JPS61215772A - Production of carbon fiber code - Google Patents
Production of carbon fiber codeInfo
- Publication number
- JPS61215772A JPS61215772A JP60053323A JP5332385A JPS61215772A JP S61215772 A JPS61215772 A JP S61215772A JP 60053323 A JP60053323 A JP 60053323A JP 5332385 A JP5332385 A JP 5332385A JP S61215772 A JPS61215772 A JP S61215772A
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- fiber bundle
- coating material
- aqueous dispersion
- fibers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000049 Carbon (fiber) Polymers 0.000 title claims description 34
- 239000004917 carbon fiber Substances 0.000 title claims description 34
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000006185 dispersion Substances 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 31
- 238000000576 coating method Methods 0.000 claims description 29
- 239000011248 coating agent Substances 0.000 claims description 28
- 239000003822 epoxy resin Substances 0.000 claims description 17
- 229920000647 polyepoxide Polymers 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 229920000126 latex Polymers 0.000 claims description 13
- 239000004816 latex Substances 0.000 claims description 10
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000835 fiber Substances 0.000 description 47
- 229920001228 polyisocyanate Polymers 0.000 description 13
- 239000005056 polyisocyanate Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 8
- 239000005060 rubber Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229960001755 resorcinol Drugs 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- -1 tolylene isocyanate Chemical class 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- QUEICCDHEFTIQD-UHFFFAOYSA-N buta-1,3-diene;2-ethenylpyridine;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=N1 QUEICCDHEFTIQD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- USDNTLSSMWDFHG-UHFFFAOYSA-N 2-ethenylpyridine;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=N1 USDNTLSSMWDFHG-UHFFFAOYSA-N 0.000 description 1
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- DYBIGIADVHIODH-UHFFFAOYSA-N 2-nonylphenol;oxirane Chemical compound C1CO1.CCCCCCCCCC1=CC=CC=C1O DYBIGIADVHIODH-UHFFFAOYSA-N 0.000 description 1
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 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 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920003006 Polybutadiene acrylonitrile Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 229960000878 docusate sodium Drugs 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Tyre Moulding (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔技術分野〕
本発明は、炭素繊維束に有機系被覆材を付着させて炭素
繊維コードを製造する方法に関するものである。本発明
により得られる製品は、特にゴムやプラスチックスと複
合化して浸れた接着性を発揮し、タイレなどの工業材料
の分野で使用される。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for producing a carbon fiber cord by attaching an organic coating material to a carbon fiber bundle. The products obtained according to the invention exhibit excellent adhesion properties, especially when composited with rubber or plastics, and are used in the field of industrial materials such as tiles.
近年、炭素繊維（炭素含有量９５重量％以上の高い比強
度、比弾性率を有していることから、長繊維、短繊維の
形で各種のマトリックス材と複合化されて使用されてい
る。特に、レゾルシ素繊維束は、ゴムやプラスチックス
の補強材として使用されタイヤ、ベルトなどの工業材料
、スポーツ用品をはじめ航空宇宙分野にも用途が拡がっ
ている。In recent years, carbon fibers (because they have a high specific strength and specific modulus with a carbon content of 95% by weight or more) have been used in the form of long fibers or short fibers in composites with various matrix materials. In particular, resorcinol fiber bundles are used as reinforcing materials for rubber and plastics, and their applications are expanding to industrial materials such as tires and belts, sporting goods, and the aerospace field.
一般に、これら被覆材は炭素繊維の束としての取り扱い
易さを改善するだけでなく、炭素繊維相互を十分に接着
させるためのものである。In general, these coating materials not only improve the ease of handling the carbon fibers as a bundle, but also allow the carbon fibers to be sufficiently bonded to each other.
その被覆方法としては、例えば繊維束を被覆材の水系若
しくは有機系の分散液は又は同溶液に浸漬するか、ある
いは分散液又は溶液をスプレーするなどの方法が用いら
れている。しかしながら、特に水分散液の形で炭素繊維
束に被覆する場合炭素繊維の太さが通常１５ミクロン以
下と極めて細いのに対し被覆材の粒径の大きさが５〜の
ため、被覆材を炭素繊維束の外部に付着させることは可
能であるが、繊維内部にまで含浸させ、構成する単ｍＭ
に被覆させることが難しい傾向にあった。このようにし
て得られた被覆材を有する炭素繊維束を取り扱うと、被
覆されていない繊維束内部にある単繊維が露出され易く
、繊維束の毛羽が増大する傾向となる。また、マトリッ
クスと複合化した場合には、繊維束内部にある単ｍ雑が
被覆されていないために、接着性が低くなり、従って、
ａｍの特性を充分発揮し得ないという欠点を示す。As a coating method, for example, the fiber bundle is immersed in an aqueous or organic dispersion of the coating material, or the fiber bundle is sprayed with the dispersion or solution. However, especially when coating carbon fiber bundles in the form of an aqueous dispersion, the thickness of carbon fibers is usually extremely thin, 15 microns or less, whereas the particle size of the coating material is 5 to 5 microns. Although it is possible to attach it to the outside of the fiber bundle, it is possible to impregnate the inside of the fiber to form a monomM
It has tended to be difficult to coat the When a carbon fiber bundle having a coating material thus obtained is handled, the uncoated single fibers inside the fiber bundle are likely to be exposed, and the fuzz of the fiber bundle tends to increase. In addition, when composited with a matrix, the adhesion becomes low because the monomers inside the fiber bundle are not covered.
