JPH0342306B2 - - Google Patents
Info
- Publication number
- JPH0342306B2 JPH0342306B2 JP57190068A JP19006882A JPH0342306B2 JP H0342306 B2 JPH0342306 B2 JP H0342306B2 JP 57190068 A JP57190068 A JP 57190068A JP 19006882 A JP19006882 A JP 19006882A JP H0342306 B2 JPH0342306 B2 JP H0342306B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- carbon fibers
- thermoplastic resin
- surface treatment
- treatment agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 24
- 239000004917 carbon fiber Substances 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 229920005992 thermoplastic resin Polymers 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011342 resin composition Substances 0.000 claims description 4
- 239000012756 surface treatment agent Substances 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 239000004797 high-impact polystyrene Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000011199 continuous fiber reinforced thermoplastic Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 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 1
- 238000009863 impact test Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は炭素繊維含有複合材料において、炭素
繊維、マトリツクス樹脂間の接着性を向上させ、
優れた機械的性質を持たせることを特徴とする、
表面処理を行なつた炭素繊維を配合してなる炭素
繊維強化熱可塑性樹脂組成物に関関するものであ
る。
これまで、炭素繊維の表面処理は種々検討され
ている。しかしほとんどは熱硬化性樹脂用に関す
るものが多く実用的にはエポキシ樹脂を表面処理
したものがほとんどである。熱可塑性樹脂をマト
リツクスとする際の炭素繊維用表面処理剤の検討
はこれまでほとんど検討されておらず、炭素繊維
の集束剤としてポリアミド、ポリスルホン、ポリ
ビニルアルコール等が検討されているにすぎず、
これらの重合体炭素繊維に被覆しても充分な界面
効果は得られない。しかも他フイラ含有複合材料
と同様に、炭素繊維強化熱可塑性樹脂（以下
CFRTPと略す）においても、炭素繊維とマトリ
ツクス樹脂である各種熱可塑性樹脂との接着性は
複合効果の発現上極めて重要な因子となる。そこ
で、本発明者等は、前者の炭素繊維の集束と炭素
繊維、熱可塑性樹脂間の接着性向上の２つの目的
を兼ね備えた表面処理剤を見出すべく鋭意検討し
た結果、AS樹脂で炭素繊維の表面被覆すること
によりチヨツプドストランド製造時及び熱可塑性
樹脂との複合時の作業性に優れ、又複合材料とし
ての機械的性質が著じるしく向上することを見出
し、本発明を完成した。
本発明に用いるAS樹脂としては比粘度ηsp／ｃ
（0.1％DMF、25℃で測定）は、0.3〜0.7ml／ｇで
ある。粘度が低すぎると炭素繊維の集束性が悪く
毛羽立ちが多くなり、チヨツプドストランド製造
時及び熱可塑性樹脂との複合時の作業性が悪くな
る。ηsp／ｃが高すぎると各単繊維への表面処理
が困難になり、複合材料中で各単繊維が分散した
とき、マトリクス樹脂との接着性が悪くなる。
又、AS樹脂の炭素繊維の被覆量は、炭素繊維と
表面処理剤の総重量の３〜７重量％である。一般
に表面処理剤被覆量が少量でありすぎると、スト
ランドの毛羽立ちが多くなり、チヨツプドストラ
ンド製造時及び熱可塑性樹脂との複合時の作業性
が悪くなる。又、表面処理剤の被覆量が多量であ
りすぎると、処理後の炭素繊維ストランドの巻き
取り性が悪くなつたり、表面処理剤が影響して複
合材料全体としての物性が劣るようになる。AS
樹脂の組成においてはアクリロニトリル：スチレ
ン＝５：95〜30：70が適当である。表面処理の方
法は特に限定されないが、好適な具体例として
は、表面処理剤を適当な溶剤、例えばメチルエチ
ルケトン、塩化メチレンに溶解し、その中に炭素
繊維を一定速度で浸漬通過させ、その後溶剤を蒸
発させて乾燥する方法が挙げられる。炭素繊維へ
の表面処理剤の被覆量は、この表面処理剤濃度と
炭素繊維の通過速度によつて調節される。
本発明の樹脂組成物において用いる熱可塑性樹
脂の具体例としてはナイロン６、ナイロン６，
６、ナイロン６，12、ABS，AS，PC，PE，
PAC，MMA，PPS，ポリスチレン、ハイインパ
クトポリスチレンなどいずれのものでも適用でき
るが、特に有効であるのはABS，AS，ポリスチ
レン、ハイインパクトポリスチレンを挙げること
ができる。
本発明で用いる炭素繊維は、AS樹脂が被覆さ
れているため従来開発されてきた表面処理を施し
た炭素繊維に比べ、上記熱可塑性樹脂との親和性
が著るしく改良されており、機械的特性の優れた
熱可塑性樹脂組成物とすることができる。
以下実施例により具体的に説明する。
実施例 １
アクリロニトリル；スチレン＝15：85の組成比
で、比粘度ηsp／ｃ（0.1％DMF，25℃で測定）が
表１に示されたAS樹脂をメチルエチルケトンに
溶解し、それに炭素繊維を浸漬通過させ表１に示
した被覆量のAS樹脂を被覆させ、乾燥した後、
チヨツプドストランドにカツトし、表１に示され
た熱可塑性樹脂に含有率20wt％で押出機にかけ、
ペレツトを得た。そのペレツトを射出成形し、物
性を測定した結果を表１に示した。実験番号１〜
４は本発明のものを、実験番号５〜10は比較例を
示す。
尚、物性評価は、引張試験はASTM−D638、
曲げ試験はASTM−D790、アイゾツト衝撃試験
