JPH0532494B2 - - Google Patents
Info
- Publication number
- JPH0532494B2 JPH0532494B2 JP58150036A JP15003683A JPH0532494B2 JP H0532494 B2 JPH0532494 B2 JP H0532494B2 JP 58150036 A JP58150036 A JP 58150036A JP 15003683 A JP15003683 A JP 15003683A JP H0532494 B2 JPH0532494 B2 JP H0532494B2
- Authority
- JP
- Japan
- Prior art keywords
- pitch
- weight
- heat
- less
- oil
- 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.)
- Expired - Lifetime
Links
- 239000011295 pitch Substances 0.000 claims description 54
- 238000009987 spinning Methods 0.000 claims description 30
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 27
- 239000004917 carbon fiber Substances 0.000 claims description 27
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 20
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 239000010692 aromatic oil Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- 239000011280 coal tar Substances 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- WHRZCXAVMTUTDD-UHFFFAOYSA-N 1h-furo[2,3-d]pyrimidin-2-one Chemical compound N1C(=O)N=C2OC=CC2=C1 WHRZCXAVMTUTDD-UHFFFAOYSA-N 0.000 claims description 2
- 235000006173 Larrea tridentata Nutrition 0.000 claims description 2
- 244000073231 Larrea tridentata Species 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 229960002126 creosote Drugs 0.000 claims description 2
- 238000005087 graphitization Methods 0.000 claims description 2
- 238000009826 distribution Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 239000003245 coal Substances 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011338 soft pitch Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000001454 anthracenes Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011294 coal tar pitch Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011302 mesophase pitch Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011269 tar Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- -1 tahir Substances 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】
本発明は、ピツチ系高特性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 relates to a method for producing pitch-based high-performance carbon fiber.
周知のように、重質油、タール、ピツチ等の炭
素質原料を350〜500℃に加熱すると、それら物質
中に粒径が数ミクロンから数百ミクロンの偏光下
光学的異方性を示す小球体が生成する。そして、
更に加熱するとこれらの小球体は成長合体し、つ
いには全体が光学的異方性を示す状態となる。こ
の異方性組織は炭素質原料の熱重縮合反応により
生成した高分子芳香族炭化水素が層状に積み重な
り配向したもので、黒鉛結晶構造の前駆体とみな
されている。 As is well known, when carbonaceous raw materials such as heavy oil, tar, and pitch are heated to 350 to 500°C, small particles with particle sizes ranging from several microns to several hundred microns exhibit optical anisotropy under polarized light. A sphere is generated. and,
When heated further, these small spheres grow and coalesce, and finally the whole becomes in a state exhibiting optical anisotropy. This anisotropic structure is composed of polymeric aromatic hydrocarbons produced by a thermal polycondensation reaction of carbonaceous raw materials, stacked and oriented in layers, and is considered to be a precursor of graphite crystal structure.
この様な熱処理物は、ノズルを通し、溶融紡
糸、不融化、炭化、更に場合により黒鉛化するこ
とによつて、高強度、高弾性率などの特徴をもつ
ピツチ系の高特性炭素繊維の原料として提案され
ている。 This heat-treated material is passed through a nozzle, melt-spun, made infusible, carbonized, and optionally graphitized to produce a raw material for pitch-based high-performance carbon fiber, which has characteristics such as high strength and high modulus. It is proposed as.
炭素繊維は、比強度、比弾性率が高い材料で、
高性能複合材料のフイラー繊維として最も注目さ
れており、中でもピツチ系高特性炭素繊維は、原
料コストが安価である、炭化工程での歩留が大き
い、繊維の弾性率が高い等、ポリアクリロニトリ
ル系炭素繊維に比べて様々な利点を持つている。 Carbon fiber is a material with high specific strength and specific modulus.
Pitch-based high-performance carbon fibers are attracting the most attention as filler fibers for high-performance composite materials, and among them, polyacrylonitrile-based carbon fibers have low raw material costs, high yields in the carbonization process, and high fiber elastic modulus. It has various advantages compared to carbon fiber.
従来、ピツチ系高特性炭素繊維は、通常、所謂
メソフエーズピツチを紡糸原料とし、このメソフ
エーズピツチから繊維状ピツチを紡糸し、次い
で、不融化し、焼成（炭化、黒鉛化）して製造さ
れている。 Conventionally, pitch-based high-performance carbon fibers are produced by using so-called mesophase pitch as a spinning raw material, spinning fibrous pitch from this mesophase pitch, then making it infusible and firing it (carbonization, graphitization). Manufactured.
