JPH03220320A - Carbon fiber for producing electrically conductive composite material and thermoplastic resin composition using same fiber - Google Patents
Carbon fiber for producing electrically conductive composite material and thermoplastic resin composition using same fiberInfo
- Publication number
- JPH03220320A JPH03220320A JP1636190A JP1636190A JPH03220320A JP H03220320 A JPH03220320 A JP H03220320A JP 1636190 A JP1636190 A JP 1636190A JP 1636190 A JP1636190 A JP 1636190A JP H03220320 A JPH03220320 A JP H03220320A
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- fiber
- thermoplastic resin
- resin composition
- 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.)
- Pending
Links
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 59
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 59
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000000835 fiber Substances 0.000 title claims abstract description 28
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 13
- 239000011342 resin composition Substances 0.000 title claims abstract description 8
- 239000002131 composite material Substances 0.000 title claims description 3
- 125000000524 functional group Chemical group 0.000 claims abstract description 15
- 238000001941 electron spectroscopy Methods 0.000 claims abstract description 8
- 239000002344 surface layer Substances 0.000 claims abstract 3
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000004918 carbon fiber reinforced polymer Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 6
- 230000003068 static effect Effects 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract 1
- -1 polyoxymethylene Polymers 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000004513 sizing Methods 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- 238000000441 X-ray spectroscopy Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229920006324 polyoxymethylene Polymers 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 description 3
- 239000012783 reinforcing fiber Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003733 fiber-reinforced composite Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 208000032365 Electromagnetic interference Diseases 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- QZHBYNSSDLTCRG-WUUYCOTASA-N brimonidine tartrate Chemical compound [H+].[H+].[O-]C(=O)[C@@H](O)[C@H](O)C([O-])=O.C1=CC2=NC=CN=C2C(Br)=C1NC1=NCCN1 QZHBYNSSDLTCRG-WUUYCOTASA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920012287 polyphenylene sulfone Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Inorganic Fibers (AREA)
- Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、繊維強化樹脂組成物およびそれに使用する炭
素繊維に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a fiber-reinforced resin composition and carbon fibers used therein.
（従来の技術）
近年、炭素繊維は、高強度、高剛性、低比重、高電気伝
導性、低熱膨張率、高耐摩耗性等の優れた特長を有する
ことから各種樹脂の強化繊維として使用され工業的に重
要な材料として注目されている。特に最近では、ＯＡ機
器や歯車等の帯電防止や！磁遮蔽の為に繊維強化複合材
の機械的物性を保持しつつ導電性を付与する強化繊維が
求められている。(Prior art) In recent years, carbon fibers have been used as reinforcing fibers for various resins due to their excellent features such as high strength, high rigidity, low specific gravity, high electrical conductivity, low coefficient of thermal expansion, and high abrasion resistance. It is attracting attention as an industrially important material. Especially recently, it is used to prevent static electricity on OA equipment and gears! There is a need for reinforcing fibers that provide electrical conductivity while maintaining the mechanical properties of fiber-reinforced composite materials for magnetic shielding.