This shows the drawback that the characteristics of am cannot be fully exhibited.
特にＲＦＬを被覆材とし水媒体で付与する場合は、！Ｉ
！雑束内部にまで含浸させることが難しく、得られた炭
素繊維束（以下ＣＦコードと称する）の強度やゴムとの
接着力は極めて低い値しか得られないという欠点があっ
た。Especially when applying RFL as a coating material using an aqueous medium! I
! It is difficult to impregnate the inside of the miscellaneous bundle, and the resulting carbon fiber bundle (hereinafter referred to as CF cord) has the disadvantage that the strength and adhesive strength with rubber are only extremely low.
本発明者らは、上記のごとき欠点を有しない、 、被
覆材を有する炭素繊維束をつくることについて検討の結
果、本発明に至ったものである。The present inventors have arrived at the present invention as a result of studies on creating a carbon fiber bundle having a covering material that does not have the above-mentioned drawbacks.
特に、本発明は、ＲＦＬやエポキシ樹脂の水分散液を用
いて、炭素ｓ１Ｍ束内部に含浸させ、構成される単繊維
に充分に付与することにより、毛羽を抑制した１１８束
とゴムとの高い接着力を有するＣＦコードを作る方法を
提供するものである。In particular, the present invention uses an aqueous dispersion of RFL or epoxy resin to impregnate the inside of the carbon s1M bundle and sufficiently apply it to the constituent single fibers, thereby making it possible to combine the 118 bundle with suppressed fluff and rubber. The present invention provides a method for making a CF cord with adhesive strength.
本発明は、炭素繊維束に有機系被覆材を含浸させて炭素
繊維コードをｙＪ造するに当り、該被覆材の水分散液に
炭素繊維束を浸漬し両者間に直流電流を通すことを特徴
とする炭素繊維コードの製造方法である。The present invention is characterized in that when a carbon fiber cord is manufactured by impregnating a carbon fiber bundle with an organic coating material, the carbon fiber bundle is immersed in an aqueous dispersion of the coating material and a direct current is passed between the two. This is a method for manufacturing carbon fiber cord.
本発明における炭素繊維束は、アクリロニトリルを主成
分とする公知の重合体繊維を空気中２００〜３００℃に
て０．１〜１００分間酸化処理したのち、窒素又は不活
性ガス中６００〜３０００℃で焼成して得られる公知の
炭素繊維の束であり、また、石油又は石炭のピッチを繊
維状となし不融化処理したのち６００〜３０００℃で窒
素、アルゴン、ヘリウム等の雰囲気中で焼成して得られ
る公知の炭素繊維の束である。このものは、炭素含有量
８０重置火以上で、断面積２Ｘ１０ ’〜５Ｘ １０
１０−６ＩＩ１を有する単ｍ雑の１００〜１００，００
０本から構成された繊維束である。特に好ましいものは
、体積電気抵抗値１０”〜１０−４ΩＣｒａを有し、強
度１００ｋｏｆ／ ｌｌ１ｍ’以上、弾性率１０ＸＩＯ
” ｋｇｒ ／Ｉ１ｍ’以上の繊維束である。The carbon fiber bundle in the present invention is obtained by oxidizing known polymer fibers containing acrylonitrile as a main component at 200 to 300°C in air for 0.1 to 100 minutes, and then oxidizing the fibers at 600 to 3000°C in nitrogen or inert gas. It is a known bundle of carbon fibers obtained by firing, and it is also obtained by turning petroleum or coal pitch into a fiber, treating it to infusible, and then firing it at 600 to 3000°C in an atmosphere of nitrogen, argon, helium, etc. This is a bundle of known carbon fibers. This product has a carbon content of 80 or more and a cross-sectional area of 2X10' to 5X10
100-100,00 of single m miscellaneous with 10-6II1
It is a fiber bundle composed of 0 fibers. Particularly preferable ones have a volume electrical resistance value of 10" to 10-4 ΩCra, a strength of 100 kof/ll1 m' or more, and an elastic modulus of 10XIO.
"kgr/I1m' or more fiber bundle.
本発明に用いられる有機系被覆材は、有機繊維や炭素繊
維のタイヤコードを得るための処理剤や炭素繊維のサイ
ジング剤に用いられる処理剤で、水溶液又は水分散液と
して得られるものから選ばれる。特に好ましいものは、
ＲＦＬ （レゾルシンホルマリンラテックス）、エポキ
シ樹脂、ポリイソシアネートｅ＋＋ｍ含有ブロック化合
物の単独又はこれらの混合物で、ＲＦＬを有効成分とし
て１０重量％以上含んだものである。ＲＦＬは、レゾル
シンホルマリン初期綜合物とゴムラテックスの混合水分
散液の形で使用され、この場合、レゾルシンホルマリン
初期縮合物とゴムラテックスの重量比を５／ １００〜
３０／ １００とし、且つレゾルシンとホルマリンのモ
ル比を１／ ０，５〜１／３としたものが好ましい。The organic coating material used in the present invention is a treatment agent used for obtaining tire cords made of organic fibers or carbon fibers or a sizing agent for carbon fibers, and is selected from those obtained as an aqueous solution or an aqueous dispersion. . Particularly preferred are
RFL (resorcin formalin latex), epoxy resin, polyisocyanate e++m-containing block compound, singly or as a mixture thereof, containing 10% by weight or more of RFL as an active ingredient. RFL is used in the form of a mixed aqueous dispersion of resorcin formalin initial condensate and rubber latex, and in this case, the weight ratio of resorcin formalin initial condensate and rubber latex is 5/100 ~
Preferably, the ratio is 30/100, and the molar ratio of resorcinol to formalin is 1/0.5 to 1/3.
