JPH0351319A - Treating agent for pitch-based carbon fiber - Google Patents
Treating agent for pitch-based carbon fiberInfo
- Publication number
- JPH0351319A JPH0351319A JP18507989A JP18507989A JPH0351319A JP H0351319 A JPH0351319 A JP H0351319A JP 18507989 A JP18507989 A JP 18507989A JP 18507989 A JP18507989 A JP 18507989A JP H0351319 A JPH0351319 A JP H0351319A
- Authority
- JP
- Japan
- Prior art keywords
- fibers
- pitch
- treating agent
- silicone oil
- treatment
- 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
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 35
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 26
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 26
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229920002545 silicone oil Polymers 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- -1 fatty acid amine salt Chemical class 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 6
- 239000000194 fatty acid Substances 0.000 claims abstract description 6
- 229930195729 fatty acid Natural products 0.000 claims abstract description 6
- 230000001804 emulsifying effect Effects 0.000 claims abstract 2
- 238000011282 treatment Methods 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 37
- 230000004927 fusion Effects 0.000 abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 229910002804 graphite Inorganic materials 0.000 abstract description 5
- 239000010439 graphite Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 abstract description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 abstract description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 239000011295 pitch Substances 0.000 description 22
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 238000003763 carbonization Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002074 melt spinning Methods 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 239000011269 tar Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 239000011300 coal pitch Substances 0.000 description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 239000011301 petroleum pitch Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- WYJZNQHLXZZSDH-UHFFFAOYSA-N C(CCCCCCCCCCCCC)(=O)O.CN(CCO)C Chemical compound C(CCCCCCCCCCCCC)(=O)O.CN(CCO)C WYJZNQHLXZZSDH-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Chemical group 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- GGKUSPVRJLZUBK-UHFFFAOYSA-N dodecanoate;2-hydroxyethyl(dimethyl)azanium Chemical compound C[NH+](C)CCO.CCCCCCCCCCCC([O-])=O GGKUSPVRJLZUBK-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000570 polyether Chemical group 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002569 water oil cream Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は石炭系ピッチ、石油系ピッチ、高分子焼成ピッ
チ等のピッチ類から炭素繊維を製造する際に、繊維の取
扱いを容易にすると同時に繊維相互間の接着や融着のな
い高品質の炭素繊維を製造する工程で使用されるピンチ
系炭素繊維用処理剤に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention facilitates the handling of fibers when producing carbon fibers from pitches such as coal-based pitch, petroleum-based pitch, and fired polymer pitch. This invention relates to a pinch-type carbon fiber processing agent used in the process of manufacturing high-quality carbon fibers without adhesion or fusion between fibers.
(従来の技術)
ピッチ系炭素繊維は、通常原料ピッチを溶融紡糸し、得
られたピッチ繊維を不融化処理及び炭化処理を行なうこ
とにより製造されている。(Prior Art) Pitch-based carbon fibers are usually produced by melt-spinning raw material pitch and subjecting the resulting pitch fibers to infusibility treatment and carbonization treatment.
ピッチ系炭素繊維は、ポリアクリロニトリル(PAN)
系等の炭素繊維に比較して高収率で工業的有利に製造で
きる利点がある反面、ピッチ繊維等が極めて脆弱なため
、不融化処理や炭化処理での取扱いが難しく、これらの
工程において繊維の毛羽立ち、ガイドローラーへの捲き
つき、糸切れ等を起こしやすい。更に不融化処理、炭化
処理時に繊維相互間の接着や融着が生じ、かつ得られた
炭素繊維に損傷を生じ易いという難点があった。Pitch-based carbon fiber is polyacrylonitrile (PAN)
Although pitch fibers have the advantage of being industrially advantageous and can be produced in higher yields than other carbon fibers, pitch fibers are extremely fragile and difficult to handle during infusibility and carbonization treatments. It is easy to cause fuzzing, wrapping around the guide roller, thread breakage, etc. Furthermore, during the infusibility treatment and carbonization treatment, adhesion or fusion between fibers occurs, and the obtained carbon fibers are easily damaged.
