JPH0680438A - Glass fiber - Google Patents
Glass fiberInfo
- Publication number
- JPH0680438A JPH0680438A JP25356892A JP25356892A JPH0680438A JP H0680438 A JPH0680438 A JP H0680438A JP 25356892 A JP25356892 A JP 25356892A JP 25356892 A JP25356892 A JP 25356892A JP H0680438 A JPH0680438 A JP H0680438A
- Authority
- JP
- Japan
- Prior art keywords
- glass fiber
- sizing
- lubricant
- coupling agent
- strength
- 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
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Reinforced Plastic Materials (AREA)
- Glass Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ＦＲＰ部材の強化繊維
として用いられるガラス繊維に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to glass fibers used as reinforcing fibers for FRP members.
【０００２】[0002]
【従来の技術】従来、ＦＲＰ部材用のガラス繊維はポリ
エステル用として開発され、ハンドリングを中心として
考えられてきた。そしてポリエステル用、エポキシ用に
開発されたサイジング剤は多数あり、フェノール樹脂用
のサイジング剤に関しては特開昭６０−１３９７１５号
公報に示されたものがある。一方市販のガラス繊維とし
てフェノール用にはアミノシラン系カップリング剤、エ
ポキシシラン系カップリング剤が用いられる。しかし、
本来アミノシラン系カップリング剤はエポキシ樹脂また
はナイロン等をターゲットとする。またγ−アミノプロ
ピルトリエトキシシランをフェノール樹脂に添加して成
形を行なう方法も行なわれているが。強化材に短繊維や
粒状物を用いる場合にのみを行なわれる。2. Description of the Related Art Conventionally, glass fibers for FRP members have been developed for polyester and have been considered mainly for handling. There are many sizing agents developed for polyesters and epoxies, and a sizing agent for phenolic resins is disclosed in JP-A-60-139715. On the other hand, as a commercially available glass fiber, an aminosilane coupling agent and an epoxysilane coupling agent are used for phenol. But,
Originally, the aminosilane coupling agent targets epoxy resin or nylon. Also, a method of adding γ-aminopropyltriethoxysilane to a phenol resin and performing molding has been carried out. This is done only when short fibers or granules are used as the reinforcing material.
【０００３】[0003]
【発明が解決しようとする課題】従来のフェノール樹脂
をターゲットとした市販のガラス繊維では、引抜き成形
でＦＲＰ部材を成形した場合十分な強度が得られなかっ
た。With the commercially available glass fiber targeting the conventional phenol resin, sufficient strength was not obtained when the FRP member was formed by pultrusion.
【０００４】本発明は上記のことにかんがみなされたも
ので、フェノール樹脂をターゲットとし、ＵＰ／ＧＦＲ
Ｐと同等以上の強度をもつＦＲＰ部材を得ることができ
るガラス繊維を提供することを目的とするものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above points, and targets a phenolic resin to improve UP / GFR.
An object of the present invention is to provide a glass fiber capable of obtaining an FRP member having a strength equal to or higher than P.
【０００５】[0005]
【課題を解決するための手段】上記目的を達成するため
に、本発明に係るガラス繊維は、カップリング剤とし
て、γ−アミノプロピルトリエトキシシランを強熱減量
で０．１％以上、好ましくは０．２％サイジングし、潤
滑剤として、ジアミノシランあるいは／及びカチオン系
の界面活性剤などのフェノール樹脂の硬化触媒として作
用するものを使用し、さらにビニルアルコールや酢酸ビ
ニルなどの反応基をもたない収束剤を用い、これらをサ
イジンした構成となっている。In order to achieve the above object, the glass fiber according to the present invention contains γ-aminopropyltriethoxysilane as a coupling agent in an ignition loss of 0.1% or more, preferably. Sizing 0.2%, using a lubricant such as diaminosilane or / and a cationic surfactant that acts as a curing catalyst for the phenol resin, and further have a reactive group such as vinyl alcohol or vinyl acetate. A sizing agent is used with no sizing agent.
【０００６】[0006]
【作 用】γ−アミノプロピルトリエトキシシランを
カップリング剤としてサイジングしたガラス繊維を用い
たフェノール樹脂ＦＲＰ部材はその曲げ強度が大幅に増
大される。そしてさらに上記ガラス繊維にジアミノシラ
ンあるいは／及びカチオン系の界面活性剤を潤滑剤とし
て、またビニルアルコール等の収束剤をサイジングする
ことによりガラス繊維のハンドリングが得られる。[Working] The bending strength of a phenol resin FRP member using glass fibers sized with γ-aminopropyltriethoxysilane as a coupling agent is greatly increased. Further, handling of the glass fiber can be obtained by sizing the above-mentioned glass fiber with a diaminosilane and / or cationic surfactant as a lubricant and with a sizing agent such as vinyl alcohol.
