JPH03269164A - Surface modification of carbon fiber - Google Patents
Surface modification of carbon fiberInfo
- Publication number
- JPH03269164A JPH03269164A JP2068968A JP6896890A JPH03269164A JP H03269164 A JPH03269164 A JP H03269164A JP 2068968 A JP2068968 A JP 2068968A JP 6896890 A JP6896890 A JP 6896890A JP H03269164 A JPH03269164 A JP H03269164A
- Authority
- JP
- Japan
- Prior art keywords
- alkali
- carbon fiber
- treatment
- carbon fibers
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 22
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 22
- 230000004048 modification Effects 0.000 title claims description 4
- 238000012986 modification Methods 0.000 title claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 abstract description 9
- 239000011737 fluorine Substances 0.000 abstract description 9
- 229910052788 barium Inorganic materials 0.000 abstract description 2
- 229910052700 potassium Inorganic materials 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 238000009736 wetting Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 150000001721 carbon Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 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
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005087 graphitization Methods 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
- -1 hydroxide ions Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical class [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、炭素繊維の表面改質方法に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a method for surface modification of carbon fibers.
（従来の技術）
炭素繊維は、“実質的に炭素元素だけからなる繊維状の
炭素材料”であり、物質としての炭素と形態としての繊
維に由来する多様な特性をあわせもつ特異な材料である
。すなわち、耐熱性、化学安定性、ｉ電性、熱伝導性、
摺動特性、生体親和性などの炭素材料に固有の特性を持
っている。また、繊維状に賦形することによって得られ
る特性の第一は柔軟性であり繊維構造が賦与された場合
には高剛性１寸法安定性などの特性も発現される。(Prior art) Carbon fiber is a "fibrous carbon material consisting essentially only of carbon elements," and is a unique material that has various properties derived from carbon as a substance and fiber as a form. . That is, heat resistance, chemical stability, i-electricity, thermal conductivity,
It has properties unique to carbon materials, such as sliding properties and biocompatibility. Furthermore, the first property obtained by shaping into a fibrous form is flexibility, and when a fibrous structure is imparted, properties such as high rigidity and 1-dimensional stability are also expressed.
このような炭素繊維はその耐熱性、軽量、高剛性などの
多くの優れた特性を利用して傘などの日用品やラケット
などのスポーツ用具から航空機や人工衛星の構造材料ま
でのほとんどの産業や民生の分野で巾広く使用されてい
る。また、合成繊維とは異なり、糸や、糸だけからなる
中間基材の形で使用されることは少なく、大半は複合材
料の形で使用されている。Utilizing its many excellent properties such as heat resistance, light weight, and high rigidity, carbon fiber is used in most industrial and consumer products, from daily necessities such as umbrellas, sports equipment such as rackets, to structural materials for aircraft and artificial satellites. It is widely used in the field of Also, unlike synthetic fibers, they are rarely used in the form of threads or intermediate substrates made only of threads, and are mostly used in the form of composite materials.
しかし、炭素化あるいは黒鉛化を経て得られる炭素繊維
は表面の濡れ性が悪くマトリクス樹脂との接着性が小さ
い。そこで、接着性改良のための繊維の濡れ性向上の方
法としては、繊維を化学的に処理して官能基を導入する
方法、表面に接着性のよい物質を固着させる方法などが
検討されている。However, carbon fibers obtained through carbonization or graphitization have poor surface wettability and poor adhesion to matrix resins. Therefore, methods to improve the wettability of fibers to improve adhesion include methods of chemically treating fibers to introduce functional groups, and methods of fixing highly adhesive substances to the surface. .
後者においては炭化ケイ素のウィスカを成長させること
が試みられ改善効果があると報告されている。しかしな
がら、数千本の単繊維に均一にウィスカを成長させるこ
とが難しいうえ処理に時間がかかるため、この方法は実
用されていない。In the latter case, attempts have been made to grow silicon carbide whiskers, and this has been reported to have an improvement effect. However, this method has not been put to practical use because it is difficult to uniformly grow whiskers on thousands of single fibers and the process takes time.
また、前者においては酸化処理が通常用いられており、
表面に水酸基、カルボニル基、カルボキシル基が形成さ
れる他に、表面の緻密層が除去される、表面積が大きく
なる、表面に凹凸が生じるなどの変化が濡れ性の向上、
接着性改良に効果を表わす。In addition, in the former case, oxidation treatment is usually used,
In addition to the formation of hydroxyl, carbonyl, and carboxyl groups on the surface, changes such as removing the dense layer on the surface, increasing the surface area, and creating irregularities on the surface improve wettability.
Effective in improving adhesion.
また、そのほかの化学的手法の一つとしてフッ素ガスを
用いて炭素材とマトリクスとの親和性を増す方法が報告
されている（特開昭６０−１９１０１１号公報）。Furthermore, as one of the other chemical methods, a method has been reported in which fluorine gas is used to increase the affinity between the carbon material and the matrix (Japanese Patent Application Laid-Open No. 191011/1982).