そこで、かかるピンチ系炭素繊維に特有の難点を解消し
て高品質のピッチ系炭素繊維を安定的に製造し得る方法
について種々検討し、処理剤として特定の物性を有する
シリコーンオイルを用いる方法(特開昭60−2468
19号公報)及びシリコーンオイル水エマルジョンを用
いる方法(特開昭61−70017号公報)について、
既に特許出願を行なっているものの、これらの処理剤で
は紡糸集束工程における繊維の毛羽立ち、ガイドローラ
ーへの捲きつき、糸切れ等の問題点は解決できたが、酸
化性雰囲気下、約り00℃〜約300℃程度の加熱帯域
で行なう不融化処理あるいはかかる不融化処理に後続す
る不活性雰囲気下で少なくとも400℃以上で加熱処理
する炭化処理において繊維相互間の融着や接着を十分に
解消するには未だ改善する余地を残していた。Therefore, we investigated various methods for stably producing high-quality pitch-based carbon fibers by solving the problems peculiar to pinch-based carbon fibers. Kaisho 60-2468
19) and the method using a silicone oil water emulsion (Japanese Patent Application Laid-Open No. 61-70017),
Although a patent application has already been filed, these processing agents were able to solve problems such as fuzzing of the fibers, winding around guide rollers, and yarn breakage during the spinning and convergence process, but they did not work properly in an oxidizing atmosphere at about 00°C. - Sufficiently eliminates fusion and adhesion between fibers during infusibility treatment performed in a heating zone of approximately 300°C or carbonization treatment performed at least at 400°C or higher in an inert atmosphere following such infusibility treatment. There was still room for improvement.
このような融着あるいは接着という現象の原因は、不融
化処理あるいは炭化処理等の加熱処理時に、処理剤に含
有される成分の一部が分解あるいはタール化することに
起因することが判明した。It has been found that the cause of such a phenomenon of fusion or adhesion is that some of the components contained in the processing agent decompose or turn into tar during heat treatment such as infusibility treatment or carbonization treatment.
そこで、かかる課題を解決するために、25℃ニオケる
粘度2〜20cs tのシリコーンオイルを、300℃
での加熱残量が5%以下であり、かつ30〜350℃で
の微分発熱曲線(DTA)において実質的に発熱ピーク
を有さない界面活性剤で水中に乳化した処理剤(特開昭
64−26720号公報)を提案した。Therefore, in order to solve this problem, silicone oil with a viscosity of 2 to 20 cst, which is hot at 25°C, was heated to 300°C.
A processing agent emulsified in water with a surfactant that has a heating residual amount of 5% or less at 30 to 350°C and has virtually no exothermic peak in the differential exothermic curve (DTA) at 30 to 350°C (JP-A-64 -26720) was proposed.
(発明が解決しようとする課題)
しかしながら、かかる処理剤は、繊維相互間の接着ある
いは融着については十分に改善されるものの、最終の製
品形態である繊維のストランド強度が十分に向上しない
という課題を残していた。(Problems to be Solved by the Invention) However, although such treatment agents can sufficiently improve adhesion or fusion between fibers, the problem is that the strand strength of the fibers in the final product form is not sufficiently improved. was left behind.
(課題を解決するための手段)
そこで、本発明者等は、かかる問題点を解決すべく鋭意
検討を行なった結果、ピッチ系炭素繊維製造工程で使用
される処理剤としては、25℃での粘度2〜20cst
のシリコーンオイルを特定の脂肪酸アミン塩で水中に乳
化したものを使用することにより、最終繊維のストラン
ド強度が大幅に向上するということを見い出し、従来の
課題を解決し本発明に到達した。すなわち、本発明の目
的は、ピンチ系炭素繊維を製造する際に繊維の毛羽立ち
、ローラーへの捲き付き、糸切れ等の問題は勿論のこと
、加熱処理時における繊維相互間の融着、接着等を解消
し、糸揃いの良好な高ストランド強度のピッチ系炭素繊
維を安定的に製造し得るための工程処理剤を提供するも
のである。(Means for Solving the Problems) Therefore, the present inventors conducted intensive studies to solve these problems, and as a result, they found that the treatment agent used in the pitch-based carbon fiber manufacturing process was Viscosity 2~20cst
We have discovered that the strand strength of the final fiber can be significantly improved by using a silicone oil emulsified in water with a specific fatty acid amine salt, and have solved the conventional problems and arrived at the present invention. That is, the purpose of the present invention is to solve not only problems such as fuzzing of fibers, sticking to rollers, and yarn breakage when producing pinch carbon fibers, but also problems such as fusion and adhesion between fibers during heat treatment. The purpose of the present invention is to provide a process treatment agent that can eliminate the above problems and stably produce pitch-based carbon fibers with good thread alignment and high strand strength.