しかしながら、従来の方法により得られるピツ
チ系炭素繊維はその強度分布の範囲が広く、均等
化した高強度のピツチ系炭素繊維が得られるとは
言い難い状況にあつた。すなわち、紡糸ピツチの
組成を規定して、ピツチ系炭素繊維を製造する方
法は知られているものの、いずれの組成を有する
紡糸ピツチが力学的特性の優れた強度分布のバラ
ツキの小さい炭素繊維を与えるものかは今だ充分
には明らかではなく、この点につき、本発明者等
は鋭意検討を重ね、その結果、紡糸ピツチが実質
的に光学的異方性相を有し、しかもキノリン不溶
分が低いものが一般に有効ではあるが、この様な
特性値のみでは必ずしも充分でなく、かゝる特性
値を得るに至つた覆歴も重要であることを見い出
した。すなわち、紡糸ピツチを調製する際に、炭
素質原料を予備処理することにより、特定の範囲
の組成を有する炭素質原料とすること、換言すれ
ば、幅広い分子量分布を有する炭素質原料を加熱
処理し、熱処理物を取得し、次いで芳香族油と接
触させることにより、以後の処理では適性物質に
変換困難な高分子量部分を予じめ除去し、前記の
有効な紡糸ピツチに変換しうる特定の組成を有す
る炭素質原料を取得することが肝要であり、引続
き、この特定組成の炭素質原料を再び加熱処理
し、紡糸ピツチの光学的異方性相とキノリン不溶
分を特定の範囲に制御することにより、紡糸性を
低下させることなく、強度が向上し、かつ、強度
分布のバラつきの小さいピツチ系炭素繊維を製造
し得ることを見出し、本発明に到達した。 However, pitch-based carbon fibers obtained by conventional methods have a wide range of strength distribution, and it is difficult to say that pitch-based carbon fibers with uniform high strength can be obtained. That is, although methods for producing pitch-based carbon fibers by specifying the composition of a spinning pitch are known, it is difficult to determine whether a spinning pitch having any composition can yield carbon fibers with excellent mechanical properties and small variations in strength distribution. It is still not fully clear whether this is the case, and the inventors of the present invention have conducted extensive studies on this point, and have found that the spinning pitch has a substantially optically anisotropic phase and that the quinoline-insoluble content is Although a low value is generally effective, it has been found that such a characteristic value alone is not necessarily sufficient, and that the history of obtaining such a characteristic value is also important. That is, when preparing a spinning pitch, the carbonaceous raw material is pre-treated to produce a carbonaceous raw material having a composition within a specific range.In other words, the carbonaceous raw material having a wide molecular weight distribution is heat-treated. By obtaining the heat-treated product and then contacting it with an aromatic oil, high molecular weight portions that are difficult to convert into suitable substances in subsequent treatments are removed in advance, and a specific composition that can be converted into the above-mentioned effective spinning pitch is obtained. It is important to obtain a carbonaceous raw material having a specific composition.Subsequently, this carbonaceous raw material with a specific composition is heat-treated again to control the optically anisotropic phase and quinoline insoluble content in the spinning pitch within a specific range. The inventors have discovered that it is possible to produce pitch-based carbon fibers with improved strength and small variations in strength distribution without reducing spinnability, and have arrived at the present invention.
本発明の目的は、力学的特性の優れた強度分布
のバラツキの小さい炭素繊維う製造することであ
り、しかして、かかる目的は、炭素質原料を加熱
処理し、光学的異方性部分を少なくとも30％以上
含む第一次熱処理物を取得し、該第一次熱処理物
を沸点又は初留点が150℃以上の芳香族油と接触
させ、該芳香族油相を分離取得することにより、
ベンゼン不溶分60重量％以下、かつキノリン不溶
分20重量％以下の光学的に実質的に等方性のピツ
チ類を取得して、該ピツチ類を加熱処理し、光学
的異方性相が90％以下であり、しかも、キノリン
不溶分が40重量％以下の紡糸ピツチを取得し、該
紡糸ピツチを紡糸、不融化、炭化必要に応じて黒
鉛化することにより達成される。 An object of the present invention is to produce carbon fibers with excellent mechanical properties and small variations in strength distribution. By obtaining a first heat-treated product containing 30% or more, contacting the first heat-treated product with an aromatic oil having a boiling point or initial boiling point of 150°C or higher, and separating and obtaining the aromatic oil phase.
