JP2816433B2 - Carbon fiber for cement - Google Patents
Carbon fiber for cementInfo
- Publication number
- JP2816433B2 JP2816433B2 JP28644289A JP28644289A JP2816433B2 JP 2816433 B2 JP2816433 B2 JP 2816433B2 JP 28644289 A JP28644289 A JP 28644289A JP 28644289 A JP28644289 A JP 28644289A JP 2816433 B2 JP2816433 B2 JP 2816433B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- cement
- surfactant
- fiber
- silane coupling
- 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
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、炭素繊維とセメントの均一な配合性と付着
力に優れ、セメント系複合材にした時に強度発現性の良
好な炭素繊維を提供するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides a carbon fiber which is excellent in uniform compoundability and adhesion of carbon fiber and cement, and has good strength development when made into a cement-based composite material. Is what you do.
従来セメント類の水硬性紛体を用いた混練物は各種の
建築材料、土木材料に広く用いられている。このような
混練物を補強し、亀裂発生を防止するため、繊維材料を
配合することも行われてきた。しかし補強繊維として石
綿を用いることは、発癌性の点から好ましくなく、また
ガラス繊維は耐アルカリ性が劣つているため、セメント
中でガラス繊維自体の強度が劣化するという欠点を持つ
ている。このため各種の有機繊維或いは耐アルカリガラ
ス等が強化材として検討されているが、有機繊維では耐
火性の点に問題があり、耐アルカリガラスに用いてもセ
メント等のアルカリ性環境下では、長期間使用すると強
度が低下するという問題がある。そこで耐熱性、耐薬品
性に優れた炭素繊維が注目されている。ところが炭素繊
維をセメントに添加混合すると均一に分散しにくく、さ
らに均一な分散を得るため強度に撹拌を行うと、繊維の
切断が起つたり、フアイバーボールと呼ばれる繊維の毛
羽だまりができてしまい、補強材として充分な効果を発
揮し得なかつた。Conventionally, kneaded materials using hydraulic powders of cements have been widely used for various building materials and civil engineering materials. In order to reinforce such a kneaded material and to prevent the occurrence of cracks, a fiber material has been blended. However, the use of asbestos as a reinforcing fiber is not preferable from the viewpoint of carcinogenicity, and has the disadvantage that the strength of the glass fiber itself is deteriorated in cement because the glass fiber has poor alkali resistance. For this reason, various types of organic fibers or alkali-resistant glass have been studied as reinforcing materials.However, organic fibers have a problem in terms of fire resistance. There is a problem that the strength is reduced when used. Therefore, carbon fibers having excellent heat resistance and chemical resistance have attracted attention. However, when carbon fiber is added to and mixed with cement, it is difficult to uniformly disperse it, and if stirring is performed to obtain a more uniform dispersion, the fiber may be cut or a fiber ball called a fiber ball may be formed. A sufficient effect as a reinforcing material could not be exhibited.
この問題を解決するため、繊維補強材に界面活性剤を
付着させる方法（特開昭60−96554号）、炭素繊維をス
ルホン化処理する方法（特開昭60−137860号）、セメン
トに減水剤を混入する方法（特開昭61−236646号）、炭
素繊維にラテツクスコーテイングを行う方法（特開昭62
−108755号）、アルカリ金属またはアルカリ土金属の塩
化物を混入する方法（特開平１−141852号）、硫酸また
はチオ硫酸塩を混入させる方法（特開平１−141853号）
等が提案されている。In order to solve this problem, a method of attaching a surfactant to a fiber reinforcing material (Japanese Patent Application Laid-Open No. 60-96554), a method of sulfonating carbon fibers (Japanese Patent Application Laid-Open No. 60-137860), (Japanese Patent Application Laid-Open No. Sho 61-236646) and a method of performing latex coating on carbon fiber (Japanese Patent Application Laid-Open No. Sho 62-236646).
No.-108755), a method of mixing an alkali metal or alkaline earth metal chloride (JP-A-1-141852), and a method of mixing sulfuric acid or thiosulfate (JP-A-1-141853)
Etc. have been proposed.
しかし炭素繊維のスルホン化処理は処理に長時間を要
し、また炭素繊維と各種の化合物を付着させる方法また
はセメントに化合物を混入させる方法は、炭素繊維とそ
の化合物が反応しないので付着力の改善性に劣るという
問題点があつた。However, the sulfonation treatment of carbon fiber takes a long time, and the method of adhering various compounds to carbon fiber or the method of mixing compound into cement improves the adhesion because carbon fiber and the compound do not react. There was a problem that it was inferior.
