JPH03104926A - Inorganic fiber having high strength and elasticity and preparation thereof - Google Patents
Inorganic fiber having high strength and elasticity and preparation thereofInfo
- Publication number
- JPH03104926A JPH03104926A JP1206640A JP20664089A JPH03104926A JP H03104926 A JPH03104926 A JP H03104926A JP 1206640 A JP1206640 A JP 1206640A JP 20664089 A JP20664089 A JP 20664089A JP H03104926 A JPH03104926 A JP H03104926A
- Authority
- JP
- Japan
- Prior art keywords
- polycyclic aromatic
- silicon
- polymer
- fibers
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012784 inorganic fiber Substances 0.000 title claims description 42
- 239000000835 fiber Substances 0.000 claims abstract description 43
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 238000009987 spinning Methods 0.000 claims abstract description 24
- -1 polycyclic aromatic compounds Chemical class 0.000 claims abstract description 22
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 4
- 239000011882 ultra-fine particle Substances 0.000 claims abstract description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract 2
- 229920005604 random copolymer Polymers 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 14
- 229920001558 organosilicon polymer Polymers 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000011300 coal pitch Substances 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 6
- 239000011301 petroleum pitch Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 230000001747 exhibiting effect Effects 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 2
- 229910008045 Si-Si Inorganic materials 0.000 claims 2
- 229910006411 Si—Si Inorganic materials 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 241000234282 Allium Species 0.000 abstract description 4
- 235000002732 Allium cepa var. cepa Nutrition 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 1
- 239000011295 pitch Substances 0.000 description 33
- 229920000049 Carbon (fiber) Polymers 0.000 description 21
- 239000004917 carbon fiber Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 17
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 15
- 239000002994 raw material Substances 0.000 description 15
- 239000008096 xylene Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 239000002131 composite material Substances 0.000 description 12
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 11
- 238000005452 bending Methods 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 229920002239 polyacrylonitrile Polymers 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 229910010271 silicon carbide Inorganic materials 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000011316 heat-treated pitch Substances 0.000 description 4
- 238000002074 melt spinning Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000012779 reinforcing material Substances 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000013081 microcrystal Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000012643 polycondensation polymerization Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- PAFYVDNYOJAWDX-UHFFFAOYSA-L calcium;2,2,2-trichloroacetate Chemical compound [Ca+2].[O-]C(=O)C(Cl)(Cl)Cl.[O-]C(=O)C(Cl)(Cl)Cl PAFYVDNYOJAWDX-UHFFFAOYSA-L 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 229920000555 poly(dimethylsilanediyl) polymer Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、機械的性質が優れ、且つ耐酸化性、並びに複
合材用マトリックスに対する濡れ性が大幅に向上した炭
素系新規無機繊維及びその製造方法に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a new carbon-based inorganic fiber that has excellent mechanical properties, oxidation resistance, and significantly improved wettability to a composite matrix, and its production. Regarding the method.
（従来の技術及びその問題点）
炭素繊維は、軽量でしかも高強度、高弾性であるため、
スポーツ・レジャー用品をはしめ、航空機、自転車、建
材など広い分野に亙ってその利用が図られている。(Conventional technology and its problems) Carbon fiber is lightweight, has high strength and high elasticity,
It is used in a wide range of fields, including sports and leisure goods, aircraft, bicycles, and building materials.
炭素繊維としては、ポリアクリロニトリルを原料とした
ＰＡＮ系炭素繊維と、石油系、石炭系のピッチを原料と
する、所謂ピッチ系炭素繊維が知られている。As carbon fibers, PAN-based carbon fibers made from polyacrylonitrile and so-called pitch-based carbon fibers made from petroleum-based and coal-based pitches are known.
ピッチ系炭素繊維は、一般に強度がＰＡＮ系炭素繊維に
比べて劣るが、原料が安価なことから、強度を高める方
法について種々の検討がなされ、例えば、特開昭５９−
２２３３１６号公報には、効果的にメソフェーズを生威
させ、紡糸時に配向させる方法が開示されている。Pitch-based carbon fibers are generally inferior in strength to PAN-based carbon fibers, but since the raw materials are cheap, various studies have been conducted on ways to increase the strength.
Japanese Patent No. 223316 discloses a method for effectively generating mesophase and orienting it during spinning.
しかし、基本的には、炭素繊維は結晶性の繊維であるた
め、硬く、毛羽が発生し易く、また複合材料とする際マ
トリックスとの濡れ性も劣るという欠点がある。However, since carbon fibers are basically crystalline fibers, they are hard, tend to fluff, and have poor wettability with a matrix when used as a composite material.
そこで種々の炭素繊維の表面処理法が考案され、現在知
られている方法として、繊維に柔軟性を付与するととも
に、毛羽発生を抑制する目的で、ポリビニルアルコール
、不飽和ポリエステル樹脂、エボキシ樹脂のようなサイ
ジング剤を表面に塗布する方法や、マトリックスとの接
着性を向上させる目的でその表面を乾式又は湿式酸化処
理する方法等がある。Therefore, various methods for surface treatment of carbon fibers have been devised, and the currently known method uses materials such as polyvinyl alcohol, unsaturated polyester resin, and epoxy resin for the purpose of imparting flexibility to the fibers and suppressing the generation of fuzz. There are methods such as applying a suitable sizing agent to the surface, and dry or wet oxidation treatment of the surface for the purpose of improving adhesion to the matrix.
これらの処理のうち、特に表面酸化層を設ける方法では
、酸化時に繊維に損傷を与えるため物性は低下する傾向
にある。更に、炭素繊維は５００℃を超える酸化雰囲気
中では、燃焼するため使用できない。Among these treatments, the method of providing a surface oxidation layer in particular damages the fibers during oxidation and thus tends to reduce physical properties. Furthermore, carbon fiber cannot be used in an oxidizing atmosphere at a temperature exceeding 500°C because it will burn.
このような背景から、高強度、高弾性率を有し、しかも
マトリックスとの濡れ性、接着性が良好で、従来広範囲
の分野で使用されているＰＡＮ系炭素繊維よりも安価な
新繊維の開発が強く要望されてきた。Against this background, we are developing a new fiber that has high strength and high modulus, has good wettability and adhesion with the matrix, and is cheaper than the PAN-based carbon fiber that has been used in a wide range of fields. has been strongly requested.
また、炭素繊維のより高温での耐酸化性を向上させるこ
とが種々の分野で強く望まれている。Furthermore, it is strongly desired in various fields to improve the oxidation resistance of carbon fibers at higher temperatures.
この要望を満たす方法として、例えば、特開昭６２−２
０９１３９号公報、特開昭６２−２ １ ５０１６号公
報に記載された方法が提案されている。As a method to meet this demand, for example, JP-A-62-2
The methods described in Japanese Patent Application Laid-open No. 09139 and Japanese Patent Application Laid-Open No. 62-21-5016 have been proposed.
これらの公報には、石炭系又は石油系ピッチ中の有機溶
媒可溶或分とボリシランを混合・加熱反応させてオルガ
ノボリアリールシランを合威し、それを紡糸、不融化、
焼戒により炭化珪素繊維と炭素繊維の中間の性質を有す
る無機質繊維を製造する方法が記載されている。In these publications, organoboriarylsilane is formed by mixing and heating polysilane with an organic solvent-soluble portion of coal-based or petroleum-based pitch, which is then spun, made infusible,
A method for producing inorganic fibers having properties intermediate between silicon carbide fibers and carbon fibers using shakikai is described.
しかし、上記方法では、一方の出発物質として有機溶媒
不溶分を全く含まないピッチを選び、オルガノボリアリ
ールシラン製造においても前記不溶分が全く生成しない
条件下で反応を行っている。However, in the above method, pitch containing no organic solvent insoluble matter is selected as one of the starting materials, and the reaction is carried out under conditions in which the insoluble matter is not produced at all in the production of organoboriarylsilane.
従って得られる生或物である紡糸原料中には、炭素繊維
の強度発現に最も重要な戒分と言われているメソフェー
ズ状態を含む前記不溶分が全く含まれていない。Therefore, the spinning raw material obtained as a raw material does not contain any insoluble matter including the mesophase state, which is said to be the most important component for developing the strength of carbon fibers.
上記紡糸原料を紡糸、不融化、焼威して得られる無機繊
維は、条件によっては炭素の黒鉛結晶に相当する（００
２）回折線は得られるものの、ピッチ繊維特有の配向は
認められず高弾性率のものは得られない。更に上記公報
の方法では、ビッチ戒分が多くなる程、不活性ガス中の
耐熱性は向上するものの、耐酸化性は低下し、しかも機
械的特性が著しく低下するという問題点がある。Depending on the conditions, the inorganic fiber obtained by spinning, infusible, and burning the above spinning raw material corresponds to graphite crystals of carbon (00
2) Although a diffraction line is obtained, the orientation peculiar to pitch fibers is not observed, and a product with a high elastic modulus cannot be obtained. Furthermore, the method disclosed in the above-mentioned publication has the problem that as the bitch content increases, the heat resistance in an inert gas improves, but the oxidation resistance decreases, and furthermore, the mechanical properties deteriorate significantly.
（問題点を解決するための手段）
本発明の目的は、上記問題点を解決した新規な、高強度
、高弾性率を有する無機繊維及びその製造方法を提供す
ることにある。(Means for Solving the Problems) An object of the present invention is to provide a novel inorganic fiber having high strength and high modulus of elasticity, which solves the above problems, and a method for producing the same.