また、ゴムラテックスは、スチレン・ブタジェン共重合
ラテックス、ビニルピリジンスチレン・ブタジェン共重
合ラテックス、天然ゴムラテックス、アクリロニトリル
ブタジェンゴムラテックス、クロロブレンゴムラテック
ス等が好ましく、マトリックスのゴム材に応じて単独又
は併用して使用する。これらの中で特にビニルピリジン
スチレン・ブタジェン共重合体ラテックスを用いること
が１ｍ好ましい。The rubber latex is preferably styrene/butadiene copolymer latex, vinylpyridine styrene/butadiene copolymer latex, natural rubber latex, acrylonitrile butadiene rubber latex, chloroprene rubber latex, etc., which may be used alone or in combination depending on the rubber material of the matrix. and use it. Among these, it is particularly preferable to use vinylpyridine styrene-butadiene copolymer latex.
また、エポキシ樹脂は、分子中に少くとも１個のエポキ
シ基を有するもので、ビスフェノール系、フェノールノ
ボラック系、ポリフェノール系、含窒素エポキシ系など
公知のエポキシ樹脂である。好ましくはビスフェノール
Ａとエピクロルヒドリンとの反応物、ビスフェノールＡ
又はハロゲン化ビスフェノールＡとアルキレンオキシド
とを酸又はアルカリ触媒下で反応さじて得られるポリエ
ーテル型ポリグリシジルエーテル／芳香族多価アルコー
ル又は芳香族カルボン酸とエピクロルヒドリンとを反応
させて得られるポリグリシジルエーテル／グリセリント
リメチＯ−ルブロバン、ブタンジオール、ポリアルキレ
ングリコールなどの脂肪族多価アルコール又はポリエー
テルのポリグリシジルエーテルなどである。Further, the epoxy resin has at least one epoxy group in its molecule, and is a known epoxy resin such as a bisphenol type, a phenol novolac type, a polyphenol type, or a nitrogen-containing epoxy type. Preferably a reaction product of bisphenol A and epichlorohydrin, bisphenol A
or polyether-type polyglycidyl ether obtained by reacting halogenated bisphenol A and alkylene oxide under an acid or alkali catalyst/polyglycidyl ether obtained by reacting aromatic polyhydric alcohol or aromatic carboxylic acid with epichlorohydrin /Glycerin trimethy O-rubroban, butanediol, aliphatic polyhydric alcohol such as polyalkylene glycol, or polyglycidyl ether of polyether.
また、両末端にカルボキシル基を有するポリブタジェン
、イソプレン、ポリブタジェンアクリロニトリル重合物
と二官能以上のエポキシ化合物とを反応させて得られる
エポキシ樹脂である。Moreover, it is an epoxy resin obtained by reacting a polybutadiene, isoprene, or polybutadiene acrylonitrile polymer having carboxyl groups at both ends with a difunctional or higher-functional epoxy compound.
さらに、ポリイソシアネート樹脂含有ブロック化合物で
あって、このものは、ポリイソシアネート化合物とブロ
ック化剤との付加化合物である。Furthermore, there is a polyisocyanate resin-containing blocking compound, which is an addition compound of a polyisocyanate compound and a blocking agent.
ポリイソシアネート化合物としては、例えば、トリレン
イソシアネート、メタフェニレンジイソシアネート、ジ
フェニルメタンジイソシアネート、ヘキサメチレンジイ
ソシアネート、ポリメチレンポリフェニルイソシアネー
ト、トリフェニルメタントリイソシアネートなどのポリ
イソシアネート或いはこれらポリイソシアネートとトリ
メチロールプロパン、ペンタエリスリトールなどの活性
水素原子を２個以上有する化合物とを反応させて得られ
るポリアルキレングリコールアダクトポリイソシアネー
トであり、特に好ましくは、トリレンジイソシアネート
、ジフェニルメタンジイソシアネート、ポリメチレンポ
リフェニルイソシアネートなどの芳香族ポリイソシアネ
ートである。また、ブロック化剤としてはフェノール、
チオフェノール、クレゾール、レゾルシノールなどのフ
ェノール類、１−ブタノール、ｔ−ペンタノールなどの
第３級アルコール類、ジフェニルアミン、キシリジンな
どの芳香族第２級アミン類、フタル酸イミドなとのイミ
ド類などである。Examples of the polyisocyanate compound include polyisocyanates such as tolylene isocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenylisocyanate, and triphenylmethane triisocyanate, or these polyisocyanates and trimethylolpropane, pentaerythritol, etc. A polyalkylene glycol adduct polyisocyanate obtained by reacting with a compound having two or more active hydrogen atoms, particularly preferably aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and polymethylene polyphenylisocyanate. . In addition, as a blocking agent, phenol,
Phenols such as thiophenol, cresol, and resorcinol, tertiary alcohols such as 1-butanol and t-pentanol, aromatic secondary amines such as diphenylamine and xylidine, and imides such as phthalic acid imide. be.