かかる発明の目的は、ピンチ系炭素繊維を製造する工程
に使用される処理剤であって、該処理剤が25℃での粘
度2〜2 (lc s tのシリコーンオイルを下記一
般式(1)で示される脂肪酸アミン塩で水中に乳化した
状態のものであることを特徴とするピッチ系炭素繊維用
処理剤
(式中、
1
は、
炭素数5〜1
4のアルキル基を
表わし、R’1.R3及びR4は、炭素数4以下のアル
キル基又は−Ct Hs OH基を表わし、これらは互
いに異なっていてもよい。)
によって容易に達成される。The object of the invention is to provide a processing agent used in the process of producing pinch-type carbon fibers, wherein the processing agent is a silicone oil having a viscosity of 2 to 2 (lc st) at 25° C. according to the following general formula (1). A treatment agent for pitch-based carbon fibers characterized by being an emulsified state of a fatty acid amine salt in water (wherein 1 represents an alkyl group having 5 to 14 carbon atoms, and R'1 .R3 and R4 represent an alkyl group having 4 or less carbon atoms or a -CtHsOH group, which may be different from each other.).
以下本発明の詳細な説明する。本発明に用いられる原料
ピッチとしては、コールタールピンチ、石炭液化物等の
石炭系ピッチ、原油の常圧蒸留残油、減圧蒸留残油、ま
たはその熱処理物、ナフサの熱分解副生タールの熱処理
物等の石油系ピッチ及び合成樹脂や天然樹脂を乾留する
ことによって得られる高分子焼成ピッチ等が挙げられる
。The present invention will be explained in detail below. The raw material pitch used in the present invention includes coal tar pinch, coal-based pitch such as coal liquefied product, atmospheric distillation residue of crude oil, vacuum distillation residue, or heat-treated products thereof, and heat treatment of naphtha pyrolysis byproduct tar. Examples thereof include petroleum-based pitch such as synthetic resin and calcined polymer pitch obtained by carbonizing synthetic resin or natural resin.
原料ピッチの溶融紡糸はポリエステル、ポリアミドの溶
融紡糸と同様に紡糸口金を通して気相中に押出すことに
より行なうことができる。好ましくはピッチをエクスト
ルーダーその他で溶融して下向きの紡糸口金から気相中
に押し出し冷却固化させる方法を採用する。紡糸口金と
しては吐出孔の孔径が0.1〜0.3mm程度のもの−
を用いる。紡糸口金の温度は原料ピッチの種類に依存し
紡糸に適当な溶融粘度を考慮して決められるが、通常は
250〜350℃の範囲が適当である。紡糸口金の下に
は保温筒を設けておくと紡糸状態の安定化に有効である
。Melt spinning of raw material pitch can be carried out by extruding it into the gas phase through a spinneret in the same manner as melt spinning of polyester and polyamide. Preferably, a method is employed in which the pitch is melted using an extruder or the like, extruded through a downward spinneret into the gas phase, and then cooled and solidified. The spinneret is one with a discharge hole diameter of about 0.1 to 0.3 mm.
Use. The temperature of the spinneret depends on the type of raw material pitch and is determined in consideration of the melt viscosity suitable for spinning, but it is usually within the range of 250 to 350°C. Providing a heat insulating cylinder under the spinneret is effective in stabilizing the spinning state.