【０００７】[0007]
【実 施 例】本発明の実施例を以下に説明する。 （１）比較実験例 市販の旭ファイバーグラス製のガラスロービングＦＷ６
７、２４００ｔｅｘを用いて引抜成形によりフェノール
樹脂を用いたＦＲＰ部材を成形し、曲げ強度を測定した
ところ、５４２ＭＰａの強度を得た。EXAMPLES Examples of the present invention will be described below. (1) Comparative Experimental Example Commercially available Asahi Fiberglass glass roving FW6
When an FRP member using a phenolic resin was molded by pultrusion using 7,2400 tex and the bending strength was measured, a strength of 542 MPa was obtained.
【０００８】（２）実験例１ ２４００ｔｅｘのガラス繊維に、γ−アミノプロピルト
リエトキシシラン（日本コニカ製Ａ１１００）を０．
１，０．２，０．４％の強熱減量でサイジングし、引抜
成形法によりフェノールを用いたＦＲＰ部材を成形し
て、これの曲げ強度を測定したところ、それぞれ、１０
６２ＭＰａ，１１７５ＭＰａ，１０９４ＭＰａの曲げ強
度が得られた。(2) Experimental Example 1 γ-aminopropyltriethoxysilane (A1100 manufactured by Konica Japan) was added to 2400 tex of glass fiber.
Sizing was performed with a loss on ignition of 1, 0.2 and 0.4%, an FRP member using phenol was formed by a pultrusion method, and the bending strength of the FRP member was measured.
Bending strengths of 62 MPa, 1175 MPa, and 1094 MPa were obtained.
【０００９】（３）実験例２ 上記実験例１でのガラス繊維に潤滑性をもたせるため
に、カチオン系の潤滑剤であるテトラエチレンペンタシ
アン（ＴＥＰＡ）を０．０５％、γ−アミノプロピルト
リエトキシシランを０．２％サイジングした２４００ｔ
ｅｘのガラス繊維を用いて引抜成形を行なって得たフェ
ノール樹脂を用いたＦＲＰ部材の曲げ強度を測定したと
ころ、１１７１ＭＰａの強度を得た。(3) Experimental Example 2 In order to impart lubricity to the glass fiber in Experimental Example 1, 0.05% of tetraethylene pentacyan (TEPA), which is a cationic lubricant, and γ-aminopropyltriene are used. 2400t with 0.2% ethoxysilane sizing
When the bending strength of the FRP member using the phenol resin obtained by drawing using the glass fiber ex was measured, the strength was 1171 MPa.
【００１０】（４）実験例３ 上記実施例１でのガラス繊維に潤滑性をもたせるため
に、γ−（２−アミノエチル）アミノプロピルトリメト
キシシラン、γ−（２−アミノエチル）アミノプロピル
メチルジメトキシシランなどのジアミノシランを０．０
５％、γ−アミノプロピルトリメトキシシランを０．２
％サイジングした２４００ｔｅｘのガラス繊維を用いて
引抜成形を行なって得たフェノール樹脂を用いたＦＲＰ
部材の曲げ強度を測定したところ、１２１６ＭＰａの曲
げ強度を得た。(4) Experimental Example 3 In order to provide the glass fiber of Example 1 with lubricity, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyl 0.0% diaminosilane such as dimethoxysilane
5%, 0.2% γ-aminopropyltrimethoxysilane
% FRP using phenol resin obtained by pultrusion using 2400 tex glass fiber sized
When the bending strength of the member was measured, a bending strength of 1216 MPa was obtained.
【００１１】（５）実験例４ 上記各実験例にて用いたものと同じガラス繊維にカップ
リング剤としてγ−アミノプロピルトリエトキシシラン
を０．２％、カチオン系潤滑剤を０．０５％、ポリビニ
ルアルコール系収束剤を０．１５％強熱減量でサイジン
グしてフェノール樹脂ＦＲＰ部材を引抜成形を行なった
ところ、ガラス繊維のばらけや毛羽立ちがおこらずに成
形でき、その上成形品の曲げ強度は１０７０ＭＰａであ
った。(5) Experimental Example 4 γ-aminopropyltriethoxysilane was used as a coupling agent in an amount of 0.2%, and a cationic lubricant was used in an amount of 0.05% in the same glass fiber as that used in each of the above-described experimental examples. Polyvinyl alcohol-based sizing agent was sized with 0.15% loss on ignition, and the phenol resin FRP member was pultrusion molded, and it was possible to mold without glass fiber loosening or fuzzing, and the bending strength of the molded product. Was 1070 MPa.
