JPH0448739B2 - - Google Patents
Info
- Publication number
- JPH0448739B2 JPH0448739B2 JP61297707A JP29770786A JPH0448739B2 JP H0448739 B2 JPH0448739 B2 JP H0448739B2 JP 61297707 A JP61297707 A JP 61297707A JP 29770786 A JP29770786 A JP 29770786A JP H0448739 B2 JPH0448739 B2 JP H0448739B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- strength
- amount
- sio
- mgo
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
［発明の目的］
（産業上の利用分野）
本発明は繊維用硝子組成物並にFRP用硝子繊
維に関するものである。
（従来の技術）
繊維用硝子組成の一つとしてはＥ−硝子が知ら
れ、優れた諸特性を有し、FRP用補強繊維等と
して広く用いられている。Ｅ−硝子の組成は概ね
次の通りである。
SiO2 52〜56％
Al2O3 12〜16％
CaO 16〜19％
MgO ０〜６％
B2O3 ４〜11％
Ｅ−硝子は上記主要成分の他に次の微量成分を
含む。
R2Ｏ ＜１％
TiO2 ＜１％
Fe2O3 ＜１％
Ｆ ＜１％
上記成分のうち、B2O3、Ｆは硝子に望ましい
特性を与えるためのもので、これらは硝子原料溶
解工程中に大気に逸散し、歩留りを低下させるだ
けでなく、特にＦは公害の原因となりやすい。
又、Ｅ−硝子は溶融特性も優れ、工業的に最も
大量に使用されているが耐水性、強度が比較的低
く、強度の特に大きいFRPをうるための補強用
として硝子繊維を用いる場合には、引張強度の更
に大きいＳ−硝子を用いる必要がある。Ｓ−硝子
の典型的組成は次の通りである。
SiO265wt％、Al2O325wt％、MgO10wt％。
Ｓ−硝子は引張強度及び耐水性はＥ−硝子に比
し大きいが、CaO、R2Ｏ、B2O3等の溶融を促進
する成分を含有していないため失透、紡糸温度が
Ｅ−硝子に比し250〜350℃高く、Ｅ−硝子に比し
溶融、採糸が困難である欠点を有する。
（発明が解決しようとする問題点）
本発明は従来技術が有していた前述の欠点を解
消することを目的とするものである。
［発明の構成］
（問題点を解決するための手段）
本発明は前述の問題点を解決すべくなされたも
のであり、必須成分としてSiO2、Al2O3、MgO、
B2O3、TiO2を含み、且つこれらの成分の割合
が、SiO250〜60wt％、Al2O325〜35wt％、MgO8
〜15wt％、B2O3２〜6.5wt％TiO2＜1wt％であ
り、且つR2Ｏ≦1wt％、Fe2O3≦1wt％、CaO≦
2wt％であることを特徴とする繊維用硝子組成物
並びに必須成分としてSiO2、Al2O3、MgO、B2
O3、TiO2を含み、且つこれらの成分の割合が、
SiO250〜60wt％、Al2O325〜35wt％、MgO8〜
15wt％、B2O3２〜6.5wt％、TiO2＜1wt％であ
り、且つR2Ｏ≦1wt％、Fe2O3≦1wt％、CaO≦
2wt％である。
次に本発明を更に具体的に説明する。
本発明においては必須成分としてSiO2、Al2
O3、MgO、B2O3、TiO2を含有せしめる。そし
て各成分の割合を上記範囲内に定める。限定の理
由は次の通りである。
SiO2の量を大ならしめると耐熱性は向上する
が、得られた硝子繊維の弾性率が低下し、又失
透、紡糸温度が高くなる。
逆にSiO2の量を小ならしめると耐熱性が低下
する。
Al2O3の量を大ならしめると耐水性、弾性率は
向上するが、失透、紡糸温度が高くなる。逆に
Al2O3の量を小ならしめると失透、紡糸温度は低
下するが、耐水性、弾性率が低下する。
MgOの量を大ならしめると弾性率は向上する
が、失透、紡糸温度が高くなる。逆にMgOの量
を小ならしめると失透、紡糸温度は低下するが、
弾性率が低下する。
B2O3の量を大とすると失透、紡糸温度は低下
するが、強度が低下する。
B2O3の量を小ならしめると強度は向上するが、
失透、紡糸温度が高くなり、溶融、採糸が困難と
なる。
TiO2は溶融硝子の粘性を低下させ、失透、紡
糸温度を低下させ且つ耐水性を向上させる効果を
有するが、TiO2の量が１％を超えると硝子が着
色する。
本発明においては上記必須成分の他に2wt％以
下のCaO及び夫々1wt％以下のR2Ｏ、Fe2O3を含
有せしめることができる。
Fe2O3の量が１％を超えると硝子が着色する。
R2Ｏは失透、紡糸温度を低下させる効果を有
するが、R2Ｏの量が１％を超えると電気的特性
が低下する。
CaOを含有せしめると溶融、紡糸温度を低下さ
せることができるが、この量が2wt％を超える
と、耐水性、強度が低下する。
そして各成分の割合を上記範囲内とすることに
より、溶融特性某他の特性をＥ−硝子と同等であ
り、且つ強度、耐水性もＳ−硝子と同等な硝子繊
維をうることができ、この硝子繊維をFRPの補
強用として用いることにより、強度の極めて大き
いFRPを得ることができる。
又本発明硝子はＦ成分を含有しないので、硝子
溶融炉の廃ガス中に弗素が含有されることなく、
公害問題も発生しない。
本発明硝子繊維は、溶融中のB2O3の揮発逸散
を考慮した所定組成を有するバツチを常法に従つ
て溶融し、得られた溶融硝子をブツシングに穿つ
た小孔から流出せしめ、高速で回転するコレツト
に巻取ることにより硝子繊維とすることができ
る。
硝子繊維の好適な太さは３〜20μ、望ましくは
９〜13μである。
（実施例）
Al2O326.5wt％、MgO12wt％、B2O34.0wt％、