本発明は、上記の方法で得られたピンチ繊維や不融化処
理された繊維等に対して付着使用するシリコーンオイル
を界面活性剤により水中に分散した処理剤であるが、シ
リコーンオイルとしては2〜20cst (25℃)
のジメチルポリシロキサンあるいは種々の変性ポリシロ
キサンを用いるのが重要である。ここで2cst(25
℃)未満では揮発性が高い為、処理剤を炭素繊維上に添
着した後、処理剤が揮散してしまい、処理剤としての充
分な効果を示さないので好ましくなく、又20cst(
25℃)より大きいと、不融化時あるいは炭化時に炭素
繊維の単糸同志の融着を引き起し、繊維物性を低下させ
るので好ましくない。The present invention is a treatment agent prepared by dispersing silicone oil in water using a surfactant to adhere to the pinched fibers obtained by the above method or the fibers treated to make it infusible. 20cst (25℃)
It is important to use dimethylpolysiloxane or various modified polysiloxanes. Here 2 cst (25
If the treatment agent is less than 20 cst (°C), it is undesirable because it is highly volatile, so the treatment agent will volatilize after being attached to the carbon fiber, and it will not have sufficient effect as a treatment agent.
If the temperature is higher than 25°C, it is not preferable because it causes fusion of carbon fiber single filaments during infusibility or carbonization, resulting in deterioration of fiber properties.
かかるシリコーンオイルとしては、具体的には、例えば
、ジメチルポリシロキサン、メチルフヱニルポリシロキ
サン、ハイドロジエンポリシロキサンが挙げられるが、
その他エポキシ基、エチル、プロピル基等のアルキル基
、アミン基、カルボキシル基、アルコール、フェニル基
、ポリエーテル基の1種又は2種以上で変性したものが
用いられる。また、これらのシリコーンオイルは、1種
又は2種以上の混合物を用いてもよい。Specific examples of such silicone oils include dimethylpolysiloxane, methylphenylpolysiloxane, and hydrogenpolysiloxane, but
In addition, those modified with one or more of alkyl groups such as epoxy groups, ethyl and propyl groups, amine groups, carboxyl groups, alcohols, phenyl groups, and polyether groups are used. Moreover, these silicone oils may be used alone or in a mixture of two or more thereof.
上記シリコーンオイルを乳化する界面活性剤としては、
下記一般式(1)で示される脂肪酸アミン塩を使用する
。The surfactant that emulsifies the silicone oil is as follows:
A fatty acid amine salt represented by the following general formula (1) is used.
式中、RI=炭素数5〜14のアルキル基、R2、R:
l 、 R4=炭素数4以下のアルキル基又は−C2H
s OH基を表わし、これらは互いに同じものでもよい
し、異なっていてもよい。In the formula, RI=alkyl group having 5 to 14 carbon atoms, R2, R:
l, R4 = alkyl group having 4 or less carbon atoms or -C2H
s Represents an OH group, and these may be the same or different.
好ましくは、R1は炭素数8〜14の高級アルキル基、
R1、R,3、R4では少なくともひとつが−C2Hs
OH基であり、他がメチル又はエチル基の様な炭素数
の少ないアルキル基がよい。Preferably, R1 is a higher alkyl group having 8 to 14 carbon atoms,
At least one of R1, R, 3, and R4 is -C2Hs
It is preferably an OH group, and the other is an alkyl group with a small number of carbon atoms such as a methyl or ethyl group.
具体的には、ラウリン酸ジメチルエタノールアミン塩あ
るいはミリスチン酸ジメチルエタノールアミン塩が好ま
しい。Specifically, lauric acid dimethylethanolamine salt or myristic acid dimethylethanolamine salt is preferred.
以上の界面活性剤の使用量は、シリコーンオイルに対し
て0.1%〜20%の使用が好ましい。0゜1%未満で
はシリコーンオイルの乳化物が生じず、20%より多い
と不融化等の加熱処理後の炭素繊維性状に悪影響を及ぼ
す。The above surfactant is preferably used in an amount of 0.1% to 20% based on the silicone oil. If it is less than 0.1%, no emulsion of silicone oil will be formed, and if it is more than 20%, it will have an adverse effect on the carbon fiber properties after heat treatment such as infusibility.
又、本発明の処理剤に、固体微粒子を分散・混合してお
くと繊維相互間の接着もしくは融着を防止する効果が増
大するので好ましい。Further, it is preferable to disperse and mix solid fine particles into the treatment agent of the present invention, since this increases the effect of preventing adhesion or fusion between fibers.