そこで本発明は上記従来の問題点に鑑み、炭素繊維と
セメントの均一な分散性及び炭素繊維とセメントの付着
力を効率的にしかも効果的に解決した炭素繊維を提供す
るものである。Accordingly, the present invention has been made in view of the above-mentioned conventional problems, and has as its object to provide a carbon fiber in which the uniform dispersibility of carbon fiber and cement and the adhesive force between carbon fiber and cement are efficiently and effectively solved.
即ち本発明の要旨は、炭素繊維をシランカツプリング
剤処理した後、界面活性剤を付着させてなるセメント用
炭素繊維である。That is, the gist of the present invention is a carbon fiber for cement obtained by treating a carbon fiber with a silane coupling agent and then adhering a surfactant.
本発明の炭素繊維はポリアクリルニトリル（以下PAN
と略記）またはピツチを主成分とするプレカーサーを焼
成してなる弾性率3t/mm2以上、強度50kg/mm2以上の炭素
繊維であり、好ましくは弾性率20t/mm2以上、強度100kg
/mm2以上の炭素繊維である。The carbon fiber of the present invention is made of polyacrylonitrile (hereinafter referred to as PAN).
Or a carbon fiber having an elastic modulus of 3 t / mm 2 or more and a strength of 50 kg / mm 2 or more, and preferably an elastic modulus of 20 t / mm 2 or more and a strength of 100 kg.
/ mm 2 or more carbon fiber.
本発明のシランカツプリング剤は下記の一般式（１）
であらわされるもので、後で付着させる界面活性剤と反
応するもの或いは界面活性剤と強固に相互作用するもの
である必要がある。The silane coupling agent of the present invention has the following general formula (1)
And must react with a surfactant to be attached later or must strongly interact with the surfactant.
YRSiX3 ……（１） ここでＸは、ケイ素原子に結合している加水分解基で
あり、Cl,OCH3,OC2H5,OC2H4OCH3,OCOCH3,N（CH3）２等
である。YRSiX 3 ... (1) Here, X is a hydrolyzable group bonded to a silicon atom, and is Cl, OCH 3 , OC 2 H 5 , OC 2 H 4 OCH 3 , OCOCH 3 , N (CH 3 ) Second magnitude.
ここでYRは、界面活性剤と反応する或いは強固に相互
作用する有機官能基であり、CH2＝CH−,CH2＝CCH3COO
−， −NH2,−NH2CONH等である。Here, YR is an organic functional group that reacts or strongly interacts with a surfactant, and CH 2 CHCH—, CH 2 CCCH 3 COO
−, —NH 2 , —NH 2 CONH and the like.
一般式（１）で示される化合物の具体例としてはγ−
グリシドキシプロピルトリメトキシシラン、γ−クロロ
プロピルトリメトキシシラン、γ−メルカプトプロピル
トリメトキシシラン、γ−アミノプロピルトリエトキシ
シラン等を挙げることができる。Specific examples of the compound represented by the general formula (1) include γ-
Glycidoxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and the like can be mentioned.
使い易さと価格の面から、γ−グリシドキシプロピル
トリメトキシシランが好ましい。In terms of ease of use and price, γ-glycidoxypropyltrimethoxysilane is preferred.
本発明の界面活性剤はセメント系スラリーに空気を連
行しセメントのワーカビリテイを増加させるAE剤（air
−entraining admixture）に用いられるアルキルベンゼ
ンスルホン酸塩、アルキルスルホン酸トリエタノール等
またはセメント粒子を水中に分散させやすくする分散剤
（減水剤）に用いられるリグニンスルホン酸塩、オキシ
カルボン酸塩、アルキルアリルスルホン酸塩、高級アル
コール、アルキルベンゼンスルホン酸ソーダ系のものを
いう。The surfactant of the present invention is an AE agent (air) which entrains air into the cement slurry to increase the workability of the cement.
Lignin sulfonate, oxycarboxylate, alkylallyl sulfone used as an alkylbenzene sulfonate, triethanol alkyl sulfonate, etc. used for entraining admixture or as a dispersant (water reducing agent) for easily dispersing cement particles in water. Acid salts, higher alcohols, and sodium alkylbenzene sulfonates.
好ましくはシランカツプリング剤との反応性から考え
て、ポリエチレンオキサイド化合物、硫酸塩が選択さ
れ、ポリオキシエチレンステアリン酸エステル、リグニ
ンスルホン酸ソーダ等好ましい。Preferably, polyethylene oxide compounds and sulfates are selected from the viewpoint of reactivity with the silane coupling agent, and polyoxyethylene stearate, sodium ligninsulfonate and the like are preferable.