本発明によれば、ピッチ系炭素繊維、ＰＡＮ系炭素繊維
に比べて複合材料用マトリックスに対する濡れ性が非常
に良好で、炭化珪素繊維に比べてはるかに弾性率が高く
、しかもピッチ系炭素繊維、ＰＡＮ系炭素繊維に比べて
２００〜３００℃も耐酸化性の向上した新規繊維及びそ
の製造方法が提供される。According to the present invention, pitch-based carbon fibers have very good wettability with respect to a matrix for composite materials compared to pitch-based carbon fibers and PAN-based carbon fibers, and have a much higher elastic modulus than silicon carbide fibers. A new fiber with improved oxidation resistance by 200 to 300°C compared to PAN-based carbon fibers and a method for producing the same are provided.
本発明によれば、珪素含有多環状芳香族重合体から得ら
れる無機繊維であって、その構成戒分が、）該重合体を
構成するメソフエーズ状態にある多環状芳香族化合物か
ら導かれるラジアル構造、オニオン構造、ランダム構造
、コアラジアル構造、スキンオニオン構造及びモザイク
構造からなる群から選ばれる少なくとも一種の結晶配列
状態を示す炭素質、
ｉｉ）該重合体を構成する有機溶媒不溶分を含む光学的
等方性の多環状芳香族化合物から導かれる、無配向状態
の結晶質炭素及び／又は非品質炭素、及び
（ｉｉｉ）Ｓｉ，Ｃ及びＯから実質的になる非晶質相及
び／又は粒径が５００人以下の実質的にβＳｉＣからな
る結晶質超微粒子と非品質のＳｉＯＸ （０〈Ｘ≦２）
からなる集合体であり、
構成元素の割合が、Ｓ ｌ ｉ ３ ０〜７０重量％、
Ｃ；２０〜６０重量％及びＯ ； ０． ５〜１０重量
％であるＳｔ−Ｃ−０物質
であることを特徴とする高強度・高弾性率無機繊維が提
供される。According to the present invention, there is provided an inorganic fiber obtained from a silicon-containing polycyclic aromatic polymer, the constituent components of which are:) a radial structure derived from a polycyclic aromatic compound in a mesophase state constituting the polymer; , a carbon material exhibiting at least one type of crystalline arrangement selected from the group consisting of an onion structure, a random structure, a core-radial structure, a skin-onion structure, and a mosaic structure; ii) an optical material containing an organic solvent-insoluble component constituting the polymer; Non-oriented crystalline carbon and/or non-quality carbon derived from an isotropic polycyclic aromatic compound, and (iii) an amorphous phase and/or grain size consisting essentially of Si, C and O. is less than 500 and crystalline ultrafine particles consisting essentially of βSiC and non-quality SiOX (0<X≦2)
It is an aggregate consisting of S l i 3 0 to 70% by weight, and the proportion of the constituent elements is
C; 20-60% by weight and O; 0. A high strength, high modulus inorganic fiber is provided which is characterized by being a St-C-0 material of 5 to 10% by weight.
さらに本発明によれば、
ｉ）結合単位（Ｓ ｉ−ＣＨ． ） 、または結合単位
（Ｓｔ ＣＨ２）と結合単位（Ｓｉ−Ｓｉ）から主と
してなり、珪素原子の側鎖に水素原子、低級アルキル基
、フェニル基及びシリル基からなる群から選ばれる側鎖
基を有し、結合単位（Ｓｉ ＧＨ２）の全数対結合単
位（Ｓｉ−Ｓｔ）の全数の比が１００〜２０の範囲にあ
る有機珪素重合体の珪素原子の少なくとも一部が、石油
系又は石炭系のピッチあるいはその熱処理物の芳香族環
と珪素一炭素連結基を介して結合したランダム共重合体
１００重量部、及び
ｉｉ）石油系又は石炭系ピッチを熱処理して得られるメ
ソフェーズ状態又はメソフェーズと光学的等方相との両
相からなる多環状芳香族化合物（以下両者を総称してメ
ソフェーズ多環状芳香族化合物と言うことがある。）５
〜５００００重量部を、
２００〜５００℃の範囲の温度で加熱反応及び／又は加
熱溶融して、珪素含有多環状芳香族重合体を得る第１工
程、
上記珪素含有多環状芳香族重合体の紡糸原液を調製して
紡糸する第２工程、
該紡糸原糸を張力下あるいは無張力下で不融化する第３
工程、及び
不融化した前記紡糸繊維を真空中あるいは不活性ガス雰
囲気中で８００〜３０００℃の範囲の温度で焼成する第
４工程
からなることを特徴とする実質的に炭素、珪素、酸素か
らなる高強度・高弾性率無機繊維の製造方法が提供され
る。Furthermore, according to the present invention, i) mainly consists of a bonding unit (S i-CH. , a phenyl group, and a silyl group, and the ratio of the total number of bonding units (Si GH2) to the total number of bonding units (Si-St) is in the range of 100 to 20. 100 parts by weight of a random copolymer in which at least a part of the silicon atoms of the union are bonded to the aromatic ring of petroleum-based or coal-based pitch or a heat-treated product thereof via a silicon-carbon linking group, and ii) petroleum-based or A mesophase state obtained by heat treating coal-based pitch, or a polycyclic aromatic compound consisting of both a mesophase and an optically isotropic phase (hereinafter both may be collectively referred to as a mesophase polycyclic aromatic compound). 5
A first step of obtaining a silicon-containing polycyclic aromatic polymer by heat-reacting and/or heat-melting ~50,000 parts by weight at a temperature in the range of 200 to 500°C, spinning of the silicon-containing polycyclic aromatic polymer. A second step of preparing a stock solution and spinning it, and a third step of infusibleizing the spun yarn under tension or without tension.
and a fourth step of firing the infusible spun fibers at a temperature in the range of 800 to 3000°C in vacuum or in an inert gas atmosphere. A method for producing a high strength, high modulus inorganic fiber is provided.
本発明の無機繊維についてまず説明する。なお、以下の
記載において、「部」はすべて「重量部」であり、戒分
含有率の単位としてのパーセント（％）は全て「重量％
」である。First, the inorganic fiber of the present invention will be explained. In addition, in the following description, all "parts" are "parts by weight", and all percentages (%) as a unit of precept content are "% by weight".
”.
本発明の無機繊維は前述した構ｔ２或分ｊ）、ｉｉ）及
びｉｉｉ）からなっており、Ｓｉ；０．０１〜２９％、
Ｃｉ７０〜９９．９％及びＯ；０．００１−１０％、好
ましくはＳｉ；０．１〜２５％、Ｃ；７４〜９９．８％
及びＯ ｉ ０． ０ １〜８％から実質的に構威され
ている。The inorganic fiber of the present invention consists of the above-mentioned structures t2 or j), ii) and iii), Si; 0.01 to 29%,
Ci 70-99.9% and O; 0.001-10%, preferably Si; 0.1-25%, C; 74-99.8%
and O i 0. 0.01% to 8%.
この無機繊維の構ｅ．戒分である結晶質炭素は５００人
以下の結晶子サイズを有し、１．５人の分解能を有する
高分解能電子顕微鏡において、繊維軸方向に配向した３
．２人の（００２）面に相当する微細なラティスイメー
ジ像が観察されうる超微粒子のグラファイト結晶である
。無機繊維中の結晶質炭素は、ラジアル構造、オニオン
構造、ランダム構造、コアラジアル構造、スキンオニオ
ン構造、モザイク構造及び一部ラジアル構造を含むラン
ダム構造等をとることができる。これは、原料中にメソ
フェーズ多環状芳香族化合物が存在することに起因する
。Structure of this inorganic fiber e. Crystalline carbon, which is a precept, has a crystallite size of less than 500 and is oriented in the fiber axis direction in a high-resolution electron microscope with a resolution of 1.5.
．． It is an ultrafine graphite crystal in which a fine lattice image corresponding to two (002) planes can be observed. The crystalline carbon in the inorganic fibers can have a radial structure, an onion structure, a random structure, a core radial structure, a skin onion structure, a mosaic structure, a random structure including a partial radial structure, and the like. This is due to the presence of mesophase polycyclic aromatic compounds in the raw materials.
この無機繊維における構成或分ｉ）及びｉｉ）の総和１
００部に対する構戒成分ｉｉｉ）の割合は０．０１５〜
２００部であり、且つ構成或分ｉ）、ｉｉ）の比率は１
：０．０２〜４である。The sum of components i) and ii) in this inorganic fiber 1
The ratio of component iii) to 00 parts is 0.015~
200 copies, and the ratio of components i) and ii) is 1
:0.02-4.
構戒戊分ｉ）及びｉｉ）の総和１００部に対する構戒戒
分ｉｉｉ）の割合が０．０１５未満の場合は、ほとんど
ビノチ繊維と変わらず、耐酸化性や濡れ性の向上は望め
ず、上記割合が２００部を越えた場合はグラファイトの
微細結晶が効果的には生成せず、高弾性率の繊維が得ら
れない。If the ratio of 3) to the total of 100 parts of 1) and 2) is less than 0.015, it will be almost the same as the binotch fiber, and no improvement in oxidation resistance or wettability can be expected. If the above ratio exceeds 200 parts, fine graphite crystals will not be effectively generated and fibers with a high elastic modulus will not be obtained.
本発明の無機繊維では、層間隔が小さく三次元的配列が
付与された微結晶が効果的に生戒している。In the inorganic fiber of the present invention, microcrystals with a small interlayer spacing and three-dimensional arrangement are effectively preserved.