固体微粒子としては、好ましくは炭素質微粒子、無機酸
化物微粒子、無機塩微粒子あるいはこれらの混合物が用
いられるが、具体的には、黒鉛、カーボンブラック、シ
リカ、炭酸カルシウム、酸化チタン、タルク、クレー、
硫酸バリウム、チタン酸カリ、二硫化モリブデン等の微
細な粒子が用いられるが、中でも黒鉛、カーボンブラッ
ク、ソリ力、炭酸カルシウム、の使用が好ましい。これ
らの粒子をピンチ繊維の間に好ましく浸透させるために
は、平均粒子径が15μ以下、好ましくは0゜01〜5
μ、更に好ましくは0.05〜3μの大きさのものが用
いられる。As solid particles, carbonaceous particles, inorganic oxide particles, inorganic salt particles, or mixtures thereof are preferably used, and specifically, graphite, carbon black, silica, calcium carbonate, titanium oxide, talc, clay,
Fine particles of barium sulfate, potassium titanate, molybdenum disulfide, and the like are used, and among them, graphite, carbon black, warping force, and calcium carbonate are preferably used. In order to preferably infiltrate these particles between the pinch fibers, the average particle diameter is 15 μm or less, preferably 0°01 to 5 μm.
A size of μ, more preferably 0.05 to 3 μ is used.
黒鉛は天然又は合成の何れでも使用できる。カーボンブ
ラックは、ファーネスブランク、サーマルブラック、ラ
ンフブラック、コンタクトブランク等種々の方法で得ら
れたものが用いられる。シリカは、例えばハロゲン化ケ
イ素の熱分解、ケイ酸ソーダの酸分解等の乾式法又は湿
式法で得られるヒユームドシリカ又はホワイトカーボン
と称されるシリカ微粒子が用いられる。炭酸カルシウム
は、石灰石を機械粉砕又は化学的沈降法で処理して得ら
れる極微細沈降製炭酸カルシウム、コロイド性炭酸カル
シウム、活性化炭酸カルシウムが用いられる。Graphite can be either natural or synthetic. Carbon black obtained by various methods such as furnace blank, thermal black, lump black, and contact blank can be used. As the silica, fine silica particles called fumed silica or white carbon, which are obtained by a dry method or a wet method such as thermal decomposition of silicon halide or acid decomposition of sodium silicate, are used. As the calcium carbonate, ultrafine precipitated calcium carbonate, colloidal calcium carbonate, and activated calcium carbonate obtained by mechanically crushing limestone or treating it with a chemical precipitation method are used.
タルク、クレー、酸化チタン、硫酸バリウム、チタン酸
カリ、二硫化モリブデンは、プラスチックやゴム等の充
填剤として市販されているものの中、前記の粒子径を有
する微細なものが用いられる。Talc, clay, titanium oxide, barium sulfate, potassium titanate, and molybdenum disulfide are commercially available as fillers for plastics, rubber, etc., and those having the above-mentioned particle size are used.
処理剤を繊維に付着させる方法としては、スプレーによ
り吹付ける方法、ローラーに付けて接触させる方法、浸
漬させる方法等がある。Methods for attaching the treatment agent to the fibers include a method of spraying, a method of applying the treatment agent to the fibers, and a method of bringing the treatment agent into contact with the fibers, a method of immersing the fibers, and the like.
処理剤の付着量としては、オイル分として0.02重量
%〜15重量%付着させることが好ましい。The amount of the treatment agent deposited is preferably 0.02% to 15% by weight in terms of oil content.
0゜02重量%以下では、繊維の集束性が悪く、15重
量%以上では不融化後の糸外状に悪影響を及ぼす。If it is less than 0.02% by weight, the fiber cohesiveness will be poor, and if it is more than 15% by weight, it will adversely affect the outer shape of the fiber after infusibility.
処理剤が付着され、集束されたピッチ繊維は周知の方法
に従って不融化処理及び炭化処理が行なわれる。例えば
、不融化処理は、繊維を酸素、オゾン、空気、窒素酸化
物、ハロゲン、亜硫酸ガス等の酸化性雰囲気下、150
〜360℃の温度に5分〜10時間加熱することによっ
て行なわれる。The pitch fibers to which the treatment agent has been attached and bundled are subjected to infusibility treatment and carbonization treatment according to well-known methods. For example, the infusibility treatment is carried out by subjecting the fibers to 150%
This is done by heating to a temperature of ~360°C for 5 minutes to 10 hours.