（発明が解決しようとする課題）
上記酸化処理においては、表面処理の程度を強くしても
活性点の量は処理の程度に比例して増加するわけでなく
、また表面の粗化は欠陥の導入に他ならずより一層の濡
れ性の改善が求められている。(Problem to be solved by the invention) In the above oxidation treatment, even if the degree of surface treatment is strengthened, the amount of active sites does not increase in proportion to the degree of treatment, and the roughening of the surface does not cause defects. There is a need for further improvement in wettability.
（課題を解決するための手段）
本発明者らは炭素繊維とマトリクスとの親和力を向上さ
せる目的で、種々検討を行ない、炭素繊維のフッ素化と
アルカリ処理とを併用することにより、著しく濡れ性が
向上することを見いだし、本発明に到達した。(Means for Solving the Problem) The present inventors have conducted various studies for the purpose of improving the affinity between carbon fibers and the matrix, and found that by combining fluorination of carbon fibers and alkali treatment, the wettability is significantly improved. The present invention has been achieved based on the discovery that this can be improved.
すなわち、本発明は、炭素繊維の表面をフッ素化処理し
、ついでアルカリで処理することを特徴とする炭素繊維
の表面改質方法を要旨とする。That is, the gist of the present invention is a method for surface modification of carbon fibers, which is characterized in that the surface of carbon fibers is fluorinated and then treated with an alkali.
以下、本発明の詳細な説明する。まず、本発明において
用いられる炭素繊維は、公知の各種原料から製造しうろ
ことができ、たとえば、石炭タールピッチ、石油ピッチ
、ポリアクリロニトリル。The present invention will be explained in detail below. First, the carbon fibers used in the present invention can be manufactured from various known raw materials, such as coal tar pitch, petroleum pitch, and polyacrylonitrile.
セルロース、ポリビニルアルコール等かう製造され、炭
素化処理された炭素繊維もしくは黒鉛化処理された黒鉛
化繊維、又は気相法によるウィスカ等も用いることがで
きる。Carbon fibers or graphitized fibers produced in this manner such as cellulose or polyvinyl alcohol, which have been carbonized, or graphitized fibers which have been graphitized, or whiskers produced by a vapor phase method can also be used.
本発明におけるフッ素化処理は、フッ素ガスにより行な
われる。その温度は９０℃以下、望ましくは３０℃以下
のＣ−Ｆの共有結合を十分形成しない温度域が好適であ
る。また、フッ素化処理時間は炭素材料に均一にフッ素
が供給されれば短時間の処理でよく、時間が長くなって
もそれ相応の効果は期待できないため通常は１〜３０分
の処理時間であり、より好ましくは１０分以下である。The fluorination treatment in the present invention is performed using fluorine gas. The temperature is preferably 90° C. or lower, preferably 30° C. or lower, which is a temperature range in which C-F covalent bonds are not sufficiently formed. In addition, the fluorination treatment time may be short as long as fluorine is uniformly supplied to the carbon material, and the treatment time is usually 1 to 30 minutes, as no corresponding effect can be expected even if the time is longer. , more preferably 10 minutes or less.
フッ素ガスのフッ素分圧は加圧〜減圧まで特に制限ない
が、好ましくはｌｍＨｇ〜５０ｍＨｇで処理するのがよ
い。The fluorine partial pressure of the fluorine gas is not particularly limited, and may range from increased pressure to reduced pressure, but it is preferably 1 mHg to 50 mHg.
また、フッ素ガスとしてはそれ単独で用いても、窒素、
アルゴンなどの不活性ガスを混合しても用いることがで
きる。更に、酸素等のガスを含んでいても用いることが
出来る。In addition, even if fluorine gas is used alone, nitrogen,
A mixture of an inert gas such as argon can also be used. Furthermore, it can be used even if it contains a gas such as oxygen.
本発明においては、上記フッ素化処理後に、炭素繊維の
表面をアルカリ処理する。In the present invention, after the fluorination treatment, the surface of the carbon fiber is treated with an alkali.
アルカリとしては、カリウム、ナトリウム等のアルカリ
金属の水酸化物、炭酸塩、バリウム等のアルカリ土金属
の水酸化物等、溶液中で水酸イオンを形成するものが挙
げられる。Examples of the alkali include those that form hydroxide ions in solution, such as hydroxides of alkali metals such as potassium and sodium, carbonates, and hydroxides of alkaline earth metals such as barium.
これらのアルカリの濃度は通常１Ｎ以下、好適には０．
１〜０．００１ Ｎで用いられる。The concentration of these alkalis is usually 1N or less, preferably 0.
It is used at 1 to 0.001N.
上記アルカリ処理は、前段のフッ素化処理の程度、アル
カリ濃度によっても異なるが、通常室温〜１００℃程度
の温度で、数秒〜数日間の条件から選択される。The alkali treatment is usually carried out at a temperature of room temperature to about 100° C. and for a period of several seconds to several days, although it varies depending on the degree of the previous fluorination treatment and the alkali concentration.