また、珪素の分布状態は、焼或時の雰囲気や原料中のメ
ソフェーズの大きさ、濃度によっても制御することがで
きる。例えば、メソフエーズを大きく戒長させた場合、
珪素含有ボリマーは繊維表面相に押し出され易く、焼或
後繊維表面に珪素に富む層が生或する。Furthermore, the distribution state of silicon can also be controlled by the atmosphere during firing and the size and concentration of mesophase in the raw material. For example, if the mesophase is greatly increased,
Silicon-containing polymers tend to be extruded into the fiber surface phase, resulting in a silicon-rich layer on the fiber surface after sintering.
次に、本発明の無機繊維の製造方法を説明する。Next, the method for producing inorganic fibers of the present invention will be explained.
第１工程：
出発原料の一つである結合単位（Ｓｉ ＣＨ２）、ま
たは結合単位（Ｓ ｉ ＣＨｚ ）と結合単位（Ｓｔ
−Ｓｔ）からなる有機珪素重合体は、例えば、ジメチル
ジク口ロシランと金属ナトリウムの反応により得られる
ポリメチルシランを不活性ガス中で４ ０ ０ ’Ｃ以
上に加熱することにより得られる。この有機珪素重合体
の重量平均分子量（Ｍ，）は、一般的には３００〜１０
００で、Ｍ，１が４００〜８００のものが、優れた炭素
系無機繊維を得るための中間原料であるランダム共重合
体を調製するために特に好ましい。First step: A bonding unit (Si CH2), which is one of the starting materials, or a bonding unit (S i CHz ) and a bonding unit (St
The organosilicon polymer consisting of -St) can be obtained, for example, by heating polymethylsilane obtained by the reaction of dimethyl dicyclosilane and metallic sodium to 400'C or higher in an inert gas. The weight average molecular weight (M,) of this organosilicon polymer is generally 300 to 10
00 and M,1 of 400 to 800 is particularly preferred for preparing a random copolymer which is an intermediate raw material for obtaining excellent carbon-based inorganic fibers.
もう一つの出発原料である多環状芳香族化合物は石油類
及び／又は石炭類から得られるピッチで、特に好ましい
ピッチは、石油類の流動接触分解により得られる重質油
、その重質油を蒸留して得た留出成分又は残渣油及びそ
れらを熱処理して得られる光学的に等方性のピッチであ
る。Another starting material, the polycyclic aromatic compound, is pitch obtained from petroleum and/or coal. Particularly preferred pitches are heavy oil obtained by fluid catalytic cracking of petroleum, and heavy oil distilled from the heavy oil. The distillate components or residual oils obtained by this method and the optically isotropic pitch obtained by heat-treating them.
上記ピッチ中には、ベンゼン、トルエン、キシレン、テ
トラヒド口フランなどの有機溶媒に不溶の戒分が５〜９
８重量％含まれていることが好ましく、５重量％未満の
ピッチを原料として用いた場合、強度、弾性率共に優れ
た無機質繊維は得られず、また、９８重量％より多いピ
ッチを原料として用いた場合、共重合体の分子量上昇が
激しく、一部コーキングの起こる場合もあり、紡糸困難
な状態になる。The above pitch contains 5 to 9 compounds that are insoluble in organic solvents such as benzene, toluene, xylene, and tetrahydrofuran.
It is preferable that the content is 8% by weight. If less than 5% by weight of pitch is used as a raw material, an inorganic fiber with excellent strength and elastic modulus cannot be obtained, and if more than 98% by weight of pitch is used as a raw material. If it is, the molecular weight of the copolymer will increase rapidly and coking may occur in some cases, making spinning difficult.
このピッチの重量平均分子量（Ｍ．）は、１００〜３０
００である。The weight average molecular weight (M.) of this pitch is 100 to 30
It is 00.
重量平均分子量は以下のようにして求めた値である。即
ち、ピッチが有機溶媒不溶分を含有しない場合はそのま
まゲルバーξユエーションクロマトグラフ（ｃｐｃ）測
定し、ピッチが有機溶媒不溶分を含有する場合は、温和
な条件で水添処理し、有機溶媒不溶分を有機溶媒可溶な
戒分に変えて後ＧＰＣ測定する。有機溶媒不溶分を含有
する重合体の重量平均分子量は、上記と同様の処理を施
し求めた値である。The weight average molecular weight is a value determined as follows. That is, if the pitch does not contain organic solvent-insoluble matter, it is directly measured using a gel bar ξ chromatography (CPC), and if the pitch contains organic solvent-insoluble matter, it is hydrogenated under mild conditions to remove the organic solvent-insoluble matter. After changing the fraction to organic solvent-soluble fraction, GPC measurement is performed. The weight average molecular weight of the polymer containing organic solvent insoluble matter is a value obtained by performing the same treatment as above.
ランダム共重合体は、有機珪素重合体に、石油系又は石
炭系ピッチを添加し、不活性ガス中で好ましくは２５０
〜５００℃の範囲の温度で加熱反応させることにより調
製される。The random copolymer is prepared by adding petroleum-based or coal-based pitch to an organosilicon polymer, and preferably reacting at 250% in an inert gas.
It is prepared by a heating reaction at a temperature in the range of ~500°C.
ピッチの使用割合は、有機珪素重合体１００部当たり８
３〜４９００部であることが好ましい。The ratio of pitch used is 8 parts per 100 parts of organosilicon polymer.
It is preferable that it is 3-4900 parts.
ピッチの使用割合が過度に小さい場合は、得られる無機
繊維中の炭化珪素成分が多くなり、高弾性率を有する無
機繊維が得られなくなり、また、その割合が過度に多い
場合は、炭化珪素威分が少なくなり、マトリックスに対
する濡れ性や耐酸化性に優れた無機繊維が得られなくな
る。If the proportion of pitch used is too small, the silicon carbide component in the resulting inorganic fiber will increase, making it impossible to obtain an inorganic fiber with a high modulus of elasticity. As a result, inorganic fibers with excellent matrix wettability and oxidation resistance cannot be obtained.
上記反応の反応温度が過度に低いと、珪素原子と芳香族
炭素の結合が生威しにくくなり、反応温度が過度に高い
と、生戒したランダム共重合体の分解及び高分子量化が
、激しく起こり好ましくない。If the reaction temperature of the above reaction is too low, the bond between the silicon atom and aromatic carbon will be difficult to form, and if the reaction temperature is too high, the random copolymer will decompose and increase its molecular weight violently. This is not a good thing to happen.
メソフェーズ多環状芳香族化合物は、例えば、石油系又
は石炭系ピッチを不活性ガス中で３００〜５００℃に加
熱し、生或する軟質留分を除去しながら縮重合すること
によって調製することができる。Mesophase polycyclic aromatic compounds can be prepared, for example, by heating petroleum-based or coal-based pitch to 300 to 500°C in an inert gas and subjecting it to condensation polymerization while removing the soft fraction. .
上記縮重合反応温度が過度に低いと縮金環の戒長が充分
でなく、またその温度が過度に高いとコーキングにより
不融化物の生成が激しくなる。If the temperature of the condensation polymerization reaction is too low, the length of the condensed ring will not be sufficient, and if the temperature is too high, the formation of infusible products will increase due to coking.
上記のメソフェーズ多環状芳香族化合物は、融点が２０
０〜４ ０ ０ ’Ｃの範囲にあり、また、重量平均分
子量が２００〜１００００である。The above mesophase polycyclic aromatic compound has a melting point of 20
It is in the range of 0 to 400'C, and has a weight average molecular weight of 200 to 10,000.
メソフェーズ多環状芳香族化合物の中でも、２０〜１０
０％の光学的異方性度を有し、３０〜１００％のベンゼ
ン、トルエン、キシレン又はテトラヒド口フランに対す
る不溶分を含むものが、機械的性能上優れた無機繊維を
得るために特に好ましい。Among mesophase polycyclic aromatic compounds, 20 to 10
Particularly preferred is one having an optical anisotropy of 0% and containing 30 to 100% of insoluble matter in benzene, toluene, xylene, or tetrahydrofuran in order to obtain an inorganic fiber with excellent mechanical performance.
第１工程では、ランダム共重合体とメソフェーズ多環状
芳香族化合物を２００〜５００℃の温度範囲で加熱溶融
及び／又は加熱反応し、珪素含有多環状芳香族重合体か
らなる紡糸ボリマーを調製する。In the first step, the random copolymer and the mesophase polycyclic aromatic compound are melted and/or heated and reacted in a temperature range of 200 to 500°C to prepare a spun polymer made of the silicon-containing polycyclic aromatic polymer.
メソフェーズ多環状芳香族化合物の使用割合はランダム
共重合体１００部当たり５〜５００００部であることが
好ましく、５部未満では、生戒物におけるメソフェーズ
含有量が不足するため、高弾性の焼或糸が得られず、ま
た、５００００部より多い場合は、珪素或分の不足のた
めマトリックスに対する濡れ性、耐酸化性に優れた無機
繊維が得られなくなる。The proportion of the mesophase polycyclic aromatic compound to be used is preferably 5 to 50,000 parts per 100 parts of the random copolymer. If it is less than 5 parts, the mesophase content in the raw materials will be insufficient, so high elastic sintered yarns If the amount is more than 50,000 parts, an inorganic fiber with excellent matrix wettability and oxidation resistance cannot be obtained due to a certain shortage of silicon.
上記珪素含有多環状芳香族重合体の重量平均分子量は２
００〜１１０００で、融点が２００〜４００℃である。The weight average molecular weight of the silicon-containing polycyclic aromatic polymer is 2
00-11000, and the melting point is 200-400°C.