最近のエレクトロニクスの発展にともない、電子機器周
辺の電子機器の誤動作いわゆる電磁波障害（ＥＭＩ；Ｅ
ｌｅｃｔｒｏ ＭａｇｎｅｔｉｃＩｎｔｅｒｆｅｒｅ
ｎｃｅ）が新たな社会問題としてクローズアップされて
いる。日本でも、一定の電界強度以上の電磁波が電子機
器から漏洩しないように法的規制が行なわれている。（
ＥＭＩシールド）この対策の一つとして、使用している
ハウジング材料であるプラスチックスの導電性化が挙げ
られている。−船釣には、プラスチックスは絶縁材料で
あるが、その量産性、デザインの自由度・軽量性等の観
点からプラスチックス、熱可塑性樹脂がハウジング材料
の主流となっている。このプラスチックスの導電化のた
めには、種々の方法が提案されており、現在は導電性塗
料や無電解メツキ等の導電性表面処理が主流である。し
かし、シールド特性の経時変化が少なく、また成形と同
時に導電性が付与でき、従って工程上低コストにできる
導電性熱可塑性樹脂が注目されている。そして、かかる
導電性熱可塑性樹脂としては、一般にポリエステル、ポ
リアミド、ポリオレフィン、アクリル樹脂、エポキシ樹
脂、フェノール樹脂等の各種マトリックスにフィラーを
混合、分散させて繊維強化樹脂材料を得、次いで導電性
を付与するに、導電性カーボンブラック、金属フィラー
や金属繊維を添加する。しかしこれら添加物は、熱可塑
性樹脂に導電性は付与するものの機械的物性を低下し、
導電性の改善は不十分という問題があった。これに対し
、炭素繊維は強化繊維としては導電性を有し上記用途に
適している。With the recent development of electronics, malfunctions of electronic equipment around electronic equipment, so-called electromagnetic interference (EMI;
electro Magnetic Interfere
nce) is attracting attention as a new social problem. In Japan, legal regulations are in place to prevent electromagnetic waves exceeding a certain electric field strength from leaking from electronic devices. (
(EMI Shielding) One of the countermeasures to this problem is to make the plastic housing material used conductive. -For boat fishing, plastics are used as insulating materials, but plastics and thermoplastic resins have become the mainstream housing materials due to their ease of mass production, freedom of design, and light weight. Various methods have been proposed to make plastics conductive, and currently, conductive surface treatments such as conductive paint and electroless plating are the mainstream. However, conductive thermoplastic resins are attracting attention because their shielding properties change little over time, and conductivity can be imparted at the same time as molding, resulting in lower manufacturing costs. Such conductive thermoplastic resins are generally made by mixing and dispersing fillers in various matrices such as polyester, polyamide, polyolefin, acrylic resin, epoxy resin, and phenolic resin to obtain fiber-reinforced resin materials, which are then imparted with conductivity. Then, conductive carbon black, metal fillers and metal fibers are added. However, although these additives impart electrical conductivity to thermoplastic resins, they reduce mechanical properties.
There was a problem that the improvement in conductivity was insufficient. On the other hand, carbon fibers have electrical conductivity as reinforcing fibers and are suitable for the above-mentioned uses.
（発明が解決しようとする課題）
しかし、通常の従来の炭素繊維を使用しても導電性は向
上するもののその変化は少なく、そのため表面を金属で
被覆した炭素繊維が使用されている。しかし、金属被覆
炭素繊維は製造コストが非常に高価でありその性能は優
れているものの使用されていないのが現状である。(Problems to be Solved by the Invention) However, even if ordinary conventional carbon fibers are used, although the conductivity is improved, the change is small, and therefore carbon fibers whose surfaces are coated with metal are used. However, metal-coated carbon fibers are extremely expensive to manufacture, and although they have excellent performance, they are not currently used.
（課題を解決するための手段）
そこで、本発明者等はかかる課題を解決すべく鋭意検討
を行なった結果、特定の表面物性を有する炭素繊維によ
り、かかる課題が解消されることを見いだし本発明に到
達した。すなわち、本発明の目的は、従来の炭素繊維の
保持している表面構造とは異なった構造を有しており、
この繊維表面構造に起因して複合材料に機械的物性を保
持しつつ優れた導電性を付与できる炭素繊維及びそれを
用いた樹脂組成物を提供することにある。(Means for Solving the Problems) Therefore, the present inventors conducted intensive studies to solve the problems, and as a result, they found that the problems could be solved by carbon fibers having specific surface properties. reached. That is, the object of the present invention is to have a surface structure different from that of conventional carbon fibers,
The object of the present invention is to provide a carbon fiber that can impart excellent electrical conductivity to a composite material while maintaining its mechanical properties due to this fiber surface structure, and a resin composition using the same.