本発明方法においては、上記フン素化処理後に、各種の
薬液酸化もしくは電解酸化等の液相酸化又は気相酸化を
行ない、ついで上記のアルカリ処理を行うこともできる
。In the method of the present invention, after the fluorination treatment, liquid phase oxidation or gas phase oxidation such as various chemical oxidation or electrolytic oxidation can be performed, and then the above alkali treatment can be performed.
本発明により表面改質された炭素繊維は、エポキシ樹脂
、不飽和ポリエステル樹脂、ビスマレイミド樹脂、ポリ
イミド樹脂、ポリスルホン樹脂、ポリエーテルエーテル
ケトン樹脂等の熱硬化及び熱可塑性樹脂との接着性が向
上し、複合材料用の繊維強化材として有用である。The surface-modified carbon fibers of the present invention have improved adhesion to thermosetting and thermoplastic resins such as epoxy resins, unsaturated polyester resins, bismaleimide resins, polyimide resins, polysulfone resins, and polyether ether ketone resins. , useful as fiber reinforcement for composite materials.
（実施例）
以下、実施例により本発明を更に詳細に説明するが、本
発明の範囲はその要旨を越えない限り実施例に限定され
るものではない。(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the scope of the present invention is not limited to the Examples unless it exceeds the gist thereof.
実施例１〜４及び比較例１〜３
ピッチ系炭素繊維（１５００℃焼成）約０．１ ｇを、
フッ素化処理用反応器内に入れ、容器内を真空に保った
後、フッ素ガスを導入し、表１に示すフッ素化条件で処
理した。ついで、得られたフッ素化処理炭素繊維を表１
に示す条件でアルカリで処理し、改質炭素繊維を得た。Examples 1 to 4 and Comparative Examples 1 to 3 About 0.1 g of pitch-based carbon fiber (calcined at 1500°C),
After placing it in a fluorination treatment reactor and keeping the inside of the container in vacuum, fluorine gas was introduced and treatment was performed under the fluorination conditions shown in Table 1. Then, the obtained fluorinated carbon fibers are shown in Table 1.
Modified carbon fibers were obtained by treatment with alkali under the conditions shown below.
これらの改質炭素繊維の水に対する濡れ性の尺度として
ウイルヘルミイ法による後退接触角の測定を行った（測
定装置：島津自動接触角測定装置“５Ｔ−Ｉ Ｓ”）。As a measure of the water wettability of these modified carbon fibers, the receding contact angle was measured by the Wilhelmy method (measuring device: Shimadzu automatic contact angle measuring device "5T-IS").
測定は５回行い、その平均値を表１に示す。The measurement was performed five times, and the average value is shown in Table 1.
（発明の効果）
本発明方法によれば、表面の濡れ性が向上し、経時的に
も安定な炭素繊維を得ることができる。(Effects of the Invention) According to the method of the present invention, carbon fibers with improved surface wettability and stability over time can be obtained.
出 代 願 理 人 人 渡 辺 信 淳 （ほか１名）Out teenager wish Reason Man Man Atsushi Watari (1 other person)
Claims (3)
リで処理することを特徴とする炭素繊維の表面改質方法
。(1) A method for surface modification of carbon fibers, which comprises fluorinating the surface of carbon fibers and then treating them with an alkali.
項１記載の方法。2. The method of claim 1, wherein the fluorination treatment is carried out at a temperature of about 90°C or less.
方法。(3) The method according to claim 1, wherein the concentration of the alkali is 1N or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2068968A JP2932582B2 (en) | 1990-03-19 | 1990-03-19 | Surface modification method for carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2068968A JP2932582B2 (en) | 1990-03-19 | 1990-03-19 | Surface modification method for carbon fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03269164A true JPH03269164A (en) | 1991-11-29 |
| JP2932582B2 JP2932582B2 (en) | 1999-08-09 |
Family
ID=13388983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2068968A Expired - Fee Related JP2932582B2 (en) | 1990-03-19 | 1990-03-19 | Surface modification method for carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2932582B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008106109A (en) * | 2006-10-24 | 2008-05-08 | Nagase Chemtex Corp | Method for producing carbon fiber-reinforced composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4938954B1 (en) * | 1970-12-24 | 1974-10-22 | ||
| JPS60191011A (en) * | 1984-03-13 | 1985-09-28 | Central Glass Co Ltd | Modified carbonaceous material |
-
1990
- 1990-03-19 JP JP2068968A patent/JP2932582B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4938954B1 (en) * | 1970-12-24 | 1974-10-22 | ||
| JPS60191011A (en) * | 1984-03-13 | 1985-09-28 | Central Glass Co Ltd | Modified carbonaceous material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008106109A (en) * | 2006-10-24 | 2008-05-08 | Nagase Chemtex Corp | Method for producing carbon fiber-reinforced composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2932582B2 (en) | 1999-08-09 |
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