第２工程：
第１工程で得られる珪素含有多環状芳香族重合体である
紡糸ポリマーを加熱溶融させて、場合によってはこれを
濾過してミクロゲル、不純物等の紡糸に際して有害とな
る物質を除去し、これを通常用いられる合或繊維紡糸装
置により紡糸する。2nd step: The spinning polymer, which is a silicon-containing polycyclic aromatic polymer obtained in the 1st step, is heated and melted, and in some cases, it is filtered to remove substances that are harmful during spinning, such as microgels and impurities. This is then spun using a commonly used joint fiber spinning device.
紡糸する際の紡糸原液の温度は原料ポリマーの軟化温度
によって異なるが、２２０〜４ ２ ０ ”Ｃの範囲の
温度が有利である。The temperature of the spinning dope during spinning varies depending on the softening temperature of the raw material polymer, but a temperature in the range of 220 to 420''C is advantageous.
前記紡糸装置において、必要に応じて紡糸筒を取付け、
該紡糸筒内の雰囲気を空気、不活性ガス、熱空気、熱不
活性ガス、スチーム、及びアンモニアガスからなる群か
ら選ばれる一種以上の雰囲気とした後、巻取り速度を大
きくすることにより細い直径の繊維を得ることができる
。前記溶融紡糸における紡糸速度は原料の平均分子量、
分子量分布、分子構造によって異なるが、５０〜５００
０ｍ／分の範囲であることが好ましい。In the spinning device, a spinning tube is attached as necessary,
After setting the atmosphere in the spinning tube to one or more atmospheres selected from the group consisting of air, inert gas, hot air, hot inert gas, steam, and ammonia gas, the winding speed is increased to create a thin diameter. fibers can be obtained. The spinning speed in the melt spinning is determined by the average molecular weight of the raw materials,
Although it varies depending on the molecular weight distribution and molecular structure, 50 to 500
A range of 0 m/min is preferable.
第３工程：
第２工程で得られる紡糸繊維を張力又は無張力の作用も
とで不融化する。Third step: The spun fibers obtained in the second step are made infusible under the action of tension or no tension.
代表的な不融化方法は、紡糸繊維を酸化性雰囲気中で加
熱する方法である。不融化の温度は好ましくは５０〜４
００℃の範囲の温度である。不融化温度が過度に低いと
紡糸原糸を構成するポリマーのはしかけが起こらず、ま
た、この温度が過度に高いとポリマーが燃焼する。A typical infusibility method is to heat spun fibers in an oxidizing atmosphere. The infusibility temperature is preferably 50 to 4
The temperature is in the range of 00°C. If the infusibility temperature is too low, the polymer constituting the spinning filament will not be fused, and if the temperature is too high, the polymer will burn.
不融化の目的は、紡糸繊維を構成するボリマーを三次元
構造の不溶・不融のはしかけ状態にし、次工程の焼戒の
際に熔融せず、且つ隣接した繊維と融着しないようにす
ることである。不融化の際の酸化性雰囲気を構成するガ
スとしては、空気、オゾン、酸素、塩素ガス、臭素ガス
、アンモニアガス、及びこれらの混合ガスが挙げられる
。The purpose of infusibility is to make the polymer that makes up the spun fibers into a three-dimensional structure that is insoluble and infusible, so that it does not melt during the next process of burning and does not fuse with adjacent fibers. That's true. Gases constituting the oxidizing atmosphere during infusibility include air, ozone, oxygen, chlorine gas, bromine gas, ammonia gas, and mixed gases thereof.
上記とは別の不融化方法として、紡糸繊維に酸化性雰囲
気あるいは非酸化性雰囲気で、張力あるいは無張力で必
要に応じて低温加熱しながら、Ｔ線照射、あるいは電子
線照射して不融化する方法も採用することができる。As an infusible method different from the above, spun fibers are infusible by T-ray irradiation or electron beam irradiation in an oxidizing or non-oxidizing atmosphere, under tension or no tension, while heating at a low temperature as necessary. method can also be adopted.
このＴ線あるいは電子線を照射する目的は、紡糸繊維を
形成するポリマーを、さらに重合させることによって、
紡糸原糸が融解し、繊維形状を失うことを防ぐことにあ
る。The purpose of irradiating this T-ray or electron beam is to further polymerize the polymer that forms the spun fibers.
The purpose is to prevent the spun yarn from melting and losing its fiber shape.
Ｔ線あるいは電子線の照射線量は１０６〜１０Ｉ０ラッ
ドが適当である。The appropriate irradiation dose of T-rays or electron beams is 106 to 10I0 rad.
照射は真空、不活性ガス雰囲気下、あるいは空気、オゾ
ン、酸素、塩素ガス、臭素ガス、アンモニアガス及びこ
れらの混合ガスのような酸化性ガス雰囲気で行うことが
できる。Irradiation can be carried out in a vacuum, an inert gas atmosphere, or an oxidizing gas atmosphere such as air, ozone, oxygen, chlorine gas, bromine gas, ammonia gas, and mixtures thereof.
照射による不融化は室温で行うこともでき、必要であれ
ば５０〜２００℃の温度範囲で加熱しながら行うことに
よって不融化をより短時間で達威させることもできる。Infusibility by irradiation can be carried out at room temperature, and if necessary, infusibility can be achieved in a shorter time by heating in the temperature range of 50 to 200°C.
不融化は、無張力下で行うと、前記紡糸繊維は収縮のた
め波状の形を呈するようになるが、次工程の焼或工程で
矯正できる場合もあり、張力は必ずしも必要ないが、張
力を作用させる場合には、その張力の大きさは不融化時
に紡糸繊維が収縮して波状となることを少なくとも防止
できる以上の張力を作用させると良い結果が得られる。If infusibility is carried out without tension, the spun fibers will shrink and take on a wavy shape, but this can sometimes be corrected in the next firing process, and tension is not necessarily required. When applied, good results can be obtained if the tension is greater than that which can at least prevent the spun fibers from shrinking and becoming wavy during infusibility.
不融化の際に、作用させる張力としては、１〜５ＱＱｇ
／ｍｍ”の範囲が好ましく、Ｉｇ／国２以下の張力を作
用させても繊維をたるませないような緊張を与えること
ができず、５ ０ ０ ｇ ／ｒｎｔｎ２以上の張力を
作用させると繊維が切断することがある。The tension to be applied during infusibility is 1 to 5QQg.
/mm'' range is preferable; even if a tension of Ig/country 2 or less is applied, it is not possible to apply tension that will not cause the fibers to sag, and if a tension of 500 g/rntn2 or more is applied, the fibers will not loosen. May be severed.
第４工程：
第３工程で得られる不融化糸を、真空あるいは不活性ガ
ス雰囲気中で８００〜３０００℃の範囲の温度で焼或す
ることによって、主として炭素、珪素、酸素からなる無
機繊維が得られる。Fourth step: By firing the infusible yarn obtained in the third step at a temperature in the range of 800 to 3000°C in a vacuum or inert gas atmosphere, inorganic fibers mainly composed of carbon, silicon, and oxygen are obtained. It will be done.
焼戒工程において、張力を作用させることは必ずしも必
要ないがＯ． Ｏ Ｏ １〜１００Ｋｇ／ｍｎ＋２の範
囲で張力を作用させながら高温焼威すると屈曲を少なく
した強度の高い無機繊維を得ることができる。In the burning process, it is not necessarily necessary to apply tension, but O. By performing high-temperature firing while applying tension in the range of O O 1 to 100 Kg/mn+2, high-strength inorganic fibers with less bending can be obtained.
加熱過程において、約７ ０ ０ ”Ｃから無機化が激
しくなり、約８ ０ ０ ’Ｃでほぼ無機化が完了する
ものと推定される。従って、焼或は、ｓ ｏ ｏ ’ｃ
以上の温度で行うことが好ましく、３０００℃より高い
温度を得るためには高価な装置を必要とし、工業的メリ
ットがないため、８００〜３０００℃範囲の温度で焼戊
するのが好ましい。In the heating process, it is estimated that mineralization becomes intense from about 700'C and is almost complete at about 800'C.Therefore, sintering or soo'c
Burning is preferably carried out at a temperature in the range of 800 to 3000°C, since obtaining a temperature higher than 3000°C requires expensive equipment and has no industrial merit.
（効果）
本発明の無ａｍ維は、高温の酸化雰囲気中においても、
珪素原子の存在により炭素原子の引き抜きが良く制され
、通常のピッチ系、ＰＡＮ系の炭素繊維よりも酸化分解
開始温度が２００〜３００℃上昇する。また、本発明の
無機繊維は、珪素原子の存在により、プラスチック等に
対する濡れ性が大幅に向上し、眉間剪断強度及び９０゜
方向の曲げ強度の大きいプラスチック複合材料を与える
ことができる。(Effect) The non-am fibers of the present invention can be used even in a high temperature oxidizing atmosphere.
Due to the presence of silicon atoms, the extraction of carbon atoms is well controlled, and the oxidative decomposition start temperature is 200 to 300° C. higher than that of ordinary pitch-based or PAN-based carbon fibers. Furthermore, due to the presence of silicon atoms, the inorganic fibers of the present invention have greatly improved wettability to plastics, etc., and can provide plastic composite materials with high glabellar shear strength and high bending strength in the 90° direction.
（実施例） 以下実施例によって本発明を説明する。(Example) The present invention will be explained below with reference to Examples.
参考例ｌ
５ｌの三口フラスコに無水キシレン２．５ｌ及びナトリ
ウム４００ｇを入れ、窒素ガス気流下でキシレンの沸点
まで加熱し、ジメチルジク口ロシラン１ｌを１時間で滴
下した。滴下終了後、ｌＯ時間加熱還流し沈＃物を生威
させた。沈澱を濾過し、メタノールついで水で洗浄して
、白色粉末のボリジメチルシラン４２０ｇを得た。Reference Example 1 2.5 liters of anhydrous xylene and 400 g of sodium were placed in a 5 liter three-necked flask, heated to the boiling point of xylene under a nitrogen gas stream, and 1 liter of dimethyl dichlorosilane was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was heated under reflux for 10 hours to incubate the precipitate. The precipitate was filtered and washed with methanol and then water to obtain 420 g of boridimethylsilane as a white powder.