又、不融化後の炭素繊維に該処理剤を工程油として使用
することもできる。炭化処理は繊維を窒素、アルゴン等
の不活性ガス雰囲気下、400〜2500℃の温度に0
.5分〜10時間加熱することによって行なわれる。Moreover, the treatment agent can also be used as a process oil for carbon fibers after infusibility. Carbonization treatment involves heating the fibers to a temperature of 400 to 2500°C in an inert gas atmosphere such as nitrogen or argon.
.. This is done by heating for 5 minutes to 10 hours.
さらに黒鉛化処理を行なう場合には、2500〜350
0℃の温度に1秒〜1時間程度加熱保持すればよい。ま
た不融化、炭化あるいは黒鉛化処理の際、必要であれば
収縮や変形等を防止する目的で、被処理体に若干の荷重
あるいは張力をかけておくこともできる。When further graphitizing treatment is performed, 2500 to 350
What is necessary is just to heat and hold at the temperature of 0 degreeC for about 1 second to 1 hour. Furthermore, during the infusibility, carbonization, or graphitization treatment, a slight load or tension may be applied to the object to be treated, if necessary, in order to prevent shrinkage, deformation, etc.
このようにして得られた炭素繊維又は黒鉛繊維は、通常
解繊した後、それぞれの用途に用いられる。The carbon fibers or graphite fibers obtained in this way are usually used for their respective purposes after being defibrated.
(実施例)
次に本発明を実施例により更に具体的に説明するが本発
明はその要旨をこえない限り以下の実施例に限定される
ものではない。(Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.
実施例1〜3
タール系の原料ピッチを防止口金温度330℃で気相中
へ溶融紡糸し、得られた糸径10μ、120フイラメン
トのピッチ繊維に、第1表に示す処理剤をオイリングガ
イドを用いて付着させ集束した0次いで集束繊維を空気
中に於いて80℃に30分間保持して乾燥した0次いで
150℃より350℃まで2時間40分を要して昇温し
た後、その温度に30分間保持して不融化処理を行なっ
た。その後アルゴン中において、室温より1400℃ま
でに2時間20分を要して昇温した後その温度に1時間
保持して炭化処理を行ない更に、炭化繊維を1000℃
から2500℃まで1時間15分で昇温し、90m1n
保持し黒鉛化糸を得た。Examples 1 to 3 Tar-based raw material pitch was melt-spun into the gas phase at a preventive spindle temperature of 330°C, and the resulting pitch fibers with a yarn diameter of 10μ and 120 filaments were coated with the treatment agent shown in Table 1 using an oiling guide. The bundled fibers were then dried by holding them at 80°C for 30 minutes in the air.Then, the temperature was raised from 150°C to 350°C over a period of 2 hours and 40 minutes, and then the temperature was increased to 350°C. The mixture was held for 30 minutes to perform infusibility treatment. After that, the temperature was raised from room temperature to 1400°C in argon over 2 hours and 20 minutes, and then maintained at that temperature for 1 hour to carry out carbonization treatment.
to 2500℃ in 1 hour 15 minutes, 90ml
A graphitized thread was obtained.
炭素繊維製造工程における糸の集束状態、不融化繊維の
性状、単糸の融着状態、黒鉛化糸ストランド強度を測定
した。その結果を第1表に記載する。The bundled state of threads, the properties of infusible fibers, the fused state of single threads, and the strength of graphitized thread strands during the carbon fiber manufacturing process were measured. The results are listed in Table 1.
比較例1〜4
集束剤種を変えて実施例1と同様に実施した結果を第1
表に示す。Comparative Examples 1 to 4 The results were carried out in the same manner as in Example 1 by changing the type of sizing agent.
Shown in the table.
第1表の結果からも、本発明に係る処理剤の優れた諸性
能は明らかである。From the results in Table 1, it is clear that the processing agent according to the present invention has excellent performance.