本発明のシランカツプリング剤は、炭素繊維表面の水
酸基と反応して炭素繊維と強固に結合する。さらにこの
シランカツプリング剤は、後で付着させる界面活性剤の
少なくとも一部と反応もしくは強固な相互作用を及ぼし
て炭素繊維表面最外部に界面活性剤がコーテイングされ
た形となる。The silane coupling agent of the present invention reacts with a hydroxyl group on the surface of carbon fiber and binds firmly to carbon fiber. Further, the silane coupling agent reacts or at least strongly interacts with at least a part of the surfactant to be attached later, so that the surfactant is coated on the outermost surface of the carbon fiber.
酸化処理を行つていない炭素繊維表面は通常水酸基が
少ないが、炭素繊維の焼成の方法によつては（例えば、
焼成温度を低くして製造する方法）、水酸基が多くつい
た炭素繊維を製造することができる。しかしPAN系炭素
繊維は、通常1000℃以上の温度で焼成されるのでCFの表
面の水酸基は少く、酸化処理を行つて表面に酸素官能基
を導入する方がシランカツプリング剤と反応しやすい。The surface of the carbon fiber that has not been oxidized is usually low in hydroxyl groups, but depending on the method of firing the carbon fiber (for example,
A method in which the firing temperature is lowered) to produce a carbon fiber having many hydroxyl groups. However, since the PAN-based carbon fiber is usually fired at a temperature of 1000 ° C. or higher, the hydroxyl groups on the surface of the CF are small, and it is easier to react with the silane coupling agent by introducing an oxygen functional group into the surface by performing an oxidation treatment.
炭素繊維の酸化処理は、樹脂をマトリツクスとする複
合材に使用される炭素繊維に一般的に行われている空気
酸化処理方法、オゾン酸化処理方法、電解酸化処理方法
などで行うことができる。The oxidation treatment of the carbon fiber can be performed by an air oxidation treatment method, an ozone oxidation treatment method, an electrolytic oxidation treatment method, etc., which are generally performed on carbon fibers used for a composite material using a matrix as a resin.
シランカツプリング剤は、炭素繊維表面と反応させる
ため好ましくは0.1〜10wt％付着させられるのが良い。
さらに好ましくは0.5〜5wt％付着させるのが良い。一方
AE剤、分散剤に使用される界面活性剤は、炭素繊維に対
して50wt％以上付着させても問題がない。好ましくは50
〜100wt％付着させるのが良い。The silane coupling agent is preferably applied in an amount of 0.1 to 10% by weight to react with the carbon fiber surface.
More preferably, 0.5 to 5 wt% is deposited. on the other hand
There is no problem if the surfactant used for the AE agent and the dispersant adheres to the carbon fiber in an amount of 50% by weight or more. Preferably 50
It is good to make it adhere to ~ 100wt%.
本発明の炭素繊維が対象とするセメントは、ポルトラ
ンドセメント、白色ポルトランドセメント、アルミナセ
メント等の水硬性セメントである。The cement targeted by the carbon fiber of the present invention is a hydraulic cement such as Portland cement, white Portland cement, and alumina cement.
以下本発明を実施例により具体的に説明する。 Hereinafter, the present invention will be described specifically with reference to Examples.
実施例１ 引張り強度350kg/mm2、引張り弾性率24t/mm2のノンサ
イズの炭素繊維を、γ−グリシドキシプロピルトリメト
キシシラン1wt％水溶液に浸漬した。その後150℃、５分
間で加熱処理し、さらに界面活性剤としてビスフエノー
ルＡのエチレンオキサイド付加物の10wt％水溶液にシラ
ンカツプリング剤処理した炭素繊維を浸漬し付着処理し
た。Example 1 A non-sized carbon fiber having a tensile strength of 350 kg / mm 2 and a tensile elasticity of 24 t / mm 2 was immersed in a 1 wt% aqueous solution of γ-glycidoxypropyltrimethoxysilane. Thereafter, heat treatment was carried out at 150 ° C. for 5 minutes, and carbon fibers treated with a silane coupling agent were immersed in a 10 wt% aqueous solution of an ethylene oxide adduct of bisphenol A as a surfactant, followed by adhesion treatment.
この炭素繊維を6mmの長さにカツトし、水／セメント
／メチルセルロース100/50/0.5重量比の混練物に加え混
合した。この混合物を30×30cmの型枠に流込み成形し
た。養生は水中20℃１日間、水中50℃２日間行つた。こ
のサンプルを４×15cmに切断して曲げ試験を行つた。曲
げ強度は180kg/cm2であつた。This carbon fiber was cut into a length of 6 mm, and added to and mixed with a kneaded product in a water / cement / methylcellulose 100/50 / 0.5 weight ratio. The mixture was cast into a 30 × 30 cm mold. Curing was carried out in water at 20 ° C. for 1 day and in water at 50 ° C. for 2 days. This sample was cut into 4 × 15 cm and subjected to a bending test. The flexural strength was 180 kg / cm 2 .