このポリジメチルシラン４００ｇを、ガス導入管、攪拌
機、冷却器及び留出管を備えた３ｌの三ロフラスコに仕
込み、攪拌しながら５０ｄ／分の窒素気流下に４ ２
０ ’Ｃで加熱処理して、留出受器に３５０ｇの無色透
明な少し粘性のある液体を得た。400 g of this polydimethylsilane was charged into a 3-liter three-lough flask equipped with a gas inlet tube, a stirrer, a condenser, and a distillation tube, and was heated under a nitrogen flow of 50 d/min while stirring.
After heating at 0'C, 350 g of a colorless and transparent slightly viscous liquid was obtained in the distillation receiver.
この液体の数平均分子量は蒸気圧浸透法で測定したとこ
ろ４７０であった。The number average molecular weight of this liquid was 470 as measured by vapor pressure osmosis.
この物質の赤外線吸収スペクトルを測定したところ、６
５０〜９００ｃ＋ｒ’と１２５０ｃｍ−’にＳｔＣ Ｈ
ｘの吸収、２ １ ０ ０ｃｍ−’にＳｔ−Ｈの吸収
、１０２０Ｃ１ｍ−’付近と１３５５ｃｍ−’にＳｉ−
ＣＨ．−Ｓｉの吸収、２９００ｃｍ−’と２９５０ｃｍ
−’にＣ−Ｈの吸収が認められ、またこの物質の遠赤外
線吸収スペクトルを測定したところ、３８０ＣＩＩ＋−
’にＳｉ−Ｓｉの吸収が認められることから、得られた
液状物質は、主として（Ｓ ｉ Ｃ Ｈｚ ）結合単
位及び（Ｓｉ−Ｓｉ）結合単位からなり、珪素の側鎖に
水素原子及びメチル基を有する有機珪素重合体であるこ
とが判明した。When the infrared absorption spectrum of this substance was measured, it was found that 6
StC H at 50~900c+r' and 1250cm-'
x absorption, St-H absorption at 2 100 cm-', Si-
CH. -Si absorption, 2900 cm-' and 2950 cm
-' absorption of C-H was observed, and when the far-infrared absorption spectrum of this substance was measured, it was found that 380CII+-
Since absorption of Si-Si is observed in It turned out to be an organosilicon polymer having the following properties.
核磁気共鳴分析及び赤外線吸収分析の測定結果から、こ
の有機珪素重合体は（Ｓｉ ＣＨ２）結合単位の全数
対（Ｓｉ−Ｓｉ）結合単位の全数の比率がほぼ１：３で
ある重合体であることが確認された。From the measurement results of nuclear magnetic resonance analysis and infrared absorption analysis, this organosilicon polymer is a polymer in which the ratio of the total number of (Si CH2) bond units to the total number of (Si-Si) bond units is approximately 1:3. This was confirmed.
上記有機珪素重合体３００ｇをエタノールで処理して低
分子量物を除去して、数平均分子量が１２００の重合体
４０ｇを得た。300 g of the above organosilicon polymer was treated with ethanol to remove low molecular weight substances to obtain 40 g of a polymer having a number average molecular weight of 1200.
この物質の赤外線吸収スペクトルを測定したところ、上
記と同様の吸収ピークが認められ、この物質は主として
（Ｓｉ−ＣＨ２）結合単位及び（Ｓｉ−Ｓｉ）結合単位
からなり、珪素の側鎖に水素原子及びメチル基を有する
有機珪素重合体であることが判明した。When the infrared absorption spectrum of this substance was measured, absorption peaks similar to those above were observed, and this substance mainly consists of (Si-CH2) bond units and (Si-Si) bond units, and hydrogen atoms in the silicon side chains. It turned out to be an organosilicon polymer having methyl groups.
核磁気共鳴分析及び赤外線吸収分析の測定結果から、こ
の有機珪素重合体は（Ｓｉ ＣＨ２）結合単位の全数
対（Ｓｉ−Ｓｉ）結合単位の全数の比率がほぼ７：１で
ある重合体であることが確認された。According to the measurement results of nuclear magnetic resonance analysis and infrared absorption analysis, this organosilicon polymer is a polymer in which the ratio of the total number of (Si CH2) bond units to the total number of (Si-Si) bond units is approximately 7:1. This was confirmed.
参考例２
石油留分のうち、軽油以上の高沸点物をシリカ・アルミ
ナ系分解触媒の存在下、５００℃の温度で流動接触分解
・精留を行い、その塔底より残清を得た。以下、この残
渣をＦＣＣスラリーオイルと呼ぶ。Reference Example 2 Fluid catalytic cracking and rectification of petroleum fractions with a boiling point higher than that of light oil was carried out at a temperature of 500° C. in the presence of a silica/alumina cracking catalyst, and a residual liquid was obtained from the bottom of the column. Hereinafter, this residue will be referred to as FCC slurry oil.
このＦＣＣスラリーオイルは、元素分析の結果、炭素原
子対水素原子の原子比（Ｃ／Ｈ）が０．７５で、核磁気
共鳴分析による芳香炭素率が０．５５であった。As a result of elemental analysis, this FCC slurry oil had an atomic ratio of carbon atoms to hydrogen atoms (C/H) of 0.75, and an aromatic carbon ratio of 0.55 as determined by nuclear magnetic resonance analysis.
実施例１
参考例２で得られたＦＣＣスラリーオイル１００ｇを１
１．／分の窒素ガス気流下４ ２ ０ ’Ｃで、２時間
加熱し、同温度における留出分を留去後、残渣を１５０
℃にて熱時濾過を行い、同温度における不融部を除去し
、軽質分除去ピンチ５７ｇを得た。Example 1 100g of FCC slurry oil obtained in Reference Example 2
1. Heated for 2 hours at 420'C under a nitrogen gas flow of 1/2 min. After distilling off the distillate at the same temperature, the residue was heated to 150'C.
Filtration was performed while hot at ℃ to remove the infusible portion at the same temperature, and 57 g of light fraction removed pinch was obtained.
この軽質分除去ピッチは６０％のキシレン不溶分を含ん
でいた。This light fraction removed pitch contained 60% xylene insoluble matter.
この軽質分除去ピッチ５７ｇに参考例１で得た有機珪素
重合体２５ｇ及びキシレン２０成を加え、攪拌しながら
昇温し、キシレンを留去後、４００℃で６時間反応させ
４３ｇのランダム共重合体を得た。To 57 g of this light fraction removed pitch, 25 g of the organosilicon polymer obtained in Reference Example 1 and 20 g of xylene were added, the temperature was raised while stirring, the xylene was distilled off, and the mixture was reacted at 400°C for 6 hours to produce 43 g of random copolymer. Obtained union.
この反応生成物は赤外線吸収スペクトル測定の結果、有
機珪素重合体中に存在するＳｉ−Ｈ結合（Ｉ Ｒ ：
２ １ ０ ０ｃｒ’）の減少、及び新たなＳｉＣ（ベ
ンゼン環の炭素）結合（ＩＲ：１１３５ｃｍ−’）の生
或が認められることより有機珪素重合体の珪素原子の一
部が多環状芳香族環と直接結合した部分を有するランダ
ム共重合体であることがわかった。As a result of infrared absorption spectrum measurement, this reaction product was found to contain Si-H bonds (IR:
2 1 0 0 cr') and the formation of new SiC (benzene ring carbon) bonds (IR: 1135 cm-'), some of the silicon atoms in the organosilicon polymer are polycyclic aromatic. It turned out to be a random copolymer with a portion directly bonded to the ring.
また、この共重合体は、キシレン不溶部を含まず、重量
平均分子量が１４００で、融点が２６５℃であった。Further, this copolymer contained no xylene-insoluble portion, had a weight average molecular weight of 1400, and a melting point of 265°C.
これを、３ ０ ０ ’Ｃで加熱溶融静置し、比重差に
より軽質部分を除去した残部４０ｇを得た。これをポリ
マー（ａ）と呼ぶ。This was heated and melted at 300'C and left to stand, to obtain 40 g of the remainder from which light parts were removed due to the difference in specific gravity. This is called polymer (a).
これと並行して、ＦＣＣスラリーオイル４００ｇを、窒
素ガス気流下４５０℃に加熱し、同温度における留出分
を留去後、残渣を２００℃にて熱時濾過を行い、同温度
における不融部を除去し、軽質分除去ピッチ１８０ｇを
得た。得られた軽質分除去ピッチ１８０ｇを窒素気流下
、反応にまり生戒する軽質分を除去しなから４ ０ ０
’Ｃで８時間縮重合を行い、熱処理ピッチ８ ０．
３ ｇを得た。In parallel, 400 g of FCC slurry oil was heated to 450°C under a nitrogen gas stream, and after distilling off the distillate at the same temperature, the residue was filtered while hot at 200°C. 180 g of light fraction-removed pitch was obtained. 180 g of the obtained pitch from which light components were removed was heated under a nitrogen stream to remove light components that were stuck in the reaction.
Polycondensation was carried out at 'C for 8 hours, and the heat treatment pitch was 80.
3 g was obtained.