本発明において、エポキシ樹脂やポリイソシアネート樹
脂含有ブロック化合物のうち水溶性のものは、主にＲＦ
Ｌなどの水分散液に混合して使われ、水不溶性のものは
、単独又は必要に応じて互いに混合し、そのまま、或い
は少凹の溶媒に溶解したものを公知の乳化剤、例えばア
ルキルベンゼンスルホン酸ソーダ、ジオクチルスルホサ
クシネートソーダ、ノニルフェノールエチレンオキシド
付加物等を用いて乳化し水に分散して用いられる。In the present invention, water-soluble block compounds containing epoxy resins and polyisocyanate resins are mainly used for RF
It is used by mixing with an aqueous dispersion such as L, and water-insoluble ones can be used alone or mixed with each other if necessary, and can be used as is or dissolved in a slightly diluted solvent with a known emulsifier, such as sodium alkylbenzenesulfonate. It is used by emulsifying it with , dioctyl sulfosuccinate soda, nonylphenol ethylene oxide adduct, and dispersing it in water.
水８分散液は、単独或いは互いに混合して用いられる。The water dispersions may be used alone or in admixture with each other.
そして、炭素繊維を被覆材の水分散液に浸漬し両者間に
直流電流を通して該被覆材を該１８８束に付着させる。Then, the carbon fibers are immersed in an aqueous dispersion of the coating material, and a direct current is passed between them to attach the coating material to the 188 bundles.
浸漬は、該被覆材の水分散液の浴にバッチ又は連続的に
ローラーを介して通す方法にて行うが、繊維束の内部へ
の含浸を高めるため、また効率的に処理するためには、
連続的に処理することが特に好ましい。′Ｒ流を該ｍ雑
束と該被覆材の水分散液の間で効率的に通すことが、該
ｌＩＨ束内部への含浸性を高めるために好ましく、その
ためには、該水分散液と該繊維束の間でのみ電流が通る
構造の設備を用いることが必要である。The immersion is carried out by passing the coating material through an aqueous dispersion bath batchwise or continuously via a roller, but in order to increase the impregnation into the inside of the fiber bundle and to process efficiently,
Particular preference is given to continuous treatment. It is preferable to efficiently pass the 'R flow between the aqueous dispersion of the m miscellaneous bundle and the aqueous dispersion of the coating material in order to improve the impregnating property inside the lIH bundle. It is necessary to use equipment that allows current to pass only between the fiber bundles.
第１図は本発明において用いられる装置の１例を概念図
である。第１図において１は１１組束、２は電気的に絶
縁された処理浴、３は電極である。電極は、銅などの金
属材、炭素材の板材、棒状、ネット状などの形状をした
ものが使用される。４．５．６．７はローラーで、その
うち４、７の各ローラーは回転可能な通電用電極ローラ
ーであり、金属、カーボン材などの１ＴＩｆ材にて造ら
れる。５．６の各ローラーは電気的に絶縁されている回
転可能なガイドローラーで、８．９は夫々供給ローラー
と引取ローラーである。１０は水分散液を示す。FIG. 1 is a conceptual diagram of an example of a device used in the present invention. In FIG. 1, 1 is a bundle of 11, 2 is an electrically insulated processing bath, and 3 is an electrode. The electrode used is a metal material such as copper, a plate material made of carbon material, a rod shape, a net shape, or the like. 4.5.6.7 are rollers, of which rollers 4 and 7 are rotatable current-carrying electrode rollers, and are made of 1TIF material such as metal or carbon material. Each roller 5.6 is an electrically insulated rotatable guide roller, and 8.9 is a supply roller and a take-off roller, respectively. 10 indicates an aqueous dispersion.
第２図は多段にて処理を行う場合の装置の１例を示す概
念図である。第２図中の各番号は第１図と同じである。FIG. 2 is a conceptual diagram showing an example of an apparatus for performing processing in multiple stages. Each number in FIG. 2 is the same as in FIG.
多段にて処理する場合、第２図においては単−浴を用い
ているが、浴を多段にすることもできる。処理を多段に
て行うと被覆材の均−且つ迅速な付着に対し特に効果的
である。When processing in multiple stages, a single bath is used in FIG. 2, but the baths can also be multi-staged. Multistage treatment is particularly effective for uniform and rapid deposition of the coating.
通電するに際して、適用される水分散液の湿度は水分散
液状態を良好に保つ適度な範囲でよく、被覆材によって
若干は異なるが、通常は５〜５０℃が適用され、また、
該分散液の濃度は、通電する電圧、電流、付着する聞に
よって異なるが、通常１〜３０％が用いられる。更に８
！漬時間は、付着量、通電圧、電流によって変化させる
必要があるが、通常１〜８０秒が適用される。When applying electricity, the humidity of the aqueous dispersion applied may be within an appropriate range to maintain a good aqueous dispersion state, and although it varies slightly depending on the coating material, it is usually 5 to 50 ° C.
The concentration of the dispersion varies depending on the applied voltage, current, and extent of adhesion, but is usually 1 to 30%. 8 more
! The soaking time needs to be changed depending on the amount of adhesion, applied voltage, and current, but usually 1 to 80 seconds is applied.
本発明において適用する電流は、直流であることが必要
で、該繊維束を必要に応じて陰極又は陽極とし、該水分
散液を逆の極とすることによって通電するが、特に該繊
維束を陽極とし、該水分散液を陰極とすることがＲＦＬ
やノニオン或いはアニオン系界面活性剤を乳化剤として
水分散液としたエポキシ樹脂、ポリイソシアネート樹脂
含有ブロック化合物の場合、付着性及び繊維内部への含
浸性の点で好ましい。The current applied in the present invention needs to be a direct current, and is applied by using the fiber bundle as a cathode or anode as necessary and the aqueous dispersion as the opposite pole. RFL is an anode and the aqueous dispersion is a cathode.
In the case of a block compound containing an epoxy resin or a polyisocyanate resin, which is made into an aqueous dispersion using a nonionic or anionic surfactant as an emulsifier, it is preferable in terms of adhesion and impregnation into the inside of the fiber.
通電する電圧は、処理する繊維束や水分散液の電気抵抗
によって異なるが、通常１ボルト以上が好ましく、また
、電流密度は咳織雑束を構成し、且つ入浴位置から１１
以内の浴中にある単繊維の単位表面積当りの電流密度が
１１Ａ／Ｉ’以上であることが好ましい。０．０１ Ａ
／！ｌ ２〜５Ａ／ｌ’が特に好ましい。０．０１
Ａ ／ｌｏ ’未満の場合、効果が少なく、５Ａ／１１
’超の場合、該繊維束のうえでＲＦＬやエポキシ樹脂が
反応し、硬い樹脂物となる傾向があるので好ましくない
。通電処理している際の該繊維にかける張力は、該繊維
束がたるまない程度から、ｍ維束の毛羽が増大しない程
度の範囲が適当であり通常１０〜１００ｎ＋ｇ ／ｄが
採用される。このようにして得られる繊維束は、被覆材
を０．１〜１０重１％付着しているが、待にＲＦＬを主
成分として付着する場合は１０〜７０重量％、エポキシ
樹脂を主成分として付着する場合は０．１〜５重量％と
することが、ゴムとの接着性、複合材としての利用の際
における［ｆｔ束の毛羽発生抑制及びマトリックス材と
の接着性の点から好ましい。ポリイソシアネート樹脂含
有ブロック化合物の場合にも、エポキシ樹脂と同じ（０
，１〜５重量％が好ましい。The applied voltage varies depending on the electrical resistance of the fiber bundle to be treated and the aqueous dispersion, but it is usually preferably 1 volt or more, and the current density is set at 1 volt or more from the bathing position.
The current density per unit surface area of the single fibers in the bath is preferably 11 A/I' or more. 0.01A
/! Particularly preferred is l2-5A/l'. 0.01
If it is less than A/lo', there is little effect and 5A/11
If it is more than 1, the RFL or epoxy resin tends to react on the fiber bundle, resulting in a hard resin material, which is not preferable. The tension applied to the fibers during the energization treatment is suitably within a range from a level that does not cause the fiber bundle to sag to a level that does not increase the fluff of the m fiber bundles, and is usually 10 to 100 n+g/d. The fiber bundle obtained in this way has a covering material of 0.1 to 10% by weight attached, but when RFL is attached as a main component, 10 to 70% by weight is attached, and an epoxy resin is attached as a main component. When adhering, it is preferable to use 0.1 to 5% by weight from the viewpoints of adhesion with rubber, prevention of fuzz generation in [ft bundles] and adhesion with matrix material when used as a composite material. In the case of polyisocyanate resin-containing block compounds, the same (0
, 1 to 5% by weight is preferred.
通電して得た被覆材の水分散液の付着した１！維束は、
通常、被覆材が反応又は分解しない濃度以下にて水を除
去し乾燥する。一般には、８０〜ｉｓｏ℃にて １〜１
０分乾燥を行う。尚、ＲＦＬ。1 to which the aqueous dispersion of the coating material obtained by applying electricity has adhered! Isshu is
Usually, water is removed and dried at a concentration below which the coating material will not react or decompose. Generally, 1-1 at 80-iso℃
Dry for 0 minutes. Furthermore, R.F.L.
エポキシ樹脂、ポリイソシアネート樹脂含有ブロック化
合物の２種以上混合物を使用する場合、付ａｍは０．１
〜３０重厘％が好ましい。この場合通電に伴って選択的
に付着する傾向があるので、付着した樹脂割合をみなが
ら浴の組成を調整して付着させる。この混合によって炭
素繊維との接着性は向上する傾向にある。When using a mixture of two or more types of block compounds containing epoxy resin and polyisocyanate resin, the am is 0.1.
~30% by weight is preferred. In this case, since there is a tendency for the resin to adhere selectively as electricity is applied, the composition of the bath is adjusted while checking the proportion of the resin adhered. This mixing tends to improve adhesion to carbon fibers.
（発明の効果）
本発明の方法は、炭素繊維束を有機系被覆材の水分散液
に浸漬している間に通電して、電気的に被覆材の微粒子
を誘引し、該繊維束内部にまで含浸させ得るために、該
＄１８束内部にある単ｍｔｒａが充分被覆されると共に
、Ｉ！ｉ雑束全体に均一に付着される。このため、ＲＦ
Ｌを主成分とする被覆材を付着した繊維束の場合は、束
としての強さが向上するだけでなく、ゴムマトリックス
との接着性も向、Ｆする。また、エポキシ樹脂やポリイ
ソシアネート樹脂含有ブロック化合物を主成分とする被
覆材の場合には、束の取り扱い性が向上し、毛羽発生抑
制効果が発揮されるだけでなく、プラスチックス特にエ
ポキシ樹脂と複合化したときの接着性が向上する。(Effects of the Invention) The method of the present invention applies electricity while a carbon fiber bundle is immersed in an aqueous dispersion of an organic coating material to electrically attract fine particles of the coating material into the interior of the fiber bundle. The single mtra inside the $18 bundle is sufficiently coated to allow impregnation up to I! It is evenly attached to the entire bundle. For this reason, R.F.
In the case of a fiber bundle to which a coating material containing L as a main component is attached, not only the strength of the bundle is improved, but also the adhesiveness with the rubber matrix is improved. In addition, in the case of coating materials whose main components are block compounds containing epoxy resins or polyisocyanate resins, they not only improve the handling of bundles and exhibit the effect of suppressing the generation of fuzz, but also combine with plastics, especially epoxy resins. Improves adhesion when bonded.
本発明の方法と通電なしで処理する従来の方法とを実施
例１．６に準じて比較したときの結果を第１表に示す。Table 1 shows the results of a comparison between the method of the present invention and the conventional method of processing without energization according to Example 1.6.
これによれば、通電を行う本発明の方法の場合、被覆材
の付着量は多く、該繊維束内部の単繊維被覆状態が優れ
、繊維束の毛羽の発生が少く、マトリックスとの接着性
が高いことがわかる。According to this, in the case of the method of the present invention in which electricity is applied, the amount of coating material deposited is large, the single fiber coating condition inside the fiber bundle is excellent, the generation of fluff in the fiber bundle is small, and the adhesiveness with the matrix is improved. I know it's expensive.
以下に本発明について実施例を挙げて更に詳しく説明す
る。特に指定しない限り「％」、「部」は重量で示す。EXAMPLES The present invention will be described in more detail below with reference to Examples. Unless otherwise specified, "%" and "part" are expressed by weight.
実施例１〜５及び比較例１〜２
アクリロニトリル系重合体繊維から得た炭素繊維束（炭
素含有１９５．５重量％、体積電気抵抗（１１１２Ｘ１
０”Ωｃｍ、単繊維直径７ミクロン、構成本数６０００
本、強度４３０ｋｇｆ／ ｍｓ’ 、弾性率２５×１０
’ ｋｇｆ ／ｕ＋” ） ！第１図に示した温良１ａ
＋％幅０．５ｍ 、浸漬長０．３ｍである装置を用いて
浸漬時間、電圧、電流密度を第２表のことく変化させた
条件下、炭素繊維束を陽極とし、下記のごとく調整した
ＲＦＬの水分散液を陰極として通電処理し、引続いて１
２０℃にて３分間乾燥し、次いで２３０℃にて２分間熱
処理して、ＲＦＬ付着コードを得た。尚、この処理の間
は張力を５０Ｉ１ｇ／ｄとした。Examples 1 to 5 and Comparative Examples 1 to 2 Carbon fiber bundles obtained from acrylonitrile polymer fibers (carbon content 195.5% by weight, volume electrical resistance (1112X1
0” Ωcm, single fiber diameter 7 microns, number of components 6000
Book, strength 430 kgf/ms', elastic modulus 25 x 10
' kgf /u+'')! Atmospheric temperature 1a shown in Figure 1
+% Using an apparatus with a width of 0.5 m and an immersion length of 0.3 m, the immersion time, voltage, and current density were varied as shown in Table 2, and the carbon fiber bundle was used as an anode and adjusted as follows. The aqueous dispersion of RFL was used as a cathode to conduct current treatment, and then 1
It was dried at 20° C. for 3 minutes and then heat treated at 230° C. for 2 minutes to obtain an RFL-attached cord. Note that the tension was set at 50I1 g/d during this treatment.
得られたコードにつき、未加硫天然ゴム組成物にコード
長さ５ＣＩＩｌで埋め込み１４８℃にて３０分間加硫し
たものについて、加硫ゴムからコードを引き抜（力を測
定する方法で接着力を調べ、また、該コード２ブライを
９０”の角度をなすようにクロスプライ（コード密度２
６エンド７２．５ｃｍ）として、上記と同じ未加硫天然
ゴム組成物に埋め込み、１４８℃にて３０分間加硫した
くプレス７ｋａ ／ｃｍ’ ）のち、両プライを剥離さ
せて該コードの肉眼観察によるコードの付着状態を調べ
た。The obtained cord was embedded in an unvulcanized natural rubber composition with a cord length of 5 CIIl and vulcanized at 148°C for 30 minutes, and the cord was pulled out from the vulcanized rubber (the adhesive strength was determined by measuring the force). Cross-ply (cord density 2
6 ends (72.5 cm) were embedded in the same unvulcanized natural rubber composition as above and vulcanized at 148°C for 30 minutes (7ka/cm'), then both plies were peeled off and the cord was visually observed. The adhesion status of the cord was investigated.
更に、炭素繊維束の単位長さ当りの！１ｍと該コードの
単位長さ当りの重量とから、該コード重量当りの付＠量
を測定した。Furthermore, per unit length of carbon fiber bundle! The amount of attachment per cord weight was measured from 1 m and the weight per unit length of the cord.
比較のために、通電しない外は、全（上記と同じように
処理して得たｍ緒についても同様に測定した。上記結果
は第２表に示すごとくであり、これによれば、本発明の
方法によって得た炭素繊維束のＲＦＬ付着コードは、ゴ
ムとの高い接着性と高い付着四を有することがわかる。For comparison, measurements were also made in the same way on all cords obtained by processing in the same manner as above, except when energized. The above results are shown in Table 2, and according to this, the present invention It can be seen that the RFL adhesion cord of the carbon fiber bundle obtained by the method has high adhesion to rubber and high adhesion.
更に、各コードについてコードの中央部にある単ｌＩ帷
の電子顕微ｔＡｖＡ察を行った結果を併せ第２表に示し
た。これによれば通電して得たコードは中心までよ＜Ｒ
ＦＬが付着し均一であることがわかる。但し実施例５の
ごとく電流密度が小さいとぎは効果が小さい。Furthermore, the results of electron microscopy tAvA observation of the single strand in the center of each cord are shown in Table 2. According to this, the cord obtained by energizing should reach the center <R
It can be seen that the FL adheres uniformly. However, when the current density is low as in Example 5, the effect is small.
（ＲＦＬのｍ製）
１０％苛性ソーダ水溶液１０ｇと２８％アンモニア水溶
液３０ｇを水２６０りに加え、よく攪拌して得た水溶液
中に酸性触媒で反応したレゾルシンホルマリン初期縮合
物（４０％アセトン溶液）６０ｇを添加して充分に攪拌
分散さゼた。次にビニルピリジンスチレンブタジェン三
元共重合体ラテックスの４０％水乳化液（日本ゼオン社
Ｍ）２４ｏｇ及びスチレンブタジエンニ元共重合体の４
０％水乳化液（日本ゼオン社製） １００Ｑを水２５０
Ｑで希釈する。この希釈液中に、上記レゾルシンホルマ
リン初期縮合物分散液をゆっくりかきまぜながら加えて
いき、更にホルマリン（３１％）２０９を添加して均一
に混合することによってＲＦＬ水分散液を調製した。(manufactured by RFL) Add 10g of 10% caustic soda aqueous solution and 30g of 28% ammonia aqueous solution to 260ml of water, stir well, and add 60g of resorcin formalin initial condensate (40% acetone solution) reacted with an acidic catalyst to the aqueous solution obtained. was added and thoroughly stirred to disperse. Next, 24 og of a 40% water emulsion of vinyl pyridine styrene butadiene terpolymer latex (Nippon Zeon M) and 4 og of styrene butadiene ternary copolymer latex were added.
0% water emulsion (manufactured by Nippon Zeon) 100Q to 250% water
Dilute with Q. The resorcin formalin initial condensate dispersion was slowly stirred into this diluted solution, and formalin (31%) 209 was further added and mixed uniformly to prepare an RFL aqueous dispersion.
実施例６〜７及び比較例３
アクリロニトリル系重合体繊維から得た炭素質議ｍ＜炭
素含有！１８５．７重量％、体積電気抵抗値２Ｘ１０
’ΩＣ１１単繊維直径１．３ミクロン、構成本数３０
００本、強度３３５ｋｏｆ／ｍａｎ’ 、弾性率１８ｘ
１Ｇ” ｋｇｆ ／ｍｇｉ’ ）を第１図の装置で実施
例１〜５と同じ電圧、電流密度、浸漬時開として次のご
とく調製したエポキシ樹脂の水分散液を陰極、該炭素質
繊維を陽極として通電処理し、引続き１１５℃にて５分
間乾燥してエポキシ樹脂を付着した。尚、この際の張力
は３０ｍ ｇ ／ｄとした。Examples 6 to 7 and Comparative Example 3 Carbonaceous material obtained from acrylonitrile polymer fiber m<carbon content! 185.7% by weight, volume electrical resistance value 2X10
'ΩC11 single fiber diameter 1.3 microns, number of components: 30
00 pieces, strength 335kof/man', elastic modulus 18x
1 G" kgf / mgi') using the apparatus shown in FIG. 1 at the same voltage, current density, and opening during immersion as in Examples 1 to 5, an aqueous dispersion of epoxy resin prepared as follows was used as a cathode, and the carbonaceous fiber was used as an anode. The epoxy resin was applied by applying an electric current at 115° C. for 5 minutes.The tension at this time was 30 mg/d.
また、比較例として、通電しないで、上記と同じ処理を
行った。これらの繊維束は第３表に示すごとくである。In addition, as a comparative example, the same process as above was performed without energizing. These fiber bundles are as shown in Table 3.
通電して得た繊維束は内部にある繊維まで均一に付着し
、また毛羽も少なかった。The fiber bundle obtained by energizing the fibers evenly adhered to the inner fibers, and had little fuzz.
また、下記のごとくして作成した複合材はボイドもな（
、破断したときの破断面にある単繊維は樹脂とよく接着
していることが電子顕微鏡により観察された。In addition, the composite material created as follows has no voids (
It was observed using an electron microscope that the single fibers on the fracture surface were well adhered to the resin.
第 ３ 表
〔エポキシ樹脂水分散液の調製〕
エピコート８２８（油、化シェルエポキシ社製＞９０部
とポリエチレングリコール（グリコール基のモル数４０
）ノニルフェノールエーテル１０部をアセトン５部と５
５℃にて混合しホモジナイザーにて激しく攪拌しながら
水１９５部を５部／分の割合で入れ粘度が急激に上昇し
相転換するまで注入したのち、残りの水をすべて注入し
て固形分５０％の乳化液とし、これを更に水で希釈して
２％の水分散液とした。Table 3 [Preparation of aqueous epoxy resin dispersion] Epicoat 828 (oil, manufactured by Shell Epoxy Co., Ltd. > 90 parts) and polyethylene glycol (number of moles of glycol group: 40 parts)
) 10 parts of nonylphenol ether with 5 parts of acetone
Mix at 5°C, add 195 parts of water at a rate of 5 parts/min while stirring vigorously with a homogenizer, and inject until the viscosity rapidly increases and phase change occurs, then all the remaining water is added to reduce the solid content to 50. % emulsion, and this was further diluted with water to obtain a 2% aqueous dispersion.
エピコート ８２８タイプ４０部、エピコート １５４
タイプ（油化シェルエポキシ社［）６０部、ジシアンジ
アミド３部を混合した樹脂のフィルム１０（１／Ｉｎり
に炭素４１維束をｆ５０ｇ／ａ＋ ’になるごとく並べ
て上下を剥離紙ではさみ１３０℃、３分間処理して樹脂
フィルムを繊維に含浸させプリプレグを作成した。この
プリプレグを積層して成形後３ｍｍ厚みになるごとくし
てモールド内に配置し１３５℃、２時間、７ｋｇｆ／ａ
ｍ’の条件下にて圧縮成形して複合材とした。Epicote 828 type 40 parts, Epicote 154
Film 10 of a resin mixed with 60 parts of Type (Yuka Shell Epoxy Co., Ltd.) and 3 parts of dicyandiamide (carbon 41 fibers were arranged in 1/In ratio f50g/a+', and the upper and lower sides were sandwiched between release paper at 130°C. The resin film was treated for 3 minutes to impregnate the fibers to create a prepreg.The prepreg was laminated and molded to a thickness of 3mm, placed in a mold, and heated at 135°C for 2 hours at 7kgf/a.
A composite material was obtained by compression molding under conditions of m'.
第１図及び第２図は本発明の実施に際し使用される装置
の概念図を示したものであり、第１図は単一浴処理、第
２図は多段処理の１例を示したものである。
１：繊維束、２：処理浴、３：電機、４．７：通電用電
極ローラー、５．６：ガイドローラー、８；供給ローラ
ー、９：引取ローラー
特許出願人 東邦ベスロソ林式会社
代理人弁理士 土 居 三 部
第１図
第２図
手続補正層
昭和６０年７月２２日Figures 1 and 2 show conceptual diagrams of the equipment used in carrying out the present invention, with Figure 1 showing an example of single bath processing and Figure 2 showing an example of multi-stage processing. be. 1: Fiber bundle, 2: Processing bath, 3: Electric machine, 4.7: Electrode roller for energization, 5.6: Guide roller, 8: Supply roller, 9: Take-up roller Patent applicant Toho Besloso Hayashi Shiki Co., Ltd. Agent and Patent Attorney 3 Part Figure 1 Figure 2 Procedure Amendment Layer July 22, 1985
Claims (6)
コードを製造するに当り、該被覆材の水分散液に炭素繊
維束を浸漬し両者間に直流電流を通すことを特徴とする
炭素繊維コードの製造方法。(1) When manufacturing a carbon fiber cord by impregnating a carbon fiber bundle with an organic coating material, the carbon fiber bundle is immersed in an aqueous dispersion of the coating material and a direct current is passed between the two. Method of manufacturing carbon fiber cord.
陰極とする特許請求の範囲（１）項記載の方法。(2) The method according to claim (1), wherein the carbon fiber bundle is used as an anode and the aqueous dispersion of an organic coating material is used as a cathode.
ポキシ樹脂を主成分として含む特許請求の範囲（１）項
記載の方法。(3) The method according to claim (1), wherein the coating material contains resorcin formalin latex or epoxy resin as a main component.
／ｍ＾２である特許請求の範囲（１）項記載の方法。(4) Voltage is 1 volt or more and current density is 0.01 A
/m^2. The method according to claim (1).
し１０〜７０重量％付着させる特許請求の範囲（１）項
記載の方法。(5) The method according to claim (1), in which 10 to 70% by weight of resorcin formalin latex is attached to carbon fibers.
付着させる特許請求の範囲（１）項記載の方法。(6) 0.1 to 5% by weight of epoxy resin based on carbon fiber
A method according to claim (1) for adhering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60053323A JPS61215772A (en) | 1985-03-19 | 1985-03-19 | Production of carbon fiber code |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60053323A JPS61215772A (en) | 1985-03-19 | 1985-03-19 | Production of carbon fiber code |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61215772A true JPS61215772A (en) | 1986-09-25 |
Family
ID=12939510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60053323A Pending JPS61215772A (en) | 1985-03-19 | 1985-03-19 | Production of carbon fiber code |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61215772A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019030164A1 (en) * | 2017-08-11 | 2019-02-14 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Fibre composite component designed as an electrochemical storage device and method for the production thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4923274A (en) * | 1972-06-27 | 1974-03-01 | ||
| JPS4924830A (en) * | 1972-06-30 | 1974-03-05 | ||
| JPS4972496A (en) * | 1972-10-24 | 1974-07-12 |
-
1985
- 1985-03-19 JP JP60053323A patent/JPS61215772A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4923274A (en) * | 1972-06-27 | 1974-03-01 | ||
| JPS4924830A (en) * | 1972-06-30 | 1974-03-05 | ||
| JPS4972496A (en) * | 1972-10-24 | 1974-07-12 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019030164A1 (en) * | 2017-08-11 | 2019-02-14 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Fibre composite component designed as an electrochemical storage device and method for the production thereof |
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