Obtain optically substantially isotropic pitches having a benzene-insoluble content of 60% by weight or less and a quinoline-insoluble content of 20% by weight or less, and heat-treat the pitches so that the optically anisotropic phase becomes 90% by weight or less. % or less, and the quinoline insoluble content is 40% by weight or less, and the spinning pitch is spun, made infusible, carbonized, and optionally graphitized.
以下、本発明を説明するに、本発明で紡糸ピツ
チを得るために炭素質原料としては、例えば石炭
系のコールタール、コールタールピツチ、石炭液
化物、石油系の重質油、タール、ピツチ等で、ベ
ンゼン不溶分60重量％以下、好ましくは、50重量
％以下、更に好ましくは、５〜45重量％、キノリ
ン不溶分20重量％以下、好ましくは15重量％以
下、更に好ましくは、５重量％以下のものが挙げ
られる。 Hereinafter, to explain the present invention, carbonaceous raw materials used to obtain the spinning pitch in the present invention include, for example, coal-based coal tar, coal tar pitch, coal liquefaction, petroleum-based heavy oil, tar, pitch, etc. The benzene insoluble content is 60% by weight or less, preferably 50% by weight or less, more preferably 5 to 45% by weight, and the quinoline insoluble content is 20% by weight or less, preferably 15% by weight or less, more preferably 5% by weight. These include:
この炭素質原料のベンゼン不溶分、キノリン不
溶分が上記範囲を超えると得られる紡糸ピツチの
溶融粘度が高くなり、従つて、高温にて紡糸しな
ければならなくなる。その為、紡糸中に以下、か
つキノリン不溶分20重量％以下の光学的に実質的
に等方性のピツチ類を取得して、該ピツチ類を加
熱処理し、光学的異方性相が90％以下であり、し
かも、キノリン不溶分が40重量％以下の紡糸ピツ
チを取得し、該紡糸ピツチを紡糸、不融化、炭化
必要に応じて黒鉛化することにより達成される。 If the benzene-insoluble content and quinoline-insoluble content of the carbonaceous raw material exceeds the above range, the resulting spinning pitch will have a high melt viscosity, and therefore, it will be necessary to perform spinning at a high temperature. Therefore, during spinning, optically substantially isotropic pitches having the following and quinoline insoluble content of 20% by weight or less are obtained, and the pitches are heat-treated to obtain an optically anisotropic phase of 90% or less. % or less, and the quinoline insoluble content is 40% by weight or less, and the spinning pitch is spun, made infusible, carbonized, and optionally graphitized.
以下、本発明を発明するに、本発明で紡糸ピツ
チを得るために炭素質原料としては、例えば石灰
系のコールタール、コールタールピツチ、石炭液
化物、石油系の重質油、タヒル、ピツチ等で、ベ
ンゼン不60重量％以下、好ましくは、50重量％以
下、更に好ましくは、５〜45重量％、キノリン不
溶分20重量％以下、好ましくは15重量％以下、更
に好ましくは、５重量％以下のものが挙げられ
る。 Hereinafter, in the present invention, the carbonaceous raw materials used to obtain the spinning pitch in the present invention include, for example, lime-based coal tar, coal tar pitch, coal liquefaction, petroleum-based heavy oil, tahir, pitch, etc. Benzene insoluble content is 60% by weight or less, preferably 50% by weight or less, more preferably 5 to 45% by weight, and quinoline insoluble content is 20% by weight or less, preferably 15% by weight or less, more preferably 5% by weight or less. Examples include:
この炭素質原料のベンゼン不溶分、キノリン不
溶分が上記範囲を超えると得られる紡糸ピツチの
溶融粘度が高くなり、従つて、高温にて紡糸しな
ければならなくなる。その為、紡糸中に紡糸ピツ
チの熱改質を生じやすくなり、好ましくない。 If the benzene-insoluble content and quinoline-insoluble content of the carbonaceous raw material exceeds the above range, the resulting spinning pitch will have a high melt viscosity, and therefore, it will be necessary to perform spinning at a high temperature. Therefore, thermal modification of the spinning pitch tends to occur during spinning, which is undesirable.