この熱処理ピンチは融点３１０℃、キシレン不溶分９７
％、キノリン不溶分２０％を含有しており、研磨面の偏
光顕微鏡観察による光学的異方性が９５％のメソフエー
ズ多環状芳香族化合物であった。This heat-treated pinch has a melting point of 310℃ and a xylene insoluble content of 97.
It was a mesophase polycyclic aromatic compound containing 20% of quinoline insoluble matter and an optical anisotropy of 95% when observed with a polarized light microscope on the polished surface.
これを再び、３５０℃に加熱溶融静置し、比重差により
軽質部分を除去した残部８０ｇを得た。This was heated and melted at 350° C. and allowed to stand again to obtain 80 g of a residue from which light portions were removed due to the difference in specific gravity.
これとポリマー（ａ） ４ ０ ｇを混合し、窒素雰囲
気下、３５０℃で１時間溶融加熱し、均一な状態にある
珪素含有多環状芳香族重合体を得た。この重合体は、融
点が２９０℃で、７０％のキシレン不溶分を含んでいた
。This and 40 g of polymer (a) were mixed and melted and heated at 350° C. for 1 hour in a nitrogen atmosphere to obtain a silicon-containing polycyclic aromatic polymer in a uniform state. This polymer had a melting point of 290°C and contained 70% xylene insolubles.
上記高分子量物を紡糸用原料とし、ノズル径０，１５帥
の金属製ノズルを用い、３６０“Ｃで溶融紡糸を行い、
得られた紡糸原糸を、空気中、３００℃で酸化、不融化
し、更にアルゴン雰囲気中、１３００℃で焼戒を行い、
直径１０μｍの無機繊維を得た。Using the above-mentioned high molecular weight material as a raw material for spinning, melt spinning is performed at 360"C using a metal nozzle with a nozzle diameter of 0.15 mm,
The obtained spun yarn was oxidized and made infusible at 300°C in air, and then burned at 1300°C in an argon atmosphere.
Inorganic fibers with a diameter of 10 μm were obtained.
この繊維は引張強度が２９５Ｋｇ／ＩＩＩＩＩ１２、引
張弾性率２６ｔ／ａ＋ｎ＋”であり、破壊面の観察より
あきらかにラジアル構造であった。This fiber had a tensile strength of 295 Kg/III12 and a tensile modulus of 26 t/a+n+'', and it clearly had a radial structure from observation of the fracture surface.
上記繊維を空気中で加熱酸化したところ、７００℃まで
ほとんど重量減少を示さず、８００℃においても全重量
の５％が消失したにすぎなかった．また、前記無機繊維
を強化材とした一方向強化エポキシ樹脂（ビスフェノー
ルＡ型）複合材料（Ｖｒ；６０％）のＯ″、９０゜方向
の曲げ強度はソレソレ、１ ９ ５ Ｋ ｇ／ｍｍ”
１ ２． ８ Ｋ ｇ／ｔａｎ”であり、通常の炭
素繊維を用いた一方向強化エポキシ複合材料（Ｖｒ；６
０％）の０゜、９０゜方向の曲げ強度１７６Ｋｇ／ｍｍ
” ７Ｋｇ／ｍｍ”に比べてはるかに優れたものであ
った。When the above fibers were heated and oxidized in air, there was almost no weight loss up to 700°C, and only 5% of the total weight was lost even at 800°C. Furthermore, the bending strength in the O'' and 90° directions of the unidirectionally reinforced epoxy resin (bisphenol A type) composite material (Vr; 60%) using the inorganic fibers as reinforcement is 195 K g/mm''.
1 2. 8 K g/tan", and is a unidirectionally reinforced epoxy composite material (Vr; 6
0%) bending strength in 0° and 90° directions 176 Kg/mm
It was much better than "7Kg/mm".
実施例２
参考例２で得られたＦＣＣスラリーオイル２００ｇを、
２ｆ／分の窒素ガス気流下、４５０℃で０． ５時間加
熱し、同温度における留出分を留去後、残渣を２ ０
０ ’Ｃにて熱時濾過を行い、同温度における不融部を
除去し、軽質分除去ピッチ５７ｇを得た。Example 2 200g of FCC slurry oil obtained in Reference Example 2 was
Under a nitrogen gas flow of 2 f/min, at 450°C, 0. After heating for 5 hours and distilling off the distillate at the same temperature, the residue was
Hot filtration was performed at 0'C to remove infusible parts at the same temperature to obtain 57 g of pitch from which light components were removed.
この軽質分除去ピッチは２５％のキシレン不溶分を含む
光学的に等方性のピッチであった。This light fraction removed pitch was an optically isotropic pitch containing 25% xylene insoluble matter.
この軽質分除去ピッチ５７ｇに参考例１で得た有機珪素
重合体２５ｇ及びキシレン２０ｄを加え、攪拌しながら
昇温し、キシレンを留去後、４００℃で６時間反応させ
５１．０ｇのランダム共重合体を得た。25 g of the organosilicon polymer obtained in Reference Example 1 and 20 d of xylene were added to 57 g of this light fraction removed pitch, the temperature was raised while stirring, the xylene was distilled off, and the mixture was reacted at 400°C for 6 hours to produce 51.0 g of random copolymer. A polymer was obtained.
この反応生ｔｃ物は、赤外線吸収スペクトル測定の結果
、実施例１と同様、有機珪素重合体の珪素原子の一部が
多環状芳香族環と直接結合した部分を有するランダム共
重合体であることがわかった。As a result of infrared absorption spectrum measurement, this reaction product was found to be a random copolymer in which some of the silicon atoms of the organosilicon polymer were directly bonded to polycyclic aromatic rings, as in Example 1. I understand.
また、この共重合体は、キシレン不溶部を含まず、重量
平均分子量が１４００で、融点が２６５℃で、軟化点が
３１０℃であった。Further, this copolymer contained no xylene-insoluble portion, had a weight average molecular weight of 1400, a melting point of 265°C, and a softening point of 310°C.
一方、前記軽質分除去ピッチ１８０ｇを窒素気流下、反
応により生戒する軽質分を除去しながら４００℃で８時
間縮重合を行い、熱処理ピッチ９７．２ｇを得た。On the other hand, 180 g of the pitch from which light components had been removed was subjected to condensation polymerization at 400° C. for 8 hours under a nitrogen stream while removing light components that were present during the reaction to obtain 97.2 g of heat-treated pitch.
この熱処理ピッチは融点２６３℃、軟化点３０８“Ｃ、
キシレン不溶分７７％、キノリン不溶分３１％を含有し
ており、研磨面の偏光顕微鏡観察による光学的異方性が
７５％のメソフェーズ多環状芳香族化合物であった。This heat-treated pitch has a melting point of 263°C, a softening point of 308"C,
It was a mesophase polycyclic aromatic compound containing 77% xylene-insoluble matter and 31% quinoline-insoluble matter, and had an optical anisotropy of 75% when observed with a polarizing microscope on the polished surface.
このメソフェーズ多環状芳香族化合物９０ｇと前記ラン
ダム共重合体６．４ｇを混合し、窒素雰囲気下、３８０
℃で一時間溶融加熱し、均一な状態にある珪素含有多環
状芳香族重合体を得た。90 g of this mesophase polycyclic aromatic compound and 6.4 g of the random copolymer were mixed, and the mixture was heated to 380 g under a nitrogen atmosphere.
The mixture was melted and heated at ℃ for one hour to obtain a silicon-containing polycyclic aromatic polymer in a uniform state.
この重合体は、融点が２６７℃で、軟化点が３１５゛Ｃ
で、７０％のキシレン不溶分を含んでいた。This polymer has a melting point of 267°C and a softening point of 315°C.
It contained 70% xylene insoluble matter.
上記高分子量物を紡糸用原料とし、ノズル径０．１５帥
の金属製ノズルを用い、３６０℃で溶融紡糸を行い、得
られた紡糸原糸を、空気中、３００℃で酸化、不融化し
、更にアルゴン雰囲気中、１３００℃で焼戒を行い、直
径８μｍの無′４ｍｔａ維を得た。Using the above-mentioned high molecular weight material as a raw material for spinning, melt spinning was performed at 360°C using a metal nozzle with a nozzle diameter of 0.15 mm, and the resulting spun yarn was oxidized and made infusible at 300°C in air. Further, the fibers were burned at 1300° C. in an argon atmosphere to obtain 4 mta-free fibers with a diameter of 8 μm.
この繊維は引張強度が３２０Ｋｇ／ＩＩＩＩ１２、引張
弾性率２ ６ ｔ ／ｃｍ”であり、破壊面の観察より
あきらかにラジアル構造であった。This fiber had a tensile strength of 320 Kg/III12 and a tensile modulus of 2 6 t/cm'', and it clearly had a radial structure from observation of the fracture surface.
この無機繊維を粉砕後、アルカリ溶融、塩酸処理を施し
、水溶液とした後高周波プラズマ発光分光分析（ＩＣＰ
）を行った結果、珪素含有率は０．９５％であった。After pulverizing the inorganic fibers, they were melted with alkali and treated with hydrochloric acid to form an aqueous solution, which was then subjected to high-frequency plasma emission spectroscopy (ICP).
), the silicon content was 0.95%.
上記繊維を空気中で加熱酸化したところ、６００℃にお
いても上記機械特性の低下は認められず、６ ０ ０
”Ｃで酸化焼失する市販炭素繊維に比べ耐酸化性に優れ
ていることが確認された。When the above fibers were heated and oxidized in air, no decrease in the above mechanical properties was observed even at 600°C, and 600°C.
It was confirmed that this product has superior oxidation resistance compared to commercially available carbon fibers, which are oxidized and burnt out by C.