R2O0.6wt％、TiO20.9wt％なる組成を有する太
さ13μの硝子繊維を6000本集束してなる硝子繊維
束を不飽和ポリエステル樹脂の補強繊維として用
い、常法に従つてGC（硝子含有率）70wt％の
FRPを製造した。
このFRPの引張り強度、引張り弾性率、及び
この強度及び弾性率から算出した硝子繊維自身の
強度及び弾性率を別表に示す。
なおこの硝子の溶融性、採糸の作業性はＥ−硝
子と同等であり、耐水性も良好であつた。
（比較例）
実施例の硝子繊維に代え夫々Ｓ−硝子繊維、Ｅ
−硝子繊維を用いて同様な試験を行なつた。結果
を別表に示す。
上記試験結果より、本発明硝子の強度Ｓ−硝子
と同等（引張り強度はＳ−硝子より低いが引張り
弾性率はＳ−硝子より大きい）であり、しかも溶
融、採糸特性はＥ−硝子と同等であることが判明
する。
[Object of the Invention] (Industrial Application Field) The present invention relates to a glass composition for fibers and a glass fiber for FRP. (Prior Art) E-glass is known as one of the glass compositions for fibers, has excellent properties, and is widely used as reinforcing fibers for FRP. The composition of E-glass is approximately as follows. SiO 2 52-56% Al 2 O 3 12-16% CaO 16-19% MgO 0-6% B 2 O 3 4-11% E-glass contains the following minor components in addition to the above main components. R 2 O ＜1% TiO 2 ＜1% Fe 2 O 3 ＜1% F ＜1% Among the above components, B 2 O 3 and F are used to impart desirable characteristics to glass, and these are used to dissolve glass raw materials. Not only does it dissipate into the atmosphere during the process, lowering the yield, but F in particular tends to cause pollution. In addition, E-glass has excellent melting properties and is used in the largest quantity industrially, but its water resistance and strength are relatively low, and when glass fibers are used for reinforcement to obtain particularly strong FRP. , it is necessary to use S-glass which has even greater tensile strength. A typical composition of S-glass is as follows. SiO2 65wt%, Al2O3 25wt %, MgO10wt%. Although S-glass has higher tensile strength and water resistance than E-glass, it does not contain components that promote melting such as CaO, R 2 O, B 2 O 3, etc., so it suffers from devitrification and a spinning temperature of E- It has the disadvantage that it is 250 to 350°C higher than glass, and it is difficult to melt and collect fibers compared to E-glass. (Problems to be Solved by the Invention) The present invention aims to eliminate the above-mentioned drawbacks of the prior art. [Structure of the Invention] (Means for Solving the Problems) The present invention has been made to solve the above-mentioned problems, and contains SiO 2 , Al 2 O 3 , MgO,
Contains B2O3 and TiO2 , and the proportions of these components are SiO2 50-60wt%, Al2O3 25-35wt %, MgO8
~15wt%, B2O3 2 ~6.5wt% TiO2 <1wt%, and R2O ≦1wt%, Fe2O3 ≦ 1wt%, CaO≦
A glass composition for fibers characterized by having a content of 2wt% and SiO 2 , Al 2 O 3 , MgO, B 2 as essential components.