そしてその目的は、Ｘ線電子分光法（Ｅ ＣＳ Ａ）に
よって検出される炭素繊維最表面の官能基量（０１Ｓ／
ＣＩ Ｓ）が０．０２〜０．０５の範囲である繊維最表
面層を有し、かつその引張弾性率が１０ ｔｏｎ／ｍｍ
” 〜３０ ｔｏｎ／ｍｍ”の範囲である炭素繊維およ
び熱可塑性樹脂１００重量部に対してＸ線電子分光法（
Ｅ ＣＳ Ａ）によって検出された炭素繊維表面の官能
基量（０１Ｓ／ＣＩ Ｓ）が０．０２〜０．０５の範囲
である繊維最表面層を有し、かつ引張弾性率が１０ ｔ
ｏｎ／＋ｍｍ”〜３０ ｔｏｎ／ａ＋ｎ＋”の範囲であ
る炭素繊維を１〜７０重量部配合してなる炭素繊維強化
熱可塑性樹脂組成物によって上記問題点を解決すること
が出来ることを見いだし本発明に到達した。The purpose is to determine the amount of functional groups (01S/
CI S) has a fiber outermost layer in the range of 0.02 to 0.05, and its tensile modulus is 10 ton/mm
X-ray electron spectroscopy (
The fiber has a fiber outermost layer in which the amount of functional groups on the carbon fiber surface (01S/CIS) detected by ECS A) is in the range of 0.02 to 0.05, and the tensile modulus is 10 t.
It has been discovered that the above problems can be solved by a carbon fiber-reinforced thermoplastic resin composition containing 1 to 70 parts by weight of carbon fibers in the range of 1 to 30 tons/a+n+'', and the present invention has been made based on the findings. Reached.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の炭素繊維を得るための手段としては、単糸引張
弾性率が１０ ｔｏｎ／ｓ＋＋＋＋”以上であって３０
ｔｏｎ／ｍｍ”以下、好ましくは２５ ｔｏｎ／ｓｖ＋
”以下さらに好ましくは２０ ｔｏｎ／ｍｎ＋”以下で
ある炭素繊維を不活性ガス下かつまた必要に応じて減圧
下にて再焼成する事によって得られる。用いる炭素繊維
はピッチ系炭素繊維であることがより好ましい。再焼成
温度としては、たとえば８００〜１５００℃、好ましく
は８５０〜１０００℃の温度範囲で０．１〜５分間加熱
処理され、Ｘ線電子分光法（ＥＣ３Ａ）によって検出さ
れる炭素繊維表面の官能基量（０１Ｓ／ＣＩ Ｓ）が０
．０２１００５（７１範囲内、好ましくは０．０２〜０
．０４の範囲にするのがよい。As a means for obtaining the carbon fiber of the present invention, the single filament tensile modulus is 10 ton/s++++" or more and 30
ton/mm” or less, preferably 25 ton/sv+
It is obtained by re-firing carbon fibers having a weight of "less than or more preferably 20 ton/mn+" under an inert gas and optionally under reduced pressure. It is more preferable that the carbon fiber used is a pitch-based carbon fiber. The re-firing temperature is, for example, 800 to 1500°C, preferably 850 to 1000°C, for 0.1 to 5 minutes, and the functional groups on the carbon fiber surface are detected by X-ray electron spectroscopy (EC3A). Quantity (01S/CIS) is 0
．． 021005 (within the range of 71, preferably 0.02 to 0
．． It is best to set it in the range of 04.
炭素繊維の弾性率が上記範囲より低い場合、炭素繊維自
体の物性が低く繊維強化樹脂組成物としたときの機械的
物性の改善が発現しにくい。また、上記範囲を載支た弾
性率の炭素繊維を用いると、糸そのものの脆さがでて樹
脂マトリックスとの混練の際にスクリューのせん断力に
よって糸が破壊され十分に機械的物性を発現できない。When the elastic modulus of the carbon fiber is lower than the above range, the physical properties of the carbon fiber itself are low and it is difficult to improve the mechanical properties when a fiber reinforced resin composition is prepared. Furthermore, if carbon fiber with an elastic modulus within the above range is used, the yarn itself becomes brittle, and when kneaded with the resin matrix, the yarn is destroyed by the shearing force of the screw, making it impossible to exhibit sufficient mechanical properties. .