また、前記無機繊維を強化材とした一方向強化エボキシ
樹脂（ビスフェノールＡ型）複合材料（Ｖｆ；６０％）
（７）０’、９０゜方向ｃ７） 曲ケ強度ハそれぞれ、
２ １ ０ Ｋｇ／ｍｍ” 、１ ３．２ Ｋｇ／ｍｔ
ｎ２であり、通常のピッチ系炭素繊維（引張強度２８０
Ｋ ｇ ／ａ＋＋２、引張弾性率５ ５ ｔ ／ｍｍ
２）を用いた一方向強化エボキシ複合材料（Ｖｒ；６０
％）のＯ’、９０’方向の曲げ強度１００Ｋｇ／凪２、
３． ５ Ｋ ｇ ／ｔｔｍ”に比べてはるかに優れた
ものであった。In addition, a unidirectionally reinforced epoxy resin (bisphenol A type) composite material (Vf: 60%) using the inorganic fiber as a reinforcing material
(7) 0', 90° direction c7) Bending strength is respectively,
2 10 Kg/mm”, 1 3.2 Kg/mt
n2, normal pitch carbon fiber (tensile strength 280
K g /a++2, tensile modulus 5 5 t /mm
2) Unidirectionally reinforced epoxy composite material (Vr; 60
%) O', bending strength in 90' direction 100Kg/calm 2,
3. 5 K g/ttm".
実施例３
実施例１と同様にして４３ｇのランダム共重合体を得た
。Example 3 In the same manner as in Example 1, 43 g of a random copolymer was obtained.
これを、３００℃で加熱溶融静置し、比重差により軽質
部分を除去した残部４０ｇを得た。This was heated and melted at 300° C. and left to stand, and the light portion was removed due to the difference in specific gravity to obtain 40 g of the remainder.
これと並行して、ＦＣＣスラリーオイル４００ｇを、窒
素ガス気流下４ ５ ０ ”Ｃに加熱し、同温度におけ
る留出分を留去後、残渣を２００℃にて熱時濾過を行い
、同温度における不融部を除去し、軽質分除去ピッチ１
８０ｇを得た。得られた軽質分除去ピッチ１８０ｇを窒
素気流下、反応にまり生或する軽質分を除去しながら４
００℃で７時間縮重合を行い、熱処理ピッチ８５ｇを得
た。In parallel with this, 400 g of FCC slurry oil was heated to 450"C under a nitrogen gas flow, and after distilling off the distillate at the same temperature, the residue was filtered while hot at 200 °C. The infusible part is removed, and the light content removal pitch 1
80g was obtained. 180 g of the obtained pitch from which light components were removed was heated under a nitrogen stream for 4 hours while removing light components that were trapped in the reaction.
Polycondensation was carried out at 00° C. for 7 hours to obtain 85 g of heat-treated pitch.
この熱処理ピッチは融点２６８℃、キシレン不溶分９２
％、キノリン不溶分１２％を含有しており、研磨面の偏
光顕微鏡観察による光学的異方性が８９％のメソフェー
ズピッチであった。This heat-treated pitch has a melting point of 268°C and a xylene insoluble content of 92%.
%, and 12% of quinoline insoluble matter, and the optical anisotropy of the polished surface was 89% when observed with a polarizing microscope.
上記ランダム共重合体１４ｇと上記メソフェーズピッチ
７０ｇを混合、窒素雰囲気下３１０℃で１時間溶融加熱
し、均一な状態にある珪素含有多環状芳香族重合体を得
た。この重合体は、融点が２７２℃で、７５％のキシレ
ン不溶分を含んでいた。14 g of the random copolymer and 70 g of the mesophase pitch were mixed and melted and heated at 310° C. for 1 hour in a nitrogen atmosphere to obtain a silicon-containing polycyclic aromatic polymer in a uniform state. This polymer had a melting point of 272°C and contained 75% xylene insolubles.
上記高分子量物を紡糸用原料とし、ノズル径０．１５ｍ
ｍの金属製ノズルを用い、３４０℃で溶融紡糸を行い、
得られた紡糸原糸を、空気中、３００℃で酸化、不融化
し、更にアルゴン雰囲気中、２１００℃で焼或を行い、
直径９．５μｍの無機繊維を得た。The above high molecular weight material is used as the raw material for spinning, and the nozzle diameter is 0.15 m.
Melt spinning was performed at 340°C using a metal nozzle of
The obtained spun yarn was oxidized and made infusible at 300°C in air, and further calcined at 2100°C in an argon atmosphere.
Inorganic fibers with a diameter of 9.5 μm were obtained.
この繊維は引張強度が２ ７ ０ Ｋｇ／ｍｍ” 、引
張弾性率４ ５ ｔ ／ｍｍ”であり、破壊面の走査型
電子顕微鏡を用いた観察より、結晶層が幾重にも重なっ
た珊瑚様のランダム、ラジアル混在構造であった。This fiber has a tensile strength of 270 Kg/mm" and a tensile modulus of 45 t/mm", and observation of the fractured surface using a scanning electron microscope reveals that it has a coral-like structure with many layers of crystals. It had a mixed random and radial structure.
上記繊維を空気中で加熱酸化したところ、７００′Ｃま
でほとんど重量減少を示さず、８００℃においても全重
量の５％が消失したにすぎなかった。When the above fibers were oxidized by heating in air, there was almost no weight loss up to 700'C, and only 5% of the total weight was lost even at 800C.
また、前記無機繊維を強化材とした一方向強化エボキシ
樹脂（ビスフェノールＡ型）複合材料（Ｖｆ；６０％）
のＯ’、９０゜方向の曲げ強度はそれぞれ、１ ８ ５
Ｋｇ／ｍｍ” 、１ ２．５ Ｋｇ／ｍｍ”であり、
通常のピッチ系炭素繊維（引張強度２８０Ｋｇ／ＩＩＯ
！ｌ２、引張弾性率５ ５ ｔ ／ｍｕ” ）を用いた
一方向強化エボキシ複合材料（Ｖｆｉ６０％）の０゜、
９０゜方向の曲げ強度１００Ｋｇ／ｍｍ”３． ５ Ｋ
ｇ ／ｎｍ＋”に比べてはるかに優れたものであった
。In addition, a unidirectionally reinforced epoxy resin (bisphenol A type) composite material (Vf: 60%) using the inorganic fiber as a reinforcing material
The bending strength in the O' and 90° directions is 1 8 5, respectively.
Kg/mm", 1 2.5 Kg/mm",
Ordinary pitch-based carbon fiber (tensile strength 280Kg/IIO
! l2, tensile modulus 5 5 t/mu”) of unidirectionally reinforced epoxy composite material (Vfi 60%),
Bending strength in 90° direction 100Kg/mm”3.5K
g/nm+''.
実施例４
実施例１で得られたプレカーサー糸を空気中、３００℃
で不融化した後、不活性ガス雰囲気中、１４００℃で焼
威し、直径９．５μｍの無機繊維を得た。透過電子顕微
鏡観察の結果、結晶質のグラファイトの間に均一にβ−
ＳｉＣ微結晶が分散していた。Example 4 The precursor yarn obtained in Example 1 was heated at 300°C in air.
After making it infusible, it was burned at 1400° C. in an inert gas atmosphere to obtain inorganic fibers with a diameter of 9.5 μm. As a result of transmission electron microscopy, β-
SiC microcrystals were dispersed.
この繊維は、ラジアル構造と一部ランダム構造から戒り
、引張強度が２３２Ｋｇ／ｍｍ”で、引張弾性率が３０
ｔ／ｍｍ”の高弾性無機繊維であった。This fiber has a radial structure and a partially random structure, has a tensile strength of 232 Kg/mm'', and a tensile modulus of 30.
It was a highly elastic inorganic fiber with a t/mm".
この繊維を強化材とした一方向強化エポキシ樹脂（ビス
フェノールＡ型）複合材料（Ｖ，；６０％）のＯ＠、９
０°方向の曲げ強度は、それぞれ、１ ５ ０ Ｋｇ／
ｍｍ” 、６．８ Ｋｇ／ｒｔｍ”であった。O@, 9 of a unidirectionally reinforced epoxy resin (bisphenol A type) composite material (V,; 60%) using this fiber as a reinforcing material.
The bending strength in the 0° direction is 1 5 0 Kg/
mm", 6.8 Kg/rtm".
実施例５
実施例２で得られたプレカーサー糸を空気中、３００℃
で不融化した後、不活性ガス雰囲気中、２４００℃で焼
威し、直径７．１μｍの無機繊維を得た。透過電子顕微
鏡観察の結果、結晶質のグラファイトの間に均一にβ−
ＳｉＣ微結晶が分散していた。Example 5 The precursor yarn obtained in Example 2 was heated in air at 300°C.
After making it infusible, it was burned at 2400° C. in an inert gas atmosphere to obtain inorganic fibers with a diameter of 7.1 μm. As a result of transmission electron microscopy, β-
SiC microcrystals were dispersed.
この繊維は、ラジアル構造と一部ランダム構造から威り
、引張強度が３４０Ｋｇ／ｍｍ”で、引張弾性率が５５
ｔ／ＩＩＩ［ｌＩ２の高弾性無機繊維であった。This fiber has a radial structure and a partially random structure, and has a tensile strength of 340 kg/mm'' and a tensile modulus of 55.
It was a highly elastic inorganic fiber of t/III[lI2.