はASTM−D256に準じて実施した。
表１に示したように、AS樹脂で表面処理した
炭素繊維を配合したCFRTDは優れた機械的性質
を持つことがわかる。
The present invention improves the adhesion between carbon fibers and matrix resin in carbon fiber-containing composite materials,
Characterized by having excellent mechanical properties,
The present invention relates to a carbon fiber-reinforced thermoplastic resin composition containing surface-treated carbon fibers. Until now, various surface treatments of carbon fibers have been studied. However, most of them are for thermosetting resins, and in practical use, most of them are surface-treated epoxy resins. Until now, there has been almost no investigation into surface treatment agents for carbon fibers when thermoplastic resin is used as a matrix, and only polyamides, polysulfones, polyvinyl alcohols, etc. have been studied as sizing agents for carbon fibers.
Even if these polymer carbon fibers are coated, sufficient interfacial effects cannot be obtained. Moreover, like other filler-containing composite materials, carbon fiber-reinforced thermoplastic resin (hereinafter referred to as
(abbreviated as CFRTP), the adhesion between carbon fibers and various thermoplastic resins as matrix resins is an extremely important factor in achieving the composite effect. Therefore, the present inventors conducted extensive research to find a surface treatment agent that has the two purposes of converging carbon fibers and improving the adhesion between carbon fibers and thermoplastic resin. The present invention was completed based on the discovery that surface coating provides excellent workability during the production of chopped strands and when composited with thermoplastic resin, and also significantly improves the mechanical properties of the composite material. . The AS resin used in the present invention has a specific viscosity ηsp/c
(0.1% DMF, measured at 25°C) is 0.3-0.7 ml/g. If the viscosity is too low, the carbon fibers will have poor cohesiveness and will become fluffy, resulting in poor workability during production of chopped strands and when composited with thermoplastic resin. If ηsp/c is too high, surface treatment of each single fiber becomes difficult, and when each single fiber is dispersed in the composite material, adhesion with the matrix resin becomes poor.
The amount of carbon fiber covered with the AS resin is 3 to 7% by weight based on the total weight of the carbon fiber and surface treatment agent. Generally, if the coating amount of the surface treatment agent is too small, the strands will become more fluffy and the workability during production of chopped strands and when compounding with thermoplastic resin will be poor. Furthermore, if the coating amount of the surface treatment agent is too large, the winding properties of the carbon fiber strand after treatment will be poor, and the physical properties of the composite material as a whole will be deteriorated due to the influence of the surface treatment agent. A.S.
