JPS625176B2 - - Google Patents
Info
- Publication number
- JPS625176B2 JPS625176B2 JP2550479A JP2550479A JPS625176B2 JP S625176 B2 JPS625176 B2 JP S625176B2 JP 2550479 A JP2550479 A JP 2550479A JP 2550479 A JP2550479 A JP 2550479A JP S625176 B2 JPS625176 B2 JP S625176B2
- Authority
- JP
- Japan
- Prior art keywords
- ammonium salt
- group
- present
- unsaturated polyester
- frp
- 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
Links
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
【発明の詳細な説明】
本発明はFRPの製造方法に係り、透明性に優
れ、硬化速度が大きく又特に耐水性の良好な
FRPを得ることをその目的とする。[Detailed Description of the Invention] The present invention relates to a method for producing FRP, which has excellent transparency, fast curing speed, and especially good water resistance.
The purpose is to obtain FRP.
補強繊維に熱硬化性樹脂を含浸させて硬化せし
めたFRPは各種用途に広く用いられ、補強繊維
としては硝子繊維が、又熱硬化性樹脂としては不
飽和ポリエステル樹脂が最も広く用いられてい
る。 FRP, which is made by impregnating reinforcing fibers with a thermosetting resin and curing them, is widely used for various purposes, and the most widely used reinforcing fibers are glass fibers, and the most widely used thermosetting resins are unsaturated polyester resins.
硝子繊維と不飽和ポリエステル樹脂を用いた
FRP（以下本FRPという）は機械的強度におい
て優れた特性を有するが、補強繊維が模様となつ
て浮出し透明性が不充分となつたりする他、長時
間水中で使用すると水分が補強硝子繊維の界面に
沿つて浸入し、ふくれ、白化、強度低下を招来す
ることがある。 Using glass fiber and unsaturated polyester resin
FRP (hereinafter referred to as "FRP") has excellent properties in terms of mechanical strength, but the reinforcing fibers may form patterns and become embossed, resulting in insufficient transparency, and if used underwater for a long time, moisture may wick away from the reinforcing glass. It can penetrate along fiber interfaces, causing blistering, whitening, and reduced strength.
本発明者はかかる難点を解決するため検討を重
ねた結果、一般式
（ここにR1は炭素数10〜18の直鎖炭化水素基、R2
はメチル、エチル、ラウリル又はステアリル基、
R3、R4はメチル、エチル又はベンジル基）で表
わされる第４級アンモニウム塩（以下本アンモニ
ウム塩という）を表面に附着せしめた補強硝子繊
維に不飽和ポリエステル樹脂を含浸せしめて硬化
せしめることにより特に良好な結果の得られるこ
とを見出し本発明として提案したものである。 As a result of repeated studies in order to solve these difficulties, the inventor found that the general formula (Here, R 1 is a straight chain hydrocarbon group having 10 to 18 carbon atoms, R 2
is a methyl, ethyl, lauryl or stearyl group,
R 3 and R 4 are methyl, ethyl, or benzyl groups) A quaternary ammonium salt (hereinafter referred to as the present ammonium salt) is attached to the surface of reinforcing glass fibers, and the reinforced glass fibers are impregnated with an unsaturated polyester resin and cured. It was discovered that particularly good results could be obtained, and the present invention was proposed.
本アンモニウム塩の作用については明らかでな
いが、本アンモニウム塩は不飽和ポリエステル樹
脂の硬化を促進しその結合を鞏固ならしめ且つ透
明性、耐水性の大きいFRPの得られる効果を有
する。このため硝子繊維補強材の表面に本アンモ
ニウム塩を附着せしめたものに不飽和ポリエステ
ル樹脂を含浸せしめて該樹脂を硬化せしめるとき
は樹脂の硬化は硝子繊維補強体と不飽和ポリエス
テル樹脂の界面において開始され、この部分で特
に鞏固な結合が形成されるため、界面に隙間が形
成されたり、この界面の隙門部分から水が侵入し
たりすることが防止されその耐水性が一段と向上
するものと思われる。 Although the action of the present ammonium salt is not clear, the present ammonium salt has the effect of accelerating the curing of the unsaturated polyester resin, hardening its bonds, and obtaining FRP with high transparency and water resistance. Therefore, when the ammonium salt is attached to the surface of a glass fiber reinforcing material and the unsaturated polyester resin is impregnated and the resin is cured, the curing of the resin starts at the interface between the glass fiber reinforcing material and the unsaturated polyester resin. Since a particularly strong bond is formed in this part, it is thought that this will prevent gaps from forming at the interface and water from entering through the cracks at this interface, further improving its water resistance. It can be done.