Contains O 3 and TiO 2 , and the proportion of these components is
SiO2 50~60wt%, Al2O3 25 ~35wt%, MgO8~
15wt%, B2O3 2-6.5wt %, TiO2 <1wt%, and R2O ≦1wt%, Fe2O3 ≦ 1wt%, CaO≦
It is 2wt%. Next, the present invention will be explained in more detail. In the present invention, SiO 2 and Al 2 are essential components.
It contains O 3 , MgO, B 2 O 3 and TiO 2 . Then, the ratio of each component is determined within the above range. The reason for the limitation is as follows. Increasing the amount of SiO 2 improves heat resistance, but reduces the elastic modulus of the obtained glass fiber, and also increases devitrification and spinning temperature. Conversely, if the amount of SiO 2 is reduced, the heat resistance will decrease. Increasing the amount of Al 2 O 3 improves water resistance and elastic modulus, but increases devitrification and spinning temperature. vice versa
When the amount of Al 2 O 3 is reduced, devitrification and spinning temperature are reduced, but water resistance and elastic modulus are reduced. Increasing the amount of MgO improves the elastic modulus, but increases devitrification and spinning temperature. Conversely, if the amount of MgO is reduced, devitrification occurs and the spinning temperature decreases, but
Elastic modulus decreases. When the amount of B 2 O 3 is increased, devitrification occurs and the spinning temperature is lowered, but the strength is lowered. Reducing the amount of B 2 O 3 improves the strength, but
Devitrification occurs, the spinning temperature becomes high, and it becomes difficult to melt and collect the fiber. TiO 2 has the effect of reducing the viscosity of molten glass, reducing devitrification and spinning temperature, and improving water resistance, but if the amount of TiO 2 exceeds 1%, the glass becomes colored. In the present invention, in addition to the above-mentioned essential components, 2 wt% or less of CaO, and 1 wt% or less of each of R 2 O and Fe 2 O 3 can be contained. When the amount of Fe 2 O 3 exceeds 1%, the glass becomes colored. R 2 O has the effect of reducing devitrification and spinning temperature, but if the amount of R 2 O exceeds 1%, the electrical properties will deteriorate. Inclusion of CaO can lower melting and spinning temperatures, but if the amount exceeds 2 wt%, water resistance and strength will decrease. By adjusting the ratio of each component within the above range, it is possible to obtain glass fibers that have melting properties and other properties equivalent to those of E-glass, and also have strength and water resistance equivalent to those of S-glass. By using glass fibers to reinforce FRP, it is possible to obtain FRP with extremely high strength. Furthermore, since the glass of the present invention does not contain the F component, no fluorine is contained in the waste gas from the glass melting furnace.
No pollution problems will occur. The glass fiber of the present invention is produced by melting a batch having a predetermined composition in consideration of the volatilization and dissipation of B 2 O 3 during melting in accordance with a conventional method, and causing the obtained molten glass to flow out through a small hole made in a bushing. It can be made into glass fiber by winding it around a collet that rotates at high speed. The suitable thickness of the glass fiber is 3-20μ, preferably 9-13μ. (Example) Al 2 O 3 26.5wt%, MgO 12wt%, B 2 O 3 4.0wt%,
A glass fiber bundle consisting of 6,000 glass fibers with a thickness of 13μ and having a composition of 0.6wt% R 2 O and 0.9wt% TiO 2 was used as a reinforcing fiber for unsaturated polyester resin, and GC ( Glass content) 70wt%
Manufactured FRP. The tensile strength and tensile modulus of this FRP, as well as the strength and modulus of the glass fiber itself calculated from this strength and modulus, are shown in the attached table. The meltability of this glass and the workability of yarn harvesting were equivalent to those of E-glass, and the water resistance was also good. (Comparative example) S-glass fiber and E glass fiber were used in place of the glass fiber in the example.
- Similar tests were conducted using glass fibers. The results are shown in the attached table. From the above test results, the strength of the glass of the present invention is equivalent to that of S-glass (tensile strength is lower than that of S-glass, but the tensile modulus is greater than that of S-glass), and the melting and thread-drawing properties are equivalent to E-glass. It turns out that.
【表】【table】
【表】
（発明の効果）
溶融、採糸特性はＥ−硝子と同等であり、強度
特性はＳ−硝子と同等であり、且つ溶融に際し弗
素化合物を発生することがない。[Table] (Effects of the invention) The melting and thread-drawing characteristics are equivalent to E-glass, the strength characteristics are equivalent to S-glass, and no fluorine compounds are generated during melting.
Claims (1)
TiO2を含み、且つこれらの成分の割合が、SiO2
50〜60wt％、Al2O325〜35wt％、MgO8〜15wt
％、B2O3２〜6.5wt％、TiO2＜1wt％であり、且
つR2Ｏ≦1wt％、Fe2O3≦1wt％、CaO≦2wt％で
あることを特徴とする繊維用硝子組成物。 ２ 必須成分としてSiO2、Al2O3、MgO、B2O3、
TiO2を含み、且つこれらの成分の割合が、SiO2
50〜160wt％、Al2O325〜35wt％、MgO8〜15wt
％、B2O3２〜6.5wt％、TiO2≦1wt％であり、且
つR2Ｏ≦1wt％、Fe2O3≦1wt％、CaO≦2wt％で
あることを特徴とするFRP用硝子繊維。[Claims] 1. SiO 2 , Al 2 O 3 , MgO, B 2 O 3 as essential components,
Contains TiO 2 and the proportion of these components is SiO 2
50~60wt%, Al2O3 25~35wt%, MgO8 ~ 15wt
%, B2O3 2 to 6.5wt%, TiO2 <1wt%, and R2O≦1wt%, Fe2O3 ≦ 1wt % , CaO≦2wt%. Composition. 2. SiO 2 , Al 2 O 3 , MgO, B 2 O 3 as essential components,
Contains TiO 2 and the proportion of these components is SiO 2
50~160wt%, Al2O3 25~35wt%, MgO8 ~ 15wt
%, B2O3 2 to 6.5wt%, TiO2 ≦1wt%, and R2O≦1wt% , Fe2O3 ≦ 1wt%, CaO≦2wt%. fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29770786A JPS63151643A (en) | 1986-12-16 | 1986-12-16 | Glass composition for fibers and glass fibers for FRP |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29770786A JPS63151643A (en) | 1986-12-16 | 1986-12-16 | Glass composition for fibers and glass fibers for FRP |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63151643A JPS63151643A (en) | 1988-06-24 |
| JPH0448739B2 true JPH0448739B2 (en) | 1992-08-07 |
Family
ID=17850121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29770786A Granted JPS63151643A (en) | 1986-12-16 | 1986-12-16 | Glass composition for fibers and glass fibers for FRP |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63151643A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000313634A (en) * | 1999-02-25 | 2000-11-14 | Nippon Sheet Glass Co Ltd | Glass composition and method for producing the same, and substrate for information recording medium, information recording medium and information recording apparatus using the same |
| CN100343188C (en) * | 2004-04-28 | 2007-10-17 | 苏州格瑞特格栅有限公司 | Phenol-formaldehyde fiberglass-reinforced plastics grating |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51107310A (en) * | 1975-03-18 | 1976-09-22 | Denki Kagaku Kogyo Kk |
-
1986
- 1986-12-16 JP JP29770786A patent/JPS63151643A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63151643A (en) | 1988-06-24 |
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