また、炭素繊維の最表面官能基量が上記範囲以下の場合
は、導電性は発現するものの、官能基量が少なすぎ樹脂
マトリックスとの接着力が低下し機械的強度が発現しに
くい。また、上記範囲を越えると樹脂との接着力は増加
するが、導電性が低下する。Furthermore, when the amount of functional groups on the outermost surface of the carbon fiber is below the above range, although conductivity is exhibited, the amount of functional groups is too small and adhesive strength with the resin matrix decreases, making it difficult to develop mechanical strength. Further, when the amount exceeds the above range, the adhesive force with the resin increases, but the conductivity decreases.
かくして得られる本発明の炭素繊維の最表層部はＸ線電
子分光法（Ｅ ＣＳ Ａ）によって検出される炭素繊維
表面の官能基量（０１Ｓ／ＣＩ Ｓ）が０．０２〜０．
０５の範囲の値を示す。The outermost layer of the carbon fiber of the present invention thus obtained has a functional group content (01S/CIS) of 0.02 to 0.02 on the carbon fiber surface as detected by X-ray electron spectroscopy (ECSA).
Indicates a value in the range of 0.05.
ここで、Ｘ線電子分光法（ＥＳＣＡ） 、単繊維弾性率
は次の測定法にしたがって測定された値である。Here, the single fiber elastic modulus is a value measured according to the following measurement method using X-ray electron spectroscopy (ESCA).
Ｘ線電子分光法（ＥＳＣＡ）：
具体的な装置として、“ＫＲＡＴＯ５ＸＳＡＭ−８００
”を用いた。X-ray electron spectroscopy (ESCA): As a specific device, “KRATO5XSAM-800
” was used.
炭素繊維（サンプル）を有機溶剤で洗浄し、サイジング
剤などの表面付着剤を除去した後、該炭素繊維をカット
し、銅製の試料支持台上にひろげて並べた後、Ｘ線源と
してＡＩＫｃｘｖＡを用い測定し、運動エネルギーが９
５５ｅＶのＯ１ｓピーク面積および１２０２ｅＶのＣ１
ｓピ一ク面積の比から表面酸素原子／表面炭素原子（０
１Ｓ／ＣＩＳ）の比を求める。After cleaning the carbon fibers (sample) with an organic solvent to remove surface adhesives such as sizing agents, the carbon fibers were cut and spread out on a copper sample support stand, and then AIKcxvA was used as an X-ray source. The kinetic energy is 9
O1s peak area of 55eV and C1 of 1202eV
Surface oxygen atom/surface carbon atom (0
1S/CIS).
平均単糸弾性率：
ＪＩＳ−Ｒ−７６０１に規定されている単繊維試験法に
準じて測定した。測定回数１００回の平均値を以て示し
た。Average single fiber elastic modulus: Measured according to the single fiber test method specified in JIS-R-7601. The average value of 100 measurements is shown.
次に、かかる炭素繊維を用いた熱可塑性樹脂組成物につ
いて説明する。Next, a thermoplastic resin composition using such carbon fibers will be explained.
用いる熱可塑性樹脂としては、例えば、ポリカーボネー
ト、ポリスチレン、ポリエステル、ポリアミド、ポリオ
レフィン、アクリル樹脂、ポリオキシメチレン、ポリフ
ェニレンサルファイド、ポリフェニレンエーテル、ポリ
フェニレンオキシド、ポリブチレンテレフタレート、ポ
リエーテルイミド、ポリエーテルエーテルケトン、ポリ
フェニレンスルホン、フッ素樹脂などのポリマー類又は
これらのコポリマー類などの公知の熱可塑性樹脂を挙げ
られ、好ましくは、ポリカーボネート、ポリオキシメチ
レン、ポリブチレンテレフタレート、ポリフェニレンオ
キシド、ポリフェニレンサルファイドを用いるのが良い
、そしてかかる熱可塑性樹脂１００重量部に対し、上述
の炭素繊維を１〜７０重量部、好ましくは５〜４０重量
部配合するのがよい、配合する炭素繊維の形態としては
特に限定されないが、繊維長０．１〜３０■■、好まし
くは１〜１５＋ｍｓ＋の短繊維状がよい。Examples of thermoplastic resins used include polycarbonate, polystyrene, polyester, polyamide, polyolefin, acrylic resin, polyoxymethylene, polyphenylene sulfide, polyphenylene ether, polyphenylene oxide, polybutylene terephthalate, polyetherimide, polyether ether ketone, and polyphenylene sulfone. , polymers such as fluororesins, or copolymers thereof, and preferably polycarbonate, polyoxymethylene, polybutylene terephthalate, polyphenylene oxide, polyphenylene sulfide, and such heat treatment. It is preferable to blend 1 to 70 parts by weight, preferably 5 to 40 parts by weight, of the above-mentioned carbon fibers to 100 parts by weight of the plastic resin.The form of the carbon fibers to be blended is not particularly limited, but the fiber length is 0.1 -30 ms+, preferably 1-15+ms+ short fibers are preferred.
また、かかる炭素繊維は、通常サイジング剤を表面に被
覆した後樹脂と含浸するが良いが、そのサイジング剤と
しては通常任意のものが使用することができ、モノフィ
ラメントの集束性の良いものが選択できる。本発明にて
使用するサイジング剤は例えばエポキシ化合物、飽和又
は不飽和ポリエステル、ポリフェニレンサルファイド、
ポリフェニレンエーテル、ポリカーボネート、ポリオキ
シメチレン、ポリスチレン、ポリオレフィン、アクリル
樹脂、酢酸ビニル樹脂、ポリアミド樹脂などのホモポリ
マー又はコポリマーが挙げられる。In addition, such carbon fibers are usually coated with a sizing agent and then impregnated with a resin, but any sizing agent can be used, and one with good monofilament cohesiveness can be selected. . Sizing agents used in the present invention include, for example, epoxy compounds, saturated or unsaturated polyesters, polyphenylene sulfide,
Examples include homopolymers or copolymers such as polyphenylene ether, polycarbonate, polyoxymethylene, polystyrene, polyolefin, acrylic resin, vinyl acetate resin, and polyamide resin.
また必要に応じて、界面活性剤、シランカップリング剤
、エポキシ硬化剤、触媒、接着剤等を配合しても良い。Additionally, surfactants, silane coupling agents, epoxy curing agents, catalysts, adhesives, etc. may be added as necessary.
その際使用するサイジング剤の付着量は繊維全量に対し
て０．１〜１０重量％好ましくは０．５〜７重量％の範
囲で選択される。そして、その表面被覆方法としては、
例えば、数百〜数十万本の炭素長繊維束に、サイジング
剤を含浸させたのち、乾燥する。表面被覆に使用するサ
イジング剤は溶剤等に溶解させるか、あるいはサイジン
グ剤を含むエマルジョンを用いても良い。用いる溶剤と
しては、２−ブタノン、テトラヒドロフラン、Ｎ、Ｎ−
ジメチルホルムアミド、アセトン、クロロホルム、ジク
ロロメタン等が有る。またエマルジョンに用いる界面活
性剤としては、例えば、ポリオキシメチレンのヒマシ油
エーテル、ノニルフェニルエーテル、スチレン化フェニ
ルエーテルなどのポリオキシエチレンアルキルエーテル
又はポリオキシエチレンアルキルアリルエーテル及びポ
リビニルアルコールなどの中から選ばれた少なくとも１
種類の界面活性剤が挙げられる。サイジング剤の付着量
が０．１重量％未満では該炭素繊維集合体の集束性が劣
り、１０重量％を越えると炭素繊維強化熱可塑性樹脂の
物性が低下するため好ましくない。また、熱可塑性樹脂
と本発明の炭素繊維との配合方法としては特に限定され
るものではないが、通常−軸押出機、二軸押出機、プレ
ス機、高速ミキサー、射出成形機、引き抜き成形機等の
方法により行なわれる。The amount of the sizing agent used at this time is selected in the range of 0.1 to 10% by weight, preferably 0.5 to 7% by weight based on the total amount of fibers. The surface coating method is as follows:
For example, a bundle of hundreds to hundreds of thousands of long carbon fibers is impregnated with a sizing agent and then dried. The sizing agent used for surface coating may be dissolved in a solvent or the like, or an emulsion containing the sizing agent may be used. Solvents used include 2-butanone, tetrahydrofuran, N, N-
Examples include dimethylformamide, acetone, chloroform, dichloromethane, etc. The surfactant used in the emulsion may be selected from polyoxyethylene alkyl ethers such as polyoxymethylene castor oil ether, nonylphenyl ether, styrenated phenyl ether, polyoxyethylene alkyl allyl ether, and polyvinyl alcohol. at least 1
types of surfactants. If the amount of the sizing agent attached is less than 0.1% by weight, the cohesiveness of the carbon fiber aggregate will be poor, and if it exceeds 10% by weight, the physical properties of the carbon fiber reinforced thermoplastic resin will deteriorate, which is not preferable. Further, the method of blending the thermoplastic resin and the carbon fiber of the present invention is not particularly limited, but usually includes a screw extruder, twin screw extruder, press machine, high-speed mixer, injection molding machine, pultrusion molding machine. This is done using methods such as
更に、上記成分以外の本発明の効果を損なわない程度に
、例えば、他種の炭素繊維、ガラス繊維、アラミド繊維
、ボロン繊維、炭化珪素繊維等の短繊維及び長繊維、ウ
ィスカー類、あるいはカーボンブラック、二硫化モリブ
デン、マイカ、タルク、炭酸カルシウム、等のフィラー
類から成る強化材、安定剤、滑剤、その他添加剤などを
加えることができる。Furthermore, to the extent that the effects of the present invention other than the above-mentioned components are not impaired, other types of carbon fibers, glass fibers, aramid fibers, boron fibers, short fibers such as silicon carbide fibers, long fibers, whiskers, or carbon black may be added. , reinforcing agents such as fillers such as molybdenum disulfide, mica, talc, calcium carbonate, stabilizers, lubricants, and other additives can be added.
（実施例） 次に実施例により本発明をさらに詳細に説明する。(Example) Next, the present invention will be explained in more detail with reference to Examples.
（Ａ）炭素繊維の処理
実施例１
市販ピッチ系炭素繊維（単糸弾性率１８Ｔｏｎ／ｍｍり
を９００℃の窒素雰囲気下で約１分間加熱して繊維中の
官能基を脱官能基した。(A) Carbon fiber treatment example 1 A commercially available pitch-based carbon fiber (single yarn elastic modulus 18T/mm) was heated in a nitrogen atmosphere at 900° C. for about 1 minute to remove functional groups in the fiber.
かくして得られた炭素繊維についてＸ線分光法（Ｅ Ｓ
ＣＡ）により、繊維最表面の官能基量（０１Ｓ／ＣＩ
Ｓ）を測定した結果、Ｑ、 ０３２であった。The carbon fiber thus obtained was subjected to X-ray spectroscopy (ES
CA), the amount of functional groups on the outermost surface of the fiber (01S/CI
The result of measuring S) was Q, 032.
実施例２
市販ピッチ系炭素繊維（単糸弾性率２３ Ｔｏｎ／ａｍ
”）を９′ｏＯ℃の窒素雰囲気下で約１分間加熱して繊
維中の官能基を脱官能基した。Example 2 Commercially available pitch-based carbon fiber (single yarn elastic modulus 23 Ton/am
) was heated for about 1 minute at 9'oO<0>C under a nitrogen atmosphere to defunctionalize the functional groups in the fiber.
かくして得られた炭素繊維についてＸ線分光法（ＥＳＣ
Ａ）により、繊維最表面の官能基！（０１Ｓ／ＣＩ Ｓ
）を測定した結果、０．０２４であった。The carbon fiber thus obtained was subjected to X-ray spectroscopy (ESC).
By A), the functional group on the outermost surface of the fiber! (01S/CI S
) was measured and found to be 0.024.
比較例１
市販ピッチ系炭素繊維（単糸弾性率１９Ｔｏｎ／ｍｍり
を４００℃の窒素雰囲気下で約１分間加熱した。Comparative Example 1 A commercially available pitch-based carbon fiber (single yarn elasticity modulus: 19T/mm) was heated at 400° C. in a nitrogen atmosphere for about 1 minute.
かくして得られた炭素繊維についてＸ線分光法（ＥＳＣ
Ａ）により、繊維最表面の官能基量（ＯＩ Ｓ／ＣＩ
Ｓ）を測定した結果、０．１５であった。The carbon fiber thus obtained was subjected to X-ray spectroscopy (ESC).
A) determines the amount of functional groups on the outermost surface of the fiber (OIS/CI
As a result of measuring S), it was 0.15.
比較例２
市販ピッチ系炭素繊維（単糸弾性率６５Ｔｏｎ／ｓ＋が
）を９００℃の窒素雰囲気下で約１分間加熱した。Comparative Example 2 A commercially available pitch-based carbon fiber (single yarn elasticity modulus of 65 Ton/s+) was heated for about 1 minute at 900° C. in a nitrogen atmosphere.
かくして得られた炭素繊維についてＸ線分光法（ＥＳＣ
Ａ）により、繊維最表面の官能基量（０１Ｓ／ＣＩ Ｓ
）を測定した結果、０．０２１であった。The carbon fiber thus obtained was subjected to X-ray spectroscopy (ESC).
A), the amount of functional groups on the outermost surface of the fiber (01S/CIS
) was measured and found to be 0.021.
（Ｂ）炭素短繊維集合体の製造
上記ピッチ系炭素長繊維を、゛′エピコート８３４”
（シェル化学社製）５０重量部と“エピコート１００４
”” （シェル化学社製）５０重量部とのエマルジョン
溶液（濃度３重量％）中に含浸させたのち、約１２０°
Ｃで２０分間加熱乾燥し、さらに切断機で６１長の炭素
短繊維集合体を製造した。(B) Production of short carbon fiber aggregate The pitch-based long carbon fibers were
(manufactured by Shell Chemical Co., Ltd.) 50 parts by weight and "Epicote 1004"
After impregnating it in an emulsion solution (concentration 3% by weight) with 50 parts by weight (manufactured by Shell Chemical Co., Ltd.),
The mixture was dried by heating at C for 20 minutes, and then a 61-length carbon short fiber aggregate was produced using a cutting machine.
得られた炭素短繊維集合体のエポキシ化合物含有量は３
．１重量％であった。The epoxy compound content of the obtained short carbon fiber aggregate was 3
．． It was 1% by weight.
（Ｃ）炭素短繊維強化成形材料の製造
前記炭素短繊維集合体２０重量部と乾燥したポリブチレ
ンテレフタレート樹脂ペレット（三菱化成株式会社製”
ノバドゥール”）８０重量部とをトライブレンドした後
、スクリュー押出機にしこみ、溶融混合してストランド
状に押出し、水冷後ベレント状に切断した。(C) Production of short carbon fiber reinforced molding material 20 parts by weight of the short carbon fiber aggregate and dried polybutylene terephthalate resin pellets (manufactured by Mitsubishi Kasei Corporation)
After tri-blending 80 parts by weight of "Novadur"), the mixture was poured into a screw extruder, melt-mixed, extruded into strands, cooled with water, and cut into strands.
このようにして得られた炭素短繊維強化成形材料を９０
°Ｃ４時間乾燥した後、射出成形にて成形し試験片を得
た。The short carbon fiber reinforced molding material obtained in this way was
After drying at °C for 4 hours, it was molded by injection molding to obtain a test piece.
ついで、これらの試験片について各物性は次のようにし
て測定した。Next, the physical properties of these test pieces were measured as follows.
成形品の物性 成形品の物性は以下の法に準拠して測定する。Physical properties of molded products The physical properties of molded products are measured in accordance with the following methods.
