layer spacing (do02
) was 3.497 people.
又、該繊維の糸径は１０μｍであり、引張強度は０．６
ＧＰａ （６０Ｋｇ／ｍｍ” ）、引張弾性率は７５Ｇ
Ｐａ （７，５ｔｏｎ／ｍｍ” ） 、伸度は０．８％
であった。The fiber has a thread diameter of 10 μm and a tensile strength of 0.6.
GPa (60Kg/mm”), tensile modulus is 75G
Pa (7.5 ton/mm”), elongation is 0.8%
Met.
この炭素繊維を２５００℃まで昇温しで得た黒鉛繊維は
、糸径が９．９μｍであり、引張強度は２．６ＧＰａ
（２６０Ｋｇ／ｍｍ” ）、引張弾性率は６５０ＧＰａ
（６５ｔｏｎ／ｍｍ” ）であった。The graphite fiber obtained by heating this carbon fiber to 2500°C has a thread diameter of 9.9 μm and a tensile strength of 2.6 GPa.
(260Kg/mm”), tensile modulus is 650GPa
(65 ton/mm”).
比較例７
実施例１と同じ材料を使用し同じ方法にて、不融化繊維
及び炭素繊維を得た。この炭化処理した炭素繊維を更に
、７００℃に保持された酸素濃度６０％冨酸素ガス雰囲
気中で（０２／Ｎ２＝６０／４０）を、３分間通して気
相酸化処理した。Comparative Example 7 Infusible fibers and carbon fibers were obtained using the same materials and the same method as in Example 1. The carbonized carbon fibers were further subjected to gas phase oxidation treatment in a rich oxygen gas atmosphere (02/N2=60/40) maintained at 700° C. with an oxygen concentration of 60% for 3 minutes.
該繊維の糸径は９．９μｍであり、引張強度は０．８Ｇ
Ｐａ、引張弾性率は８９．０ＧＰａ、伸度は０．９％で
あり、引張強度は著しく低下した。The fiber has a thread diameter of 9.9 μm and a tensile strength of 0.8 G.
Pa, tensile modulus was 89.0 GPa, elongation was 0.9%, and tensile strength was significantly decreased.
この繊維をＸ線光電子分光法により繊維の表面酸素濃度
を測定したところ繊維表面の原子数比は０．４２であり
、元素分析で求めた系中の全酸素濃度は０．４重量％で
あった。When the surface oxygen concentration of this fiber was measured using X-ray photoelectron spectroscopy, the atomic ratio on the fiber surface was 0.42, and the total oxygen concentration in the system determined by elemental analysis was 0.4% by weight. Ta.
このようにして得られた繊維を使用して層間剪断強度（
ＩＬＳＳ）は、１２．５Ｋｇ／ｍｒｒ？であった。Using the fibers obtained in this way, the interlaminar shear strength (
ILSS) is 12.5Kg/mrr? Met.
実施例１及び比較例１〜７を検討すると、本発明に従っ
た高伸度の、しかも所定レベル以上の６張強度、引張弾
性率を有した炭素繊維を得るには、不融化繊維の炭化処
理工程時に所定のテンションを掛け、更に、繊維が融着
しない範囲で迅速に炭化することが重要であると共に、
富酸素ガス中にて高温、短時間で気相酸化処理すること
により繊維の表面の酸素濃度及び繊維中の全酸素濃度を
所定範囲内に規定することが重要であることが分かる。Examining Example 1 and Comparative Examples 1 to 7, it is found that carbonization of infusible fibers is necessary to obtain carbon fibers with high elongation and tensile strength and tensile modulus of at least a predetermined level according to the present invention. It is important to apply a predetermined tension during the treatment process and to carbonize quickly without fusion of the fibers.
It can be seen that it is important to regulate the oxygen concentration on the surface of the fiber and the total oxygen concentration in the fiber within a predetermined range by carrying out a gas phase oxidation treatment in an oxygen-rich gas at high temperature for a short time.
特に、富酸素ガス中にて高温、短時間で気相酸化処理す
ることにより繊維自体の物性及びマトリクス樹脂との接
着性が向上し、層間剪断強度が増大することが分かる。In particular, it can be seen that the physical properties of the fiber itself and the adhesion to the matrix resin are improved by gas-phase oxidation treatment in an oxygen-rich gas at high temperature for a short time, and the interlaminar shear strength is increased.
発」七□」Ｌ里
本発明に係る製造方法にて作製した特異な結晶構造を有
したピッチ系炭素繊維は、伸度が１゜０％以上といった
高伸度でありながら、所定レベル以上の引張強度及び引
張弾性率を有しており、編織性に優れており、製造時の
糸扱いが非常に容易となり製造効率が大幅に改善され、
宇宙開発、自動車、建築物などの軽量構造材料用強化繊
維として極めて有効に使用し得る。又、更に２０００℃
まで加熱して炭化し、更には３０００℃まで加熱して黒
鉛化することにより、著しく高強度、高弾性率の炭素繊
維を得ることができる。更に本発明にて製造された繊維
は、複合材料用強化繊維に使用した場合にマトリクス樹
脂との接着性が極めて良好であり、高性能の炭素繊維強
化複合樹脂を得ることができるという利益がある。The pitch-based carbon fiber with a unique crystal structure produced by the manufacturing method according to the present invention has a high elongation of 1°0% or more, but has a high elongation of more than a predetermined level. It has high tensile strength and tensile modulus, and has excellent knitting and weaving properties, making it extremely easy to handle the yarn during manufacturing, greatly improving manufacturing efficiency.
It can be used extremely effectively as a reinforcing fiber for lightweight structural materials for space development, automobiles, buildings, etc. Also, further 2000℃
By heating to 3,000° C. to carbonize and further heating to 3,000° C. to graphitize, carbon fibers with extremely high strength and high elastic modulus can be obtained. Furthermore, the fibers produced according to the present invention have extremely good adhesion with matrix resins when used as reinforcing fibers for composite materials, and have the advantage that high-performance carbon fiber-reinforced composite resins can be obtained. .
第１図は、本発明に係る製造方法にて使用され紡糸装置
用紡糸口金の一実施例の断面図である。
第２図は、第１図の紡糸口金に使用される挿入部材の一
実施例の平面図である。
第３図は、第２図の紡糸口金に使用される挿入部材の一
実施例の平面図である。
１４：紡糸口金
１５：紡糸ノズル
１６：挿入部材FIG. 1 is a sectional view of one embodiment of a spinneret for a spinning device used in the manufacturing method according to the present invention. FIG. 2 is a plan view of one embodiment of an insert for use with the spinneret of FIG. 1; FIG. 3 is a plan view of one embodiment of an insert member used in the spinneret of FIG. 2; 14: Spinneret 15: Spinning nozzle 16: Insertion member
Claims (1)
にて不融化処理を行い繊維の表層を選択的に強く酸化し
た後、不活性ガス雰囲気下で最低温度４００℃、最高温
度１３００℃にて融着しない範囲で昇温して、フィラメ
ント１本当り０．００１〜０．２ｇｒの張力を付与しな
がら、３〜１５分間にて炭化処理を行い、その後酸化処
理を行うことを特徴とする高伸度、高強度ピッチ系炭素
繊維の製造方法。 ２）請求項１記載の炭化処理は、４００〜 ５５０℃までは昇温温度１０〜９０℃／分で、５５０〜
１３００℃までは昇温温度１００〜５００℃／分で行う
ことを特徴とする高伸度、高強度ピッチ系炭素繊維の製
造方法。 ３）請求項１又は２記載の炭化処理を行った後、２００
０℃まで昇温して炭化処理を行い、所望に応じて３００
０℃まで昇温して黒鉛化処理を行うことを特徴とする高
伸度、高強度ピッチ系炭素繊維の製造方法。[Claims] 1) After selectively and strongly oxidizing the surface layer of the fibers by performing infusibility treatment for 3 to 30 minutes in an oxygen-rich atmosphere at 120 to 350°C, the fibers are heated to a minimum temperature of 400°C in an inert gas atmosphere. ℃, at a maximum temperature of 1300℃, the temperature is raised within a range that does not cause fusion, and while applying a tension of 0.001 to 0.2 gr per filament, carbonization treatment is performed for 3 to 15 minutes, followed by oxidation treatment. A method for producing high-elongation, high-strength pitch-based carbon fiber. 2) The carbonization treatment according to claim 1 is performed at a heating temperature of 10 to 90°C/min from 400 to 550°C, and from 550 to 550°C.
A method for manufacturing pitch-based carbon fibers with high elongation and high strength, characterized in that heating up to 1300°C is carried out at a heating temperature of 100 to 500°C/min. 3) After performing the carbonization treatment according to claim 1 or 2, 200
Carbonization treatment is performed by increasing the temperature to 0°C, and if desired, the temperature is increased to 300°C.
A method for producing high-elongation, high-strength pitch-based carbon fiber, which comprises graphitizing the fiber by raising the temperature to 0°C.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28238989A JPH03146720A (en) | 1989-10-30 | 1989-10-30 | Production of pitch-based carbon fiber having high elongation and high strength |
| US07/601,486 US5209975A (en) | 1989-10-30 | 1990-10-22 | High elongation, high strength pitch-type carbon fiber |
| KR1019900017454A KR910008192A (en) | 1989-10-30 | 1990-10-30 | High-strength high-strength pitch carbon fiber and its manufacturing method |
| EP19900311892 EP0426438A3 (en) | 1989-10-30 | 1990-10-30 | High strength carbon fibers and method of manufacturing them |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28238989A JPH03146720A (en) | 1989-10-30 | 1989-10-30 | Production of pitch-based carbon fiber having high elongation and high strength |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03146720A true JPH03146720A (en) | 1991-06-21 |
Family
ID=17651768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28238989A Pending JPH03146720A (en) | 1989-10-30 | 1989-10-30 | Production of pitch-based carbon fiber having high elongation and high strength |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03146720A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014185400A (en) * | 2013-03-22 | 2014-10-02 | Kuraray Co Ltd | Pitch-based carbon fiber and production method of the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6253422A (en) * | 1985-09-03 | 1987-03-09 | Kawasaki Steel Corp | Production of carbon fiber |
| JPS63175122A (en) * | 1986-12-29 | 1988-07-19 | Mitsubishi Kasei Corp | Production of carbon fiber tow |
| JPH01156513A (en) * | 1987-12-11 | 1989-06-20 | Toa Nenryo Kogyo Kk | Production of pitch based carbon fiber |
-
1989
- 1989-10-30 JP JP28238989A patent/JPH03146720A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6253422A (en) * | 1985-09-03 | 1987-03-09 | Kawasaki Steel Corp | Production of carbon fiber |
| JPS63175122A (en) * | 1986-12-29 | 1988-07-19 | Mitsubishi Kasei Corp | Production of carbon fiber tow |
| JPH01156513A (en) * | 1987-12-11 | 1989-06-20 | Toa Nenryo Kogyo Kk | Production of pitch based carbon fiber |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014185400A (en) * | 2013-03-22 | 2014-10-02 | Kuraray Co Ltd | Pitch-based carbon fiber and production method of the same |
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