(発明の効果)
特定の物性を有するシリコーンオイルを特定の物性を有
する界面活性剤で水中に分散してなる本発明のピッチ系
炭素繊維用処理剤を用いることにより、簡単な操作で脆
弱な繊維の取り扱いを容易ならしめると同時に繊維間相
互間の接着や融着が防止され、ストランド強度の良好な
ピッチ系炭素繊維を連続フィラメント状で工業的有利な
条件下に製造できる。(Effects of the invention) By using the treatment agent for pitch-based carbon fibers of the present invention, which is prepared by dispersing silicone oil having specific physical properties in water with a surfactant having specific physical properties, brittle fibers can be treated with a simple operation. At the same time, it is possible to easily handle the fibers, prevent adhesion or fusion between the fibers, and produce pitch-based carbon fibers with good strand strength in the form of continuous filaments under industrially advantageous conditions.
Claims (2)
理剤であって、該処理剤が25℃での粘度2〜20cs
tのシリコーンオイルを、下記一般式( I )で示され
る脂肪酸アミン塩で水中に乳化した状態のものであるこ
とを特徴とするピッチ系炭素繊維用処理剤。▲数式、化
学式、表等があります▼( I ) (式中、R^1は炭素数5〜14のアルキル基を表わし
、R^2、R^3及びR^4は、炭素数4以下のアルキ
ル基又は−C_2H_5OH基を表わし、これらは互い
に異なっていてもよい。)(1) A processing agent used in the process of producing pitch-based carbon fiber, wherein the processing agent has a viscosity of 2 to 20 cs at 25°C.
1. A treatment agent for pitch-based carbon fibers, which is obtained by emulsifying a silicone oil of t in water with a fatty acid amine salt represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 represents an alkyl group having 5 to 14 carbon atoms, and R^2, R^3, and R^4 represent an alkyl group having 4 or less carbon atoms. represents an alkyl group or a -C_2H_5OH group, which may be different from each other.)
活性剤の添加量を0.1%〜20wt%とする請求項1
記載の処理剤。(2) Claim 1 in which the amount of surfactant added to the silicone oil in the processing agent is 0.1% to 20wt%.
Treatment agent as described.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1185079A JP2945415B2 (en) | 1989-07-18 | 1989-07-18 | Pitch-based carbon fiber treatment agent |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1185079A JP2945415B2 (en) | 1989-07-18 | 1989-07-18 | Pitch-based carbon fiber treatment agent |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0351319A true JPH0351319A (en) | 1991-03-05 |
JP2945415B2 JP2945415B2 (en) | 1999-09-06 |
Family
ID=16164453
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1185079A Expired - Fee Related JP2945415B2 (en) | 1989-07-18 | 1989-07-18 | Pitch-based carbon fiber treatment agent |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2945415B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010007216A (en) * | 2008-06-30 | 2010-01-14 | Mitsubishi Rayon Co Ltd | Oil solution composition for carbon fiber precursor acrylic fiber, carbon fiber precursor acrylic fiber bundle, and method of production thereof |
CN104452270A (en) * | 2014-12-19 | 2015-03-25 | 四川创越炭材料有限公司 | Spinning finish for asphalt carbon fiber |
CN104562299A (en) * | 2014-12-29 | 2015-04-29 | 四川创越炭材料有限公司 | Preparation method for high-dispersity carbon fiber |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01221578A (en) * | 1988-02-24 | 1989-09-05 | Takemoto Oil & Fat Co Ltd | Oiling agent for producing carbon fiber |
-
1989
- 1989-07-18 JP JP1185079A patent/JP2945415B2/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01221578A (en) * | 1988-02-24 | 1989-09-05 | Takemoto Oil & Fat Co Ltd | Oiling agent for producing carbon fiber |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010007216A (en) * | 2008-06-30 | 2010-01-14 | Mitsubishi Rayon Co Ltd | Oil solution composition for carbon fiber precursor acrylic fiber, carbon fiber precursor acrylic fiber bundle, and method of production thereof |
CN104452270A (en) * | 2014-12-19 | 2015-03-25 | 四川创越炭材料有限公司 | Spinning finish for asphalt carbon fiber |
CN104562299A (en) * | 2014-12-29 | 2015-04-29 | 四川创越炭材料有限公司 | Preparation method for high-dispersity carbon fiber |
Also Published As
Publication number | Publication date |
---|---|
JP2945415B2 (en) | 1999-09-06 |
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