引張強度 ： ＡＳＴＭ法 Ｄ６３８体積固有抵抗
： ５ＲＩＳ法 ５ＲＩＳ２３０１尚、実施例１〜２
．比較例１〜２及び炭素繊維を加えていない未強化品の
試験片の力学的および電気的特性を第１表に示す。Tensile strength: ASTM method D638 Volume resistivity: 5RIS method 5RIS2301 Examples 1 to 2
．． Table 1 shows the mechanical and electrical properties of the test specimens of Comparative Examples 1 and 2 and unreinforced specimens to which no carbon fibers were added.
第１表
（発明の効果）
本発明は繊維強化複合材の力学的、電気的特性を改善す
る炭素繊維を提供する。Table 1 (Effects of the Invention) The present invention provides carbon fibers that improve the mechanical and electrical properties of fiber-reinforced composites.
三菱化成株式会社Mitsubishi Kasei Corporation
Claims (2)
炭素繊維表面の官能基量（Ｏ１Ｓ／Ｃ１Ｓ）が０．０２
〜０．０５の範囲である繊維最表面層を有し、かつ引張
弾性率が１０ｔｏｎ／ｍｍ＾２〜３０ｔｏｎ／ｍｍ＾２
の範囲である導電性複合材料製造用炭素繊維。(1) The amount of functional groups on the carbon fiber surface (O1S/C1S) detected by X-ray electron spectroscopy (ECSA) is 0.02
It has a fiber outermost layer in the range of ~0.05 and a tensile modulus of 10 ton/mm^2 to 30 ton/mm^2
carbon fiber for the production of conductive composite materials.
法（ＥＣＳＡ）によって検出される炭素繊維表面の官能
基量（Ｏ１Ｓ／Ｃ１Ｓ）が０．０２〜０．０５の範囲で
ある繊維最表面層を有し、かつ引張弾性率が１０ｔｏｎ
／ｍｍ＾２〜３０ｔｏｎ／ｍｍ＾２の範囲である炭素繊
維を１〜７０重量部配合してなる炭素繊維強化熱可塑性
樹脂組成物。(2) The fibers have a functional group content (O1S/C1S) on the carbon fiber surface detected by X-ray electron spectroscopy (ECSA) in the range of 0.02 to 0.05 based on 100 parts by weight of the thermoplastic resin. Has a surface layer and has a tensile modulus of 10 tons
A carbon fiber-reinforced thermoplastic resin composition containing 1 to 70 parts by weight of carbon fiber having a carbon fiber content of 1 to 70 parts by weight in the range of 2 to 30 tons/mm2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1636190A JPH03220320A (en) | 1990-01-26 | 1990-01-26 | Carbon fiber for producing electrically conductive composite material and thermoplastic resin composition using same fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1636190A JPH03220320A (en) | 1990-01-26 | 1990-01-26 | Carbon fiber for producing electrically conductive composite material and thermoplastic resin composition using same fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03220320A true JPH03220320A (en) | 1991-09-27 |
Family
ID=11914200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1636190A Pending JPH03220320A (en) | 1990-01-26 | 1990-01-26 | Carbon fiber for producing electrically conductive composite material and thermoplastic resin composition using same fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03220320A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0623935A1 (en) * | 1993-05-03 | 1994-11-09 | Du Pont De Nemours International S.A. | Conductive composition |
| JP2013087269A (en) * | 2011-10-21 | 2013-05-13 | Res Inst For Prod Dev | Short carbon fiber, method for producing the same, short carbon fiber-reinforced resin composition, and short carbon fiber-reinforced cement composition |
-
1990
- 1990-01-26 JP JP1636190A patent/JPH03220320A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0623935A1 (en) * | 1993-05-03 | 1994-11-09 | Du Pont De Nemours International S.A. | Conductive composition |
| JP2013087269A (en) * | 2011-10-21 | 2013-05-13 | Res Inst For Prod Dev | Short carbon fiber, method for producing the same, short carbon fiber-reinforced resin composition, and short carbon fiber-reinforced cement composition |
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