【００１２】上記比較実験例にて得られたＦＲＰ部材と
各実験例で得られた各ＦＲＰ部材を比較すると、その曲
げ強度が極めて大きくなったことがわかる。なお、収束
剤は反応基をもたないものを用いる。また潤滑剤にアニ
オン系及び／ノニオン系のものを用いると硬化が阻害さ
れ、界面接着の強度が低下すると考えられる。収束剤に
反応基（例えばエポキシ基）をもつものを使用するとγ
−アミノプロピルシランの反応基と反応してしまいカッ
プリング剤としての効果が失なわれる。Comparing the FRP member obtained in the above comparative experiment example with each FRP member obtained in each experiment example, it can be seen that the bending strength thereof is extremely large. A sizing agent having no reactive group is used. Further, it is considered that when an anionic and / or nonionic lubricant is used as the lubricant, curing is hindered and the strength of interfacial adhesion is reduced. If a sizing agent with a reactive group (eg epoxy group) is used, γ
-Reacts with the reactive group of aminopropylsilane and loses its effect as a coupling agent.
【００１３】また本発明にあっては、基本的には実験例
１で示した構成、すなわち、カップリング剤としてγ−
アミノプロピルトリメトキシシランを強熱減量で０．１
％以上サイジングすることだけでＦＲＰ部材として十分
な強度を得ることができるが、ガラス繊維のハンドリン
グを得るために、実施例２，３，４示したように潤滑剤
及び収束剤を添付して加工を行なう。Further, according to the present invention, basically, the constitution shown in Experimental Example 1, that is, γ-is used as the coupling agent.
Aminopropyltrimethoxysilane with a loss on ignition of 0.1
%, It is possible to obtain sufficient strength as an FRP member only by sizing, but in order to obtain handling of glass fiber, as shown in Examples 2, 3 and 4, a lubricant and a sizing agent are attached and processed. Do.
【００１４】[0014]
【発明の効果】本発明に係るガラス繊維は、特にフェノ
ール樹脂をターゲットとし、ＵＰ／ＧＦＲＰと同等以上
の強度をもつＦＲＰ部材を得ることができるガラス繊維
を得ることができた。EFFECTS OF THE INVENTION The glass fiber according to the present invention is a glass fiber capable of obtaining an FRP member having a strength equal to or higher than that of UP / GFRP by using a phenol resin as a target.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｄ０６Ｍ 13/513 15/333 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display location D06M 13/513 15/333
Claims (1)
ピルトリエトキシシランを強熱減量で０．１％以上、好
ましくは０．２％サイジングし、潤滑剤として、ジアミ
ノシランあるいは／及びカチオン系の界面活性剤などの
フェノール樹脂の硬化触媒として作用するものを使用
し、さらにビニルアルコールや酢酸ビニルなどの反応基
をもたない収束剤を用い、これらをサイジンしたことを
特徴とするガラス繊維。1. A coupling agent, γ-aminopropyltriethoxysilane is sized by a loss on ignition of 0.1% or more, preferably 0.2%, and as a lubricant, a diaminosilane or / and a cationic interface. A glass fiber characterized by using an activator or the like that acts as a curing catalyst for a phenol resin, and using a sizing agent that does not have a reactive group such as vinyl alcohol or vinyl acetate, and sizing these.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25356892A JPH0680438A (en) | 1992-08-31 | 1992-08-31 | Glass fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25356892A JPH0680438A (en) | 1992-08-31 | 1992-08-31 | Glass fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0680438A true JPH0680438A (en) | 1994-03-22 |
Family
ID=17253185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25356892A Pending JPH0680438A (en) | 1992-08-31 | 1992-08-31 | Glass fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0680438A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003056095A1 (en) * | 2001-12-27 | 2003-07-10 | Asahi Fiber Glass Co., Ltd. | Binder for glass fiber, glass fiber for olefin resin reinforcement, and process for producing olefin resin composition for fiber-reinforced molding |
| CN114249962A (en) * | 2022-03-02 | 2022-03-29 | 山东墨匠新材料科技有限公司 | Glass fiber resin composite material and preparation method thereof |
-
1992
- 1992-08-31 JP JP25356892A patent/JPH0680438A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003056095A1 (en) * | 2001-12-27 | 2003-07-10 | Asahi Fiber Glass Co., Ltd. | Binder for glass fiber, glass fiber for olefin resin reinforcement, and process for producing olefin resin composition for fiber-reinforced molding |
| US6984699B2 (en) | 2001-12-27 | 2006-01-10 | Asahi Fiber Glass Co., Ltd. | Binder for glass fibers, glass fibers for olefin resin reinforcement, and process for producing olefin resin composition for fiber-reinforced molding |
| CN100363388C (en) * | 2001-12-27 | 2008-01-23 | 玻璃纤维日本株式会社 | Binder for glass fiber, glass fiber for olefin resin reinforcement, and method for producing olefin resin composition for fiber-reinforced molding |
| CN114249962A (en) * | 2022-03-02 | 2022-03-29 | 山东墨匠新材料科技有限公司 | Glass fiber resin composite material and preparation method thereof |
| CN114249962B (en) * | 2022-03-02 | 2022-05-03 | 山东墨匠新材料科技有限公司 | Glass fiber resin composite material and preparation method thereof |
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