次に本発明を更に具体的に説明する。 Next, the present invention will be explained in more detail.
本発明において不飽和ポリエステル樹脂として
は一般型の不飽和ポリエステル樹脂の他に耐水
性、耐候性、耐薬品性、低収縮性等の各種ポリエ
ステル樹脂が好適に使用できる。なお、これらの
樹脂中にメチルエチルケトンパーオキサイド等の
硬化剤、ナフテン酸コバルト等の硬化促進剤或は
着色剤充填材等（以下其他成分と総称する）を適
宜混合したものも使用しうる。 In the present invention, as the unsaturated polyester resin, in addition to general unsaturated polyester resins, various polyester resins having water resistance, weather resistance, chemical resistance, low shrinkage properties, etc. can be suitably used. It is also possible to use these resins mixed with a curing agent such as methyl ethyl ketone peroxide, a curing accelerator such as cobalt naphthenate, or a coloring filler (hereinafter collectively referred to as other components).
本アンモニウム塩においてR1としては、例え
ばラウリル基、ステアリル基等が好適に使用でき
る。本アンモニウム塩として好適に使用できるも
のとしては例えば、ラウリルトリメチルアンモニ
ムウクロライド、ステアリルベンジルジメチルア
ンモニウムクロライド、ステアリルトリメチルア
ンモニウムクロライド、ジステアリルジメチルア
ンモニウムクロライド等を挙げることができ、こ
のうちラウリルトリメチルアンモニウムクロライ
ド及びステアリルベンジルジメチルアンモニウム
クロライドが特に好適な結果を与える。 In the present ammonium salt, as R 1 , for example, a lauryl group, a stearyl group, etc. can be suitably used. Examples of ammonium salts that can be suitably used include lauryltrimethylammonium chloride, stearylbenzyldimethylammonium chloride, stearyltrimethylammonium chloride, and distearyldimethylammonium chloride, among which lauryltrimethylammonium chloride and stearyltrimethylammonium chloride. Benzyldimethylammonium chloride gives particularly suitable results.
本発明においては硝子繊維補強材に不飽和ポリ
エステル樹脂を含浸せしめて硬化せしめるに際し
硝子繊維補強材の表面に予め少量の本アンモニウ
ム塩を附着させたものを補強材として使用する。
このため既存の硝子繊維補強材の表面に本アンモ
ニウム塩を含む水性媒体を噴霧することもできる
が、硝子繊維を製造する際、使用するサイジング
剤中に本アンモニウム塩を含有させておくことも
できる。 In the present invention, when a glass fiber reinforcing material is impregnated with an unsaturated polyester resin and cured, a small amount of the ammonium salt of the present invention is preliminarily applied to the surface of the glass fiber reinforcing material to be used as a reinforcing material.
For this reason, an aqueous medium containing the present ammonium salt can be sprayed onto the surface of existing glass fiber reinforcing materials, but it is also possible to include the present ammonium salt in the sizing agent used when manufacturing glass fibers. .
本アンモニウム塩を予め混合するサイジング剤
として特に好適に使用できるものはメトキシシラ
ン、ビニールシラン等のシランカツプリング剤
0.05〜６％、酢ビエマルジヨン、ポリエステルエ
マルジヨン、エポキシエマルジヨンのようなフイ
ルムフオーマー３〜15％を含有するサイジング剤
である。サイジング中には脂肪酸アミド等の潤滑
剤を通常存在せしめるが、本アンモニウム塩を使
用した場合潤滑剤の存在は必ずしも必要でない。 Silane coupling agents such as methoxysilane and vinyl silane are particularly suitable as sizing agents to be mixed with this ammonium salt in advance.
The sizing agent contains 0.05 to 6% and 3 to 15% of a film former such as acetic acid emulsion, polyester emulsion, or epoxy emulsion. A lubricant such as a fatty acid amide is usually present during sizing, but the presence of a lubricant is not necessarily required when the present ammonium salt is used.
上述したようなサイジング剤中に本アンモニウ
ム塩を固形分として0.05〜0.5重量％程度添加し
充分に混合する。本アンモニウム塩を含むサイジ
ング剤を常法に従つてブツシングから引出された
硝子繊維に附与し硝子繊維表面に本アンモニウム
塩を附着せしめることができる。 The present ammonium salt is added in a solid content of about 0.05 to 0.5% by weight into the above-mentioned sizing agent and mixed thoroughly. A sizing agent containing the ammonium salt of the present invention can be applied to the glass fibers drawn from the bushing in accordance with a conventional method, so that the ammonium salt of the present invention is attached to the surface of the glass fibers.