予備処理としては、前記炭素質原料を350〜500
℃、常圧〜10Kg／cm3・Ｇで0.5〜20時間程度加熱
処理して光学的異方性部分を少なくとも30％以
上、好ましくは、50％以上、特に好ましくは、70
％以上含むような熱処理物を得、次いで、この熱
処理物１重量部に対して約0.1〜３重量部の沸点
又は初留点が150℃以上の芳香族油と接触させ、
その可溶分を得るものである。芳香族油として
は、ナフタリン油、吸収油、クレオソート油又は
アントラセン油が好ましい。 As a preliminary treatment, the carbonaceous raw material is
℃, normal pressure to 10 kg/cm 3 ·G for about 0.5 to 20 hours to reduce the optical anisotropy by at least 30%, preferably 50% or more, particularly preferably 70%
% or more, and then contacting 1 part by weight of this heat-treated product with about 0.1 to 3 parts by weight of an aromatic oil having a boiling point or initial boiling point of 150°C or higher,
The soluble content is obtained. Preferred aromatic oils are naphthalene oil, absorption oil, creosote oil or anthracene oil.
この予備処理の意味については、完全に明らか
ではないが、以後の処理では再び適当物質に復原
し得ない比較的高分子部分を予め削除することに
あると本発明者等によつて推測される。なお、か
かる意味を充足する手段として炭素質原料あるい
は、上記芳香族油可溶分をテトラリン、デカリ
ン、テトラヒドロキノリン、水添した芳香族油の
水素供与性溶剤と共に、あるいは、水素供与性溶
剤に容易に転換しうるキノリン、ナフタリン油、
アントラセン油等の溶剤と触媒として鉄系化合
物、Moを含む担持又は非担持触媒を触媒に添加
して、水素ガス加圧下360〜500℃にて水添処理後
必要に応じ過等で固形分を除去し、更に必要に
応じて蒸留等によつて、溶媒を除いて残渣物を得
る方法も考えられる。 The meaning of this pretreatment is not completely clear, but the inventors speculate that it is to remove in advance relatively high molecular parts that cannot be restored to appropriate substances in subsequent treatments. . In addition, as a means to satisfy this meaning, carbonaceous raw materials or the above-mentioned aromatic oil soluble components may be used together with a hydrogen-donating solvent such as tetralin, decalin, tetrahydroquinoline, or hydrogenated aromatic oil, or easily into a hydrogen-donating solvent. quinoline, naphthalene oil, which can be converted into
A solvent such as anthracene oil and a supported or unsupported catalyst containing iron-based compounds and Mo are added to the catalyst, and after hydrogenation treatment at 360 to 500°C under hydrogen gas pressure, the solid content is removed by filtration as necessary. A method can also be considered in which the solvent is removed and, if necessary, the solvent is removed by distillation or the like to obtain a residue.
本発明の紡糸ピツチは、前記の予備処理を行な
つた炭素質原料を350〜500℃、常圧〜10Kg／cm3G
で２分〜20時間程度加熱処理することにより得る
ことができる。その際、不活性ガスの吸込みや攪
拌を行なつてもよい。 The spinning pitch of the present invention uses the carbonaceous raw material that has been pretreated as described above at 350 to 500°C and normal pressure to 10 kg/cm 3G.
It can be obtained by heat treatment for about 2 minutes to 20 hours. At that time, suction of an inert gas or stirring may be performed.
本発明においては、光学的異方性相を90％以
下、好ましくは、40〜85％、特に好ましくは、50
〜80％、更に好ましくは、60〜75％含み、しか
も、キノリン不溶分が40重量％以下、好ましく
は、30重量％以下、特に好ましくは、25重量％以
下の紡糸ピツチを得るように上記加熱処理条件を
選ぶ必要がある。特に、強度分布のバラツキの小
さい炭素繊維を得るための紡糸ピツチを調製する
ためには、温度400°〜500℃、N2ガスの吸込み量
をピツチ10gあたり0.1／分〜５／分、加熱時
間は、温度、N2ガスの吸込み量によつて変化が
あるものの１時間以内とすればよい。光学的異方
性相が90％以上になると、得られる炭素繊維の強
度分布のバラツキが大きくなるので好ましくない
（第１図参照）。異方性相があまり少ないと紡糸性
が低下するので前記範囲のものが好ましい。ま
た、キノリン不溶分は前記範囲を超えると溶融温
度の増加をもたらし、紡糸が不利になる。 In the present invention, the optically anisotropic phase is 90% or less, preferably 40 to 85%, particularly preferably 50%
The above heating is carried out to obtain a spinning pitch containing ~80%, more preferably 60 to 75%, and a quinoline insoluble content of 40% by weight or less, preferably 30% by weight or less, particularly preferably 25% by weight or less. It is necessary to select processing conditions. In particular, in order to prepare a spinning pitch to obtain carbon fibers with small variations in strength distribution, the temperature is 400° to 500°C, the amount of N2 gas sucked is 0.1/min to 5/min per 10g of pitch, and the heating time is 400° to 500°C. Although it varies depending on the temperature and the amount of N 2 gas sucked in, it should be within 1 hour. If the optically anisotropic phase exceeds 90%, it is not preferable because the strength distribution of the resulting carbon fibers will vary greatly (see Figure 1). If the amount of anisotropic phase is too small, spinnability deteriorates, so those in the above range are preferable. Furthermore, if the quinoline insoluble content exceeds the above range, the melting temperature will increase, making spinning unfavorable.
尚、本発明でいう熱処理物の光学的異方性相の
含量は、常温下偏光顕微鏡での熱処理物試料中の
光学的異方性を示す部分の面積割合として求めた
値である。 Incidentally, the content of the optically anisotropic phase in the heat-treated product as used in the present invention is a value determined as the area ratio of the portion exhibiting optical anisotropy in the sample of the heat-treated product under a polarizing microscope at room temperature.
具体的には、例えば、熱処理物試料を数mm角に
粉砕したものを常法に従つて約２cm直径の樹脂の
表面のほぼ全面に試料片を埋込み、表面を研磨
後、表面全体をくまなく偏光顕微鏡（100倍率）
下で観察し、試料の全表面積に占る光学的異方性
相の面積の割合を測定することによつて求める。 Specifically, for example, a sample piece of a heat-treated product is crushed into pieces of several mm square, and the sample piece is embedded in almost the entire surface of a resin with a diameter of about 2 cm using a conventional method. Polarized light microscope (100x magnification)
It is determined by observing the area below and measuring the ratio of the area of the optically anisotropic phase to the total surface area of the sample.
この様にして得られた紡糸ピツチを公知の方法
に従い、溶融紡糸し、得られた繊維状ピツチを不
融化、炭化し、場合によつては更に黒鉛化する事
により、強度が向上し、かつ強度分布のバラツキ
が小さいピツチ系炭素繊維を得る事ができる。 The spun pitch thus obtained is melt-spun according to a known method, and the resulting fibrous pitch is made infusible, carbonized, and in some cases further graphitized to improve strength and Pitch-based carbon fibers with small variations in strength distribution can be obtained.
本発明において、特定の炭素質原料を使用し紡
糸ピツチの光学的異方性相とキノリン不溶分を制
御する事により強度が向上し、強度分布のバラツ
キが小さい炭素繊維を得る事ができる理由につい
ては、必ずしも明らかではないが、光学的異方性
相の割合があまり高いと、炭素平面の積層状態が
良好で、更に紡糸時に、剪断と延伸によつて、規
則的な配向が、促進される為、強度分布のバラツ
キの大きなものが得られると考えられる。 In the present invention, by using a specific carbonaceous raw material and controlling the optically anisotropic phase and quinoline insoluble content in the spinning pitch, it is possible to obtain carbon fibers with improved strength and small variations in strength distribution. Although it is not necessarily clear, if the proportion of the optically anisotropic phase is too high, the stacking state of carbon planes will be good, and regular orientation will be promoted by shearing and stretching during spinning. Therefore, it is thought that an intensity distribution with large variations can be obtained.
以下に実施例を挙げて更に本発明を具体的に説
明する。 EXAMPLES The present invention will be further explained in detail by giving examples below.
実施例 １
コールタール軟ピツチ（BI6.5重量％、QI0重
量％）を窒素雰囲気下で440℃、４時間加熱処理
して光学的異方性部分を約70％含む熱処理物を得
た。次いで、この熱処理物１重量部に対して0.5
重量部のアントラセン油を加えて、350℃で10分
間攪拌後、350℃の温度を維持し、30分間精静置
し、デカンテーシヨン法により上澄液を得た。こ
の上澄液は、QIが12.9重量％、BIが42.9重量％で
光学的に全体が等方性を示した。Example 1 Coal tar soft pitch (BI6.5% by weight, QI0% by weight) was heat-treated at 440° C. for 4 hours in a nitrogen atmosphere to obtain a heat-treated product containing about 70% of the optically anisotropic portion. Next, 0.5 parts by weight of this heat-treated product
After adding part by weight of anthracene oil and stirring at 350°C for 10 minutes, the mixture was left to stand still for 30 minutes while maintaining the temperature at 350°C, and a supernatant liquid was obtained by the decantation method. This supernatant had a QI of 12.9% by weight, a BI of 42.9% by weight, and was optically isotropic as a whole.
次いで、この上澄液を窒素雰囲気下、420℃で
約20分熱処理して光学的異方性相が約75％で、
200ポイズの粘度を示す温度が334℃で、QIが36.9
重量％、BIが92.2重量％であるピツチを得た。 Next, this supernatant liquid was heat-treated at 420°C for about 20 minutes in a nitrogen atmosphere to obtain an optically anisotropic phase of about 75%.
The temperature showing a viscosity of 200 poise is 334℃, and the QI is 36.9
Pitch with a BI of 92.2% by weight was obtained.
このピツチを約358℃で溶融紡糸したところ平
均径11μのピツチ繊維を得た。このピツチ繊維を
空気中で310℃にて不融化後、窒素雰囲気下、
1400℃で炭化して炭素繊維を得た。 When this pitch was melt-spun at about 358°C, pitch fibers with an average diameter of 11 μm were obtained. After making this pitch fiber infusible at 310℃ in air, under nitrogen atmosphere,
Carbon fibers were obtained by carbonization at 1400°C.
得られた炭素繊維の強度分布のバラツキは小さ
く、平均引張り強度は20.0t／cm3であつた。 The variation in strength distribution of the obtained carbon fibers was small, and the average tensile strength was 20.0 t/cm 3 .
比較例 １
実施例１の上澄液を、窒素雰囲気下、420℃で
約40分熱処理して光学的異方性相が約94％で、
200ボイスの粘度を示す温度が350℃で、QIが38.5
重量％、BIが94.4％であるピツチ得た。Comparative Example 1 The supernatant liquid of Example 1 was heat-treated at 420°C for about 40 minutes in a nitrogen atmosphere, and the optically anisotropic phase was about 94%.
The temperature that shows the viscosity of 200 voices is 350℃, and the QI is 38.5
A pitch was obtained whose BI was 94.4% by weight.
このピツチを365℃で溶融紡糸し、以下実施例
１と同条件にて不融化、炭化し、炭素繊維を得
た。得られた炭素繊維の強度分布のバラツキは大
きく、平均引張り強度は12.0t／cm2であつた。 This pitch was melt-spun at 365°C, and then infusible and carbonized under the same conditions as in Example 1 to obtain carbon fibers. The strength distribution of the obtained carbon fibers had large variations, and the average tensile strength was 12.0 t/cm 2 .
実施例 ２
実施例１のコールタール軟ピツチを窒素雰囲気
下で450℃、90分加熱処理して光学的異方性部分
を約75％含む熱処理物を得た。次いで、実施例１
と同様にしてアントラセン油処理し、QIが11.4重
量％、BIが48.5重量％で光学的に全体が等方性を
示すアントラセン油可溶分を得た。Example 2 The coal tar soft pitch of Example 1 was heat-treated at 450° C. for 90 minutes in a nitrogen atmosphere to obtain a heat-treated product containing about 75% of the optically anisotropic portion. Next, Example 1
Anthracene oil was treated in the same manner as above to obtain an anthracene oil soluble component having QI of 11.4% by weight, BI of 48.5% by weight, and exhibiting optical isotropy as a whole.
このアントラセン油可溶分を、窒素雰囲気（１
／min／10gの吹き込み量）下、420℃で約17分
加熱処理して光学的異方性相が約65％で、200ボ
イスの粘度を示す温度が316℃で、QIが19.1重量
％、BIが86.7重量％のピツチを得た。 This anthracene oil soluble content was dissolved in a nitrogen atmosphere (1
After heat treatment at 420℃ for about 17 minutes (injection amount of /min/10g), the optically anisotropic phase was about 65%, the temperature at which the viscosity of 200 voices was shown was 316℃, the QI was 19.1% by weight, Pitch with BI of 86.7% by weight was obtained.
このピツチを実施例１と同様に紡糸、不融化、
炭化して炭素繊維を得た。得られた炭素繊維の強
度分布のバラツキは小さく、平均引張り強度は
19.9t／cm2であつた。 This pitch was spun, infusible, and
Carbonization was performed to obtain carbon fibers. The variation in the strength distribution of the obtained carbon fibers was small, and the average tensile strength was
It was 19.9t/ cm2 .