この繊維を強化材とした一方向強化エボキシ樹脂（ビス
フェノールＡ型）複合材料（Ｖｒ；６０％）のＯ’、９
０”方向の曲げ強度は、それぞれ、２ ０ ５ Ｋ ｇ
／ｙｍ” 、６． ０ Ｋ ｇ／ｍｍ”であった。O', 9 of a unidirectionally reinforced epoxy resin (bisphenol A type) composite material (Vr; 60%) using this fiber as a reinforcing material
The bending strength in the 0” direction is 2 0 5 Kg, respectively.
/ym", 6.0 K g/mm".
実施例６
実施例３と同様にして得た不融化糸を、アルゴン雰囲気
中、２５００℃で焼威し、直径９．２μの無機繊維を得
た。Example 6 An infusible yarn obtained in the same manner as in Example 3 was burned at 2500° C. in an argon atmosphere to obtain inorganic fibers with a diameter of 9.2 μm.
この無機繊維は、引張強度が３ ０ ０ Ｋ ｇ ／’
ｒａｎ”で、引張弾性率が５ ３ ｔ ／ｍｍ”の高弾
性繊維であった。This inorganic fiber has a tensile strength of 300 Kg/'
ran'' and a tensile modulus of 5 3 t/mm''.
実施例７〜９
実施例１のランダム共重合体及びメソフェーズ多環状芳
香族化合物との加熱溶融混合の温度及び混合比率をいろ
いろ変えて均一な状態にある珪素含有多環状芳香族重合
体を得た。これを用いて実施例ｌと同様にして得られた
無機繊維の機械的性能を第１表に示す。Examples 7 to 9 Silicon-containing polycyclic aromatic polymers in a uniform state were obtained by varying the heating melt mixing temperature and mixing ratio of the random copolymer of Example 1 and the mesophase polycyclic aromatic compound. . Table 1 shows the mechanical performance of the inorganic fiber obtained using this in the same manner as in Example 1.
実施例１０〜１３
実施例２のランダム共重合体及びメソフエーズ多環状芳
香族化合物との加熱溶融混合の温度及び混合比率をいろ
いろ変えて均一な状態にある珪素含有多環状芳香族重合
体を得た。これを用いて実施例２と同様にして得られた
無機繊維の機械的性能を第２表に示す。Examples 10 to 13 Silicon-containing polycyclic aromatic polymers in a uniform state were obtained by varying the heating melt mixing temperature and mixing ratio of the random copolymer of Example 2 and the mesophase polycyclic aromatic compound. . Table 2 shows the mechanical performance of the inorganic fiber obtained using this in the same manner as in Example 2.
Claims (2)
維であって、その構成成分が、 （ｉ）該重合体を構成するメソフェーズ状態にある多環
状芳香族化合物から導かれるラジアル構造、オニオン構
造、ランダム構造、コアラジアル構造、スキンオニオン
構造及びモザイク構造からなる群から選ばれる少なくと
も一種の結晶配列状態を示す炭素質、 （ｉｉ）該重合体を構成する有機溶媒不溶分を含む光学
的等方性の多環状芳香族化合物から導かれる、無配向状
態の結晶質炭素及び／又は非晶質炭素、及び （ｉｉｉ）Ｓｉ、Ｃ及びＯから実質的になる非晶質相及
び／又は粒径が５００Å以下の実質的にβ−ＳｉＣから
なる結晶質超微粒子と非晶質の ＳｉＯ＿ｘ（０＜ｘ≦２）からなる集合体であり、 構成元素の割合が、Ｓｉ；３０〜７０重量％、Ｃ；２０
〜６０重量％及びＯ；０．５〜１０重量％であるＳｉ−
Ｃ−Ｏ物質 であることを特徴とする高強度・高弾性率無機繊維。(1) An inorganic fiber obtained from a silicon-containing polycyclic aromatic polymer, the constituent components of which are (i) a radial structure derived from a mesophase polycyclic aromatic compound constituting the polymer; carbon material exhibiting at least one type of crystalline structure selected from the group consisting of a random structure, a core-radial structure, a skin-onion structure, and a mosaic structure; Non-oriented crystalline carbon and/or amorphous carbon derived from a oriented polycyclic aromatic compound, and (iii) an amorphous phase and/or grain size consisting essentially of Si, C and O. It is an aggregate consisting of crystalline ultrafine particles substantially made of β-SiC with a diameter of 500 Å or less and amorphous SiO_x (0<x≦2), and the proportion of the constituent elements is Si; 30 to 70% by weight; C;20
~60% by weight and O; 0.5-10% by weight Si-
A high-strength, high-modulus inorganic fiber characterized by being a C-O substance.
単位（Ｓｉ−ＣＨ＿２）と結合単位（Ｓｉ−Ｓｉ）から
主としてなり、珪素原子の側鎖に水素原子、低級アルキ
ル基、フェニル基及びシリル基からなる群から選ばれる
側鎖基を有し、結合単位（Ｓｉ−ＣＨ＿２）の全数対結
合単位（Ｓｉ−Ｓｉ）の全数の比が１：０〜２０の範囲
にある有機珪素重合体の珪素原子の少なくとも一部が、
石油系又は石炭系のピッチあるいはその熱処理物の芳香
族環と珪素−炭素連結基を介して結合したランダム共重
合体１００重量部、及び（ｉｉ）石油系又は石炭系ピッ
チを熱処理して得られるメソフェーズ状態又はメソフェ
ーズと光学的等方相との両相からなる多環状芳香族化合
物５〜５００００重量部を、 ２００〜５００℃の範囲の温度で加熱反応及び／又は加
熱溶融して、珪素含有多環状芳香族重合体を得る第１工
程、 上記珪素含有多環状芳香族重合体の紡糸原液を調製して
紡糸する第２工程、 該紡糸原糸を張力下あるいは無張力下で不融化する第３
工程、及び 不融化した前記紡糸繊維を真空中あるいは不活性ガス雰
囲気中で８００〜３０００℃の範囲の温度で焼成する第
４工程 からなることを特徴とする実質的に炭素、珪素、酸素か
らなる高強度・高弾性率無機繊維の製造方法。(2) (i) Mainly composed of a bonding unit (Si-CH_2), or a bonding unit (Si-CH_2) and a bonding unit (Si-Si), with hydrogen atoms, lower alkyl groups, phenyl groups and An organosilicon polymer having a side chain group selected from the group consisting of silyl groups, and in which the ratio of the total number of bonding units (Si-CH_2) to the total number of bonding units (Si-Si) is in the range of 1:0 to 20. At least some of the silicon atoms of
100 parts by weight of a random copolymer bonded to an aromatic ring of petroleum-based or coal-based pitch or a heat-treated product thereof via a silicon-carbon linking group, and (ii) obtained by heat-treating petroleum-based or coal-based pitch. 5 to 50,000 parts by weight of a polycyclic aromatic compound in a mesophase state or in both a mesophase and an optically isotropic phase is heat-reacted and/or heat-melted at a temperature in the range of 200 to 500°C to obtain a silicon-containing polycyclic compound. A first step of obtaining a cyclic aromatic polymer, a second step of preparing a spinning dope of the silicon-containing polycyclic aromatic polymer and spinning it, and a third step of infusibleizing the spun yarn under tension or without tension.
and a fourth step of firing the infusible spun fibers at a temperature in the range of 800 to 3000°C in vacuum or in an inert gas atmosphere. A method for producing high-strength, high-modulus inorganic fibers.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19997688 | 1988-08-12 | ||
| JP63-199976 | 1988-08-12 | ||
| JP63-234827 | 1988-09-21 | ||
| JP23482788 | 1988-09-21 | ||
| JP30688788 | 1988-12-06 | ||
| JP63-306887 | 1988-12-06 | ||
| JP1-142096 | 1989-06-06 | ||
| JP14209689 | 1989-06-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03104926A true JPH03104926A (en) | 1991-05-01 |
| JPH07103493B2 JPH07103493B2 (en) | 1995-11-08 |
Family
ID=27472428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1206640A Expired - Lifetime JPH07103493B2 (en) | 1988-08-12 | 1989-08-11 | High-strength, high-modulus inorganic fiber and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07103493B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004036073A (en) * | 2002-07-10 | 2004-02-05 | Advanced Composite Materials Corp | Silicon carbide fiber practically containing no whisker and method for producing the same |
| JPWO2010143608A1 (en) * | 2009-06-08 | 2012-11-22 | 株式会社超高温材料研究センター | COMPOSITE INORGANIC FIBER AND METHOD FOR PRODUCING SAME, AND COMPOSITE INORGANIC FIBER PRODUCT AND METHOD FOR PRODUCING SAME |
| US9688583B2 (en) | 2006-03-30 | 2017-06-27 | Advanced Composite Materials, Llc | Composite materials and devices comprising single crystal silicon carbide heated by electromagnetic radiation |
-
1989
- 1989-08-11 JP JP1206640A patent/JPH07103493B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004036073A (en) * | 2002-07-10 | 2004-02-05 | Advanced Composite Materials Corp | Silicon carbide fiber practically containing no whisker and method for producing the same |
| JP4612287B2 (en) * | 2002-07-10 | 2011-01-12 | アドヴァンスド・コンポジット・マテリアルズ・コーポレーション | Silicon carbide fiber substantially free of whiskers and method for producing the same |
| US9688583B2 (en) | 2006-03-30 | 2017-06-27 | Advanced Composite Materials, Llc | Composite materials and devices comprising single crystal silicon carbide heated by electromagnetic radiation |
| JPWO2010143608A1 (en) * | 2009-06-08 | 2012-11-22 | 株式会社超高温材料研究センター | COMPOSITE INORGANIC FIBER AND METHOD FOR PRODUCING SAME, AND COMPOSITE INORGANIC FIBER PRODUCT AND METHOD FOR PRODUCING SAME |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07103493B2 (en) | 1995-11-08 |
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