実施例２ 表１に示す条件以外は、実施例１と同様の条件で成形
したときの物性を表１に示す。Example 2 Table 1 shows the physical properties when molded under the same conditions as in Example 1 except for the conditions shown in Table 1.
比較例１ 表２に示す条件以外は実施例１と同様にして作成した
複合材の物性を表２に示す。 Comparative Example 1 Table 2 shows the physical properties of the composite material prepared in the same manner as in Example 1 except for the conditions shown in Table 2.
〔効果〕 本発明は炭素繊維を適正に処理することによつてセメ
ントに配合したとき成形体の曲げ強度を大巾に向上せし
めるものであり、壁材、石綿セメント代替材料、構造材
料等の建築材料、土木材料として優れた性能を発揮す
る。 [Effects] The present invention is intended to greatly improve the bending strength of molded articles when compounded with cement by appropriately treating carbon fibers, and is useful for building materials such as wall materials, asbestos cement substitute materials, and structural materials. Excellent performance as a material and civil engineering material.
Claims (6)
後、界面活性剤を付着させてなるセメント用炭素繊維。1. A carbon fiber for cement obtained by treating a carbon fiber with a silane coupling agent and then adhering a surfactant.
プロピルトリメトキシシランである請求項１記載の炭素
繊維。2. The carbon fiber according to claim 1, wherein the silane coupling agent is γ-glycidoxypropyltrimethoxysilane.
求項１記載の炭素繊維。3. The carbon fiber according to claim 1, wherein the surfactant is a dispersant or an AE agent.
物である請求項１又は３記載の炭素繊維。4. The carbon fiber according to claim 1, wherein the surfactant is a polyethylene oxide compound.
記載の炭素繊維。5. The method according to claim 1, wherein the surfactant is a sulfate.
The carbon fiber as described.
維である請求項１記載の炭素繊維。6. The carbon fiber according to claim 1, wherein the carbon fiber to be treated is an oxidized carbon fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28644289A JP2816433B2 (en) | 1989-11-02 | 1989-11-02 | Carbon fiber for cement |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28644289A JP2816433B2 (en) | 1989-11-02 | 1989-11-02 | Carbon fiber for cement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03150241A JPH03150241A (en) | 1991-06-26 |
| JP2816433B2 true JP2816433B2 (en) | 1998-10-27 |
Family
ID=17704444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28644289A Expired - Lifetime JP2816433B2 (en) | 1989-11-02 | 1989-11-02 | Carbon fiber for cement |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2816433B2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2756069B2 (en) * | 1992-11-27 | 1998-05-25 | 株式会社ペトカ | Carbon fiber for concrete reinforcement |
| DE69313410T2 (en) * | 1992-11-27 | 1998-02-19 | Petoca Ltd | Carbon fibers for the reinforcement of cement and cementitious composite material |
| GB9518787D0 (en) * | 1995-09-14 | 1995-11-15 | Cape Boards Siborat Gmbh | Material for metal casting equipment |
| US7048034B2 (en) | 2000-11-10 | 2006-05-23 | Buntrock Industries, Inc. | Investment casting mold and method of manufacture |
| US7004230B2 (en) | 2000-11-10 | 2006-02-28 | Buntrock Industries, Inc. | Investment casting shells and compositions including rice hull ash |
| US7285167B2 (en) * | 2003-10-08 | 2007-10-23 | Ogden Technologies, Inc. | Fiber reinforced concrete/cement products and method of preparation |
| WO2006091185A1 (en) * | 2005-02-18 | 2006-08-31 | Ogden Technologies, Inc. | Fiber reinforced concrete/cement products and method of preparation |
| US7341627B2 (en) | 2005-02-18 | 2008-03-11 | Ogden Technologies, Inc. | Fiber reinforced concrete products and method of preparation |
| US7396403B1 (en) | 2006-02-17 | 2008-07-08 | Ogden Technologies, Inc. | Concrete reinforced with acrylic coated carbon fibers |
| JP6028240B2 (en) * | 2012-01-11 | 2016-11-16 | 小川 一文 | Method of manufacturing form-stabilized apparel product and apparel product manufactured using the same |
| KR101521442B1 (en) * | 2014-03-07 | 2015-05-21 | 한국과학기술연구원 | Inorganic particle impregnated carbon felts and method thereof |
-
1989
- 1989-11-02 JP JP28644289A patent/JP2816433B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03150241A (en) | 1991-06-26 |
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