実施例 ３
コールタール軟ピツチ（BI4重量％、QI0重量
％）を窒素雰囲気下、440℃で4.5時間加熱処理
後、実施例１と同様にしてアントラセン油処理し
て、QIが8.6重量％、BIが40.3重量％で光学的に
全体が等方性を示すアントラセン油可溶分を得
た。Example 3 Coal tar soft pitch (4 wt% BI, 0 wt% QI) was heat treated at 440°C for 4.5 hours in a nitrogen atmosphere, and then treated with anthracene oil in the same manner as in Example 1 to give a product with QI of 8.6 wt% and BI. An anthracene oil-soluble component was obtained which was 40.3% by weight and was optically isotropic as a whole.
このアントラセン油可溶分を窒素雰囲気（１
／min／10gの吹き込み量）下、420℃で約18分
加熱処理して、光学的異方性相が約71％で、200
ポイズの粘度を示す温度が318℃で、QIが22.9重
量％、BIが90.2重量％のピツチを得た。 This anthracene oil soluble content was dissolved in a nitrogen atmosphere (1
The optically anisotropic phase was about 71%, and the optically anisotropic phase was about 71%.
A pitch was obtained whose temperature indicating the viscosity of poise was 318°C, QI was 22.9% by weight, and BI was 90.2% by weight.
このピツチを実施例１と同様に紡糸、不融化
後、2000℃で炭化して炭素繊維を得た。得られた
炭素繊維の強度分布のバラツキは小さく、平均引
張り強度は20.2t／cm2であつた。 This pitch was spun and infusible in the same manner as in Example 1, and then carbonized at 2000°C to obtain carbon fibers. The variation in strength distribution of the obtained carbon fibers was small, and the average tensile strength was 20.2 t/cm 2 .
第１図は実施例１（紡糸ピツチの光学的異方性
相75％）と比較例１（同94％）の炭素繊維の引張
り強度と頻度との関係を表わしたものである。
FIG. 1 shows the relationship between the tensile strength and frequency of the carbon fibers of Example 1 (75% optically anisotropic phase in the spinning pitch) and Comparative Example 1 (94% optically anisotropic phase).
Claims (1)
を少なくとも30％以上含む第一次熱処理物を取得
し、該第一次熱処理物を沸点又は初留点が150℃
以上の芳香族油と接触させ、該芳香族油相を分離
取得することにより、ベンゼン不溶分60重量％以
下、かつキノリン不溶分20重量％以下の光学的に
実質的に等方性のピツチ類を取得して、該ピツチ
類を加熱処理し、光学的異方性相が90％以下であ
り、しかもキノリン不溶分が40重量％以下の紡糸
ピツチを取得し、該紡糸ピツチを紡糸、不融化、
炭化必要に応じて黒鉛化することを特徴とする炭
素繊維の製造方法 ２ 紡糸ピツチの光学的異方性相が40〜85％であ
る特許請求の範囲第１項記載の方法 ３ 紡糸ピツチのキノリン不溶分が20〜35重量％
である特許請求の範囲第１項記載の方法 ４ 第１次熱処理物が光学的異方性部分を50％以
上含む特許請求の範囲第１項記載の方法 ５ 炭素質原料がコールタール系ピツチである特
許請求の範囲第１項記載の方法 ６ 芳香族油が、ナフタリン油、吸収油、クレオ
ソート油、又はアントラセン油である特許請求の
範囲第１項の方法 ７ 第１次熱処理物が光学的異方性部分を70％以
上含む特許請求の範囲第１項記載の方法。[Scope of Claims] 1. Heat-treating a carbonaceous raw material to obtain a first heat-treated product containing at least 30% or more of optically anisotropic portions; 150℃
By contacting with the above aromatic oil and separating the aromatic oil phase, optically substantially isotropic pituti with a benzene insoluble content of 60% by weight or less and a quinoline insoluble content of 20% by weight or less are produced. is obtained, the pitches are heat-treated to obtain a spinning pitch having an optically anisotropic phase of 90% or less and a quinoline insoluble content of 40% by weight or less, and the spinning pitch is spun and infusible. ,
Method 2 for producing carbon fiber, characterized by carbonization and graphitization as necessary. Method 3 according to claim 1, wherein the optically anisotropic phase in the spinning pitch is 40 to 85%. Quinoline in the spinning pitch. Insoluble content is 20-35% by weight
Method 4 according to Claim 1, wherein the first heat-treated product contains 50% or more of an optically anisotropic portion Method 5 according to Claim 1, wherein the carbonaceous raw material is a coal tar-based pitch. A method 6 according to claim 1, wherein the aromatic oil is naphthalene oil, an absorption oil, a creosote oil, or an anthracene oil.A method 7 according to claim 1, wherein the first heat-treated product is optically The method according to claim 1, comprising 70% or more of anisotropic portion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15003683A JPS6045612A (en) | 1983-08-17 | 1983-08-17 | Preparation of carbon yarn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15003683A JPS6045612A (en) | 1983-08-17 | 1983-08-17 | Preparation of carbon yarn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6045612A JPS6045612A (en) | 1985-03-12 |