A suitable composition of the resin is acrylonitrile:styrene=5:95 to 30:70. The surface treatment method is not particularly limited, but a preferred example is to dissolve the surface treatment agent in a suitable solvent, such as methyl ethyl ketone or methylene chloride, and pass the carbon fiber through the solution at a constant speed, and then remove the solvent. An example is a method of drying by evaporation. The amount of the surface treatment agent coated on the carbon fibers is adjusted by the concentration of the surface treatment agent and the passing speed of the carbon fibers. Specific examples of the thermoplastic resin used in the resin composition of the present invention include nylon 6, nylon 6,
6. Nylon 6, 12, ABS, AS, PC, PE,
Any material such as PAC, MMA, PPS, polystyrene, or high-impact polystyrene can be used, but ABS, AS, polystyrene, and high-impact polystyrene are particularly effective. Since the carbon fibers used in the present invention are coated with AS resin, their affinity with the thermoplastic resin is significantly improved compared to surface-treated carbon fibers that have been developed in the past. A thermoplastic resin composition with excellent properties can be obtained. This will be explained in detail below using examples. Example 1 An AS resin with a composition ratio of acrylonitrile:styrene = 15:85 and a specific viscosity ηsp/c (measured at 25°C in 0.1% DMF) shown in Table 1 was dissolved in methyl ethyl ketone, and carbon fibers were immersed in it. After passing through and coating with AS resin in the coating amount shown in Table 1, and drying,
Cut into chopped strands, extrude into the thermoplastic resin shown in Table 1 at a content of 20wt%,
Got pellets. The pellets were injection molded and their physical properties were measured, and the results are shown in Table 1. Experiment number 1~
Experiment No. 4 shows the one of the present invention, and Experiment No. 5 to 10 show comparative examples. In addition, for physical property evaluation, tensile test is ASTM-D638,
The bending test was conducted according to ASTM-D790, and the Izot impact test was conducted according to ASTM-D256. As shown in Table 1, it can be seen that CFRTD containing carbon fibers surface-treated with AS resin has excellent mechanical properties.
【表】【table】
Claims (1)
で測定）が0.3〜0.7ml／ｇであるAS樹脂を該AS
樹脂と炭素繊維との総重量の３〜７重量となる割
合で付着した炭素繊維と熱可塑性樹脂とよりなる
炭素繊維強化樹脂組成物。1 Specific viscosity ηSP/C (0.1% by weight DMF solution at 25℃
AS resin with an AS resin of 0.3 to 0.7 ml/g
A carbon fiber reinforced resin composition comprising carbon fibers and a thermoplastic resin attached at a ratio of 3 to 7 weights of the total weight of the resin and carbon fibers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19006882A JPS5980447A (en) | 1982-10-29 | 1982-10-29 | Carbon-fiber reinforced thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19006882A JPS5980447A (en) | 1982-10-29 | 1982-10-29 | Carbon-fiber reinforced thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5980447A JPS5980447A (en) | 1984-05-09 |
| JPH0342306B2 true JPH0342306B2 (en) | 1991-06-26 |
Family
ID=16251814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19006882A Granted JPS5980447A (en) | 1982-10-29 | 1982-10-29 | Carbon-fiber reinforced thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5980447A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103993480B (en) * | 2013-02-18 | 2016-06-15 | 广州金发碳纤维新材料发展有限公司 | Carbon fiber surface modification emulsion and preparation method thereof and its modified carbon fiber prepared, moulding compound |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6439453A (en) * | 1987-08-04 | 1989-02-09 | Sekisui Chemical Co Ltd | Downspout device |
-
1982
- 1982-10-29 JP JP19006882A patent/JPS5980447A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5980447A (en) | 1984-05-09 |
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