本アンモニウム塩を附着せしめた硝子繊維補強
体に不飽和ポリエステル樹脂を含浸せしめ常法に
より樹脂を硬化せしめてFRPとすることによ
り、透明性、耐水性の特に優れたFRPを得るこ
とができる。 FRP with particularly excellent transparency and water resistance can be obtained by impregnating the glass fiber reinforcement to which the present ammonium salt has been attached with an unsaturated polyester resin and curing the resin by a conventional method to obtain FRP.
次に本発明の実施例を示す。 Next, examples of the present invention will be shown.
実施例 １
サイジング剤として濃度50％のエポキシエマル
ジヨン６％、シラン系カツプリング剤0.2％、氷
酢酸（PH調製用）ラウリルトリメチルアンモニウ
ムクロライド又はステアリルベンジルメチルアン
モニウムクロライド0.2％を含む水分散液を使用
して得られたチヨツプドストランドを補強材とし
て使用し、不飽和ポリエステル樹脂を含浸せし
め、加熱硬化せしめて、透明性の良好なFRPを
得た。このFRPは水中で200時間煮沸しても白化
が生じなかつた。これに対しラウリルトリチルア
ンモニウムクロライドの代りに脂肪酸アミドを使
用した場合、透明性が劣り水中100時間の煮沸で
白化を生じた。Example 1 An aqueous dispersion containing 6% of an epoxy emulsion with a concentration of 50%, 0.2% of a silane coupling agent, and 0.2% of glacial acetic acid (for pH adjustment) lauryltrimethylammonium chloride or stearylbenzylmethylammonium chloride was used as a sizing agent. The chopped strands obtained were used as a reinforcing material, impregnated with unsaturated polyester resin, and cured by heating to obtain FRP with good transparency. This FRP did not whiten even after being boiled in water for 200 hours. On the other hand, when fatty acid amide was used instead of lauryltritylammonium chloride, the transparency was poor and whitening occurred after boiling in water for 100 hours.
比較例
サイジング剤として濃度30％のポリエステルエ
マルジヨン10％、シラン系カツプリング剤0.2
％、脂肪酸アミド0.2％を含む水分散液を使用し
て得られたチヨツプドストランドを補強材として
使用し、不飽和ポリエステル樹脂100部中にステ
アリルベンジルジメチルアンモニウムクロライド
又はラウリルトリメチルアンモニウムクロライド
１部を混合した樹脂組成物を含浸せしめ加熱硬化
して透明性の良好なFRPを得た。このFRPは水
中で150時間煮沸しても白化が生じなかつた。Comparative example: 10% polyester emulsion with a concentration of 30% as sizing agent, 0.2 silane coupling agent
%, a chopped strand obtained using an aqueous dispersion containing 0.2% of fatty acid amide was used as a reinforcing material, and 1 part of stearylbenzyldimethylammonium chloride or lauryltrimethylammonium chloride was added to 100 parts of unsaturated polyester resin. FRP with good transparency was obtained by impregnating the resin composition with a mixture of the following and heating and curing it. This FRP did not whiten even after being boiled in water for 150 hours.
Claims (1)
チル・エチル・ラウリル又はステアリル基、
R3、R4はメチル基、エチル基、又はベンジン基
で表わされる第４級アンモニウム塩を表面に附着
させた硝子繊維補強材に不飽和ポリエステル樹脂
を含浸せしめて硬化せしめることを特徴とする
FRPの製造方法。[Claims] 1. General formula R 1 is a straight chain hydrocarbon group having 10 to 18 carbon atoms, R 2 is a methyl ethyl lauryl or stearyl group,
R 3 and R 4 are characterized by impregnating a glass fiber reinforcing material with a quaternary ammonium salt represented by a methyl group, an ethyl group, or a benzine group on its surface and hardening it with an unsaturated polyester resin.
FRP manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2550479A JPS55118929A (en) | 1979-03-07 | 1979-03-07 | Production of frp |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2550479A JPS55118929A (en) | 1979-03-07 | 1979-03-07 | Production of frp |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55118929A JPS55118929A (en) | 1980-09-12 |
| JPS625176B2 true JPS625176B2 (en) | 1987-02-03 |
Family
ID=12167889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2550479A Granted JPS55118929A (en) | 1979-03-07 | 1979-03-07 | Production of frp |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55118929A (en) |
-
1979
- 1979-03-07 JP JP2550479A patent/JPS55118929A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55118929A (en) | 1980-09-12 |
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