| JPH0532494B2 true JPH0532494B2 (en) | 1993-05-17 |
Family
ID=15488093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15003683A Granted JPS6045612A (en) | 1983-08-17 | 1983-08-17 | Preparation of carbon yarn |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6045612A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102428396B1 (en) * | 2018-05-08 | 2022-08-02 | 오씨아이 주식회사 | Method for treating high solid coal tar |
| KR102477035B1 (en) * | 2019-07-23 | 2022-12-13 | 오씨아이 주식회사 | The manufacturing method for petroleum based high softning point pitch |
| KR102498310B1 (en) * | 2021-01-18 | 2023-02-10 | 오씨아이 주식회사 | Preparation of Impregnation Pitch |
| KR102529745B1 (en) * | 2021-04-19 | 2023-05-08 | 재단법인 포항산업과학연구원 | Method of producing coal-based pitch for artificial graphite |
| KR102583031B1 (en) * | 2021-07-01 | 2023-09-27 | 한국화학연구원 | Method for manufacturing hetero-phase binder pitch and hetero-phase binder pitch manufactured therefrom |
| KR102389550B1 (en) * | 2021-09-24 | 2022-04-21 | 한국화학연구원 | Method for preparing anisotropic pitch derived from heavy oil for carbon fiber based on two-stage solvent extraction method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5818419A (en) * | 1981-07-27 | 1983-02-03 | Nippon Oil Co Ltd | Raw material pitch for carbon fiber |
| JPS58113292A (en) * | 1981-12-28 | 1983-07-06 | Mitsubishi Chem Ind Ltd | Preparation of raw material pitch for production of carbon product |
-
1983
- 1983-08-17 JP JP15003683A patent/JPS6045612A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5818419A (en) * | 1981-07-27 | 1983-02-03 | Nippon Oil Co Ltd | Raw material pitch for carbon fiber |
| JPS58113292A (en) * | 1981-12-28 | 1983-07-06 | Mitsubishi Chem Ind Ltd | Preparation of raw material pitch for production of carbon product |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6045612A (en) | 1985-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5356574A (en) | Process for producing pitch based activated carbon fibers and carbon fibers | |
| KR860001156B1 (en) | A process for the production of carbon fibers | |
| JPH0532494B2 (en) | ||
| JPS59196390A (en) | Preparation of pitch for carbon fiber | |
| JPH0150272B2 (en) | ||
| JPS6065090A (en) | Preparation of pitch for carbon fiber spinning | |
| CN107532086B (en) | Raw material pitch for carbon fiber production | |
| JP2780231B2 (en) | Carbon fiber production method | |
| JPH0432118B2 (en) | ||
| US6241923B1 (en) | Process for the production of carbon fibers | |
| JPS6030366B2 (en) | Manufacturing method for high-strength, high-modulus carbon fiber | |
| JPS60202189A (en) | Pitch for carbonaceous material and its preparation | |
| JPH058238B2 (en) | ||
| JPH0455237B2 (en) | ||
| JPS61185588A (en) | Production of pitch for spinning pitch carbon yarn | |
| JP2817232B2 (en) | Method for producing high-performance carbon fiber | |
| JP2982406B2 (en) | Method for producing spinning pitch for carbon fiber | |
| JPS5834569B2 (en) | Carbon fiber manufacturing method | |
| JPS6183319A (en) | Carbon fiber and its production | |
| JPH0437167B2 (en) | ||
| JPH0583115B2 (en) | ||
| JP3055295B2 (en) | Pitch-based carbon fiber and method for producing the same | |
| JP2533487B2 (en) | Carbon fiber manufacturing method | |
| JPS6233330B2 (en) | ||
| JPH0144751B2 (en) |