JPH0336773B2 - - Google Patents
Info
- Publication number
- JPH0336773B2 JPH0336773B2 JP55077876A JP7787680A JPH0336773B2 JP H0336773 B2 JPH0336773 B2 JP H0336773B2 JP 55077876 A JP55077876 A JP 55077876A JP 7787680 A JP7787680 A JP 7787680A JP H0336773 B2 JPH0336773 B2 JP H0336773B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- composition
- liquidus temperature
- content
- fibers
- 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
- 239000011521 glass Substances 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 21
- 239000000835 fiber Substances 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 description 7
- 239000007790 solid phase Substances 0.000 description 5
- 239000006060 molten glass Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
- C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
-
- 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)
Description
本発明は繊維用の硝子組成物に関するものであ
る。
繊維用の硝子組成物の一つとしてはＥ−硝子が
知られ、優れた諸特性を有するため広く用いられ
ている。Ｅ−硝子の典型的組成は次の通りであ
る。
SiO2 52〜56％
Al2O3 12〜16％
CaO 16〜19％
MgO ３〜６％
B2O3 ９〜11％
Ｅ−硝子は上記主要成分の他に次の微量成分を
含むことがある。
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
解工程中に大気中に逸散し、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、又
B2O3を大量に使用することはコスト的、資源的
にも問題を生ずる。
このため、B2O3或はＦの使用料を減少するた
め各種提案が行われている。例えば、米国特許公
報（第4166747号明細書）にはB2O3の含有量が少
く、しかもＥ−硝子と同等の性質を有する繊維用
の硝子組成が記載されている。その一例は次の通
りである。
SiO2 54.2
Al2O3 13.4
Fe2O3 0.3
MgO 0.3
CaO 23.0
B2O3 6.5
Na2O 0.5
Ｆ 1.4
液相温度 1190℃
前記米国特許明細書（以下本刊行物と呼ぶ）に
開示された組成を有する硝子は、B2O3の含有率
は小さいが、Ｆ含有量が大きく、さらに液相温度
が高い難点がある。
本刊行物に具体的に成組が示された硝子の液相
温度は1171℃〜1210℃であり、又Ｆ含有量は0.7
及び1.4である。
液相温度とは、溶融硝子から固相の析出する温
度を云い、この温度が高い程、硝子製造工程にお
いて固相が析出し易い傾向があり、このため糸切
れが発生し易くなり、歩留り、生産性の低下を生
じ易い。
又Ｆ含有量が大となると、公害が発生し、Ｆを
除去するための廃ガスの処理費が増大する。
上述したように、Ｆ−硝子は、優れた諸特性を
有し、硝子繊維の製造に広く用いられているが、
硝子の特性は硝子の組成によつて定まり、液相温
度も硝子の組成に応じて定まる。従つて、液相温
度を低下させるために硝子組成を変更すると、得
られた硝子繊維の特性も変化し、Ｅ−硝子の優れ
た特性が失われ易い。
又、公害防止のためＦの含有量を低下させる
と、硝子の溶融特性が悪化し易く、Ｆの含有率を
低くして、しかも溶融特性を良好ならしめようと
すると、Ｆ以外の硝子組成を変更することが必要
となり、硝子特性の低下、生産性の悪化を招来し
易い。
液相温度は、本来平衡状態によつて定まる数値
であり、速度に無関係である。一方、固相の析出
のし易さは速度論の問題である。従つて、一般的
には、液相温度が高い程、固相が析出し易い傾向
を有するが、この関係は、飽くまでも一般的なも
のであり、液相温度から固相の析出し易さを算出
することはできない。
硝子の液相温度は、小量の原料を溶融すること
により容易に測定することができ、又硝子の原料
組成から比較的容易に予測することができるが、
糸切れの発生率は、上述したように液相温度から
算出することはできず、糸切れ発生の少ない硝子
組成を決定するためには多量の溶融硝子を使用し
て、長時間のランニングテストを行う必要があ
る。
このような事情のため、Ｆの含有量、B2O3の
含有量が少なく、且つ糸切れ発生の少ない硝子を
うることは極めて困難であつた。
本発明はかかる難点を解決するための研究に基
づく新なる提案である。本発明は即ち、SiO2、
Al2O3、CaO、MgO、R2O（Na2O及び／又は
K2O）、B2O3、Ｆ、TiO2、Fe2O3、を必須成分と
して含み且つSiO253.0〜53.9％、Al2O314.5〜17.0
％、CaO＋MgO21.0〜24.％、MgO0.1〜5.0％、
Na2O＋K2O0.4〜0.9％、B2O35.8〜7.2％、F0.2〜
1.0％、TiO2＜0.6％、Fe2O3＜0.6％である繊維用
の硝子組成物に関するものである。
本発明の硝子はB2O3、Ｆの含有量、糸切れの
発生率も少なく、又、液相温度も低く、しかも強
度、耐候性等においてＥ−硝子と同等の性能を有
し、本発明は工業上有益なものである。
次表Ａに示す組成を有する溶融硝子をブツシン
グから引出し、硝子繊維束を製造した（硝子繊維
の太さ10μ、集束本数800本）。
次表Ｂに糸切れの発生状況、液相温度を示す。
なお、表中〜は本発明の硝子組成、はＥ
−硝子の組成、Ｖは「The Manufacturing
Technology of Continuous Glass Fiber」第30
頁第１欄の硝子の組成、は本刊行物table
の硝子組成、は本刊行物tableの硝子組成で
ある。
The present invention relates to glass compositions for fibers. E-glass is known as one of the glass compositions for fibers, and is widely used because it has excellent properties. A typical composition of E-glass is as follows. SiO 2 52-56% Al 2 O 3 12-16% CaO 16-19% MgO 3-6% B 2 O 3 9-11% E-glass may contain the following minor components in addition to the above main components. be. 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 give desirable properties to glass, and these are used to dissolve glass raw materials. Not only does F dissipate into the atmosphere during the process and reduce yield, but it also causes pollution, and
Using a large amount of B 2 O 3 causes problems in terms of cost and resources. Therefore, various proposals have been made to reduce the usage fee for B 2 O 3 or F. For example, US Pat. No. 4,166,747 describes a glass composition for fibers that has a low content of B 2 O 3 and has properties equivalent to E-glass. An example is as follows. SiO 2 54.2 Al 2 O 3 13.4 Fe 2 O 3 0.3 MgO 0.3 CaO 23.0 B 2 O 3 6.5 Na 2 O 0.5 F 1.4 Liquidus temperature 1190°C Disclosed in the above US patent specification (hereinafter referred to as this publication) Glass having this composition has a low B 2 O 3 content, but has a large F content and a high liquidus temperature. The liquidus temperature of the glass whose composition is specifically shown in this publication is 1171°C to 1210°C, and the F content is 0.7
and 1.4. The liquidus temperature refers to the temperature at which a solid phase precipitates from molten glass.The higher this temperature is, the more likely the solid phase is to precipitate during the glass manufacturing process, which increases the likelihood of thread breakage and reduces yield. Productivity is likely to decrease. Furthermore, when the F content increases, pollution occurs and the cost of processing waste gas to remove F increases. As mentioned above, F-glass has excellent properties and is widely used in the production of glass fibers.
The properties of glass are determined by the composition of the glass, and the liquidus temperature is also determined by the composition of the glass. Therefore, when the glass composition is changed in order to lower the liquidus temperature, the properties of the obtained glass fibers also change, and the excellent properties of E-glass are likely to be lost. Furthermore, if the F content is lowered to prevent pollution, the melting characteristics of the glass tend to deteriorate, and if an attempt is made to lower the F content and improve the melting characteristics, it is necessary to increase the glass composition other than F. It is necessary to make changes, which tends to lead to deterioration of glass properties and productivity. The liquidus temperature is originally a value determined by the equilibrium state and is unrelated to the speed. On the other hand, the ease of precipitation of the solid phase is a matter of kinetics. Therefore, in general, the higher the liquidus temperature, the easier the solid phase will precipitate, but this relationship is a general one, and the ease of solid phase precipitation can be determined from the liquidus temperature. It cannot be calculated. The liquidus temperature of glass can be easily measured by melting a small amount of raw material, and can be relatively easily predicted from the raw material composition of glass.
As mentioned above, the occurrence rate of thread breakage cannot be calculated from the liquidus temperature, and in order to determine the glass composition that will reduce the occurrence of thread breakage, it is necessary to conduct a long running test using a large amount of molten glass. There is a need to do. Due to these circumstances, it has been extremely difficult to obtain glass with a low content of F and low content of B 2 O 3 and less occurrence of thread breakage. The present invention is a new proposal based on research to solve these difficulties. The present invention includes SiO 2 ,
Al 2 O 3 , CaO, MgO, R 2 O (Na 2 O and/or
Contains K2O ), B2O3 , F, TiO2 , Fe2O3 as essential components, SiO2 53.0-53.9 %, Al2O3 14.5-17.0 %
%, CaO+MgO21.0-24.%, MgO0.1-5.0%,
Na2O + K2O0.4 ~0.9%, B2O3 5.8 ~7.2%, F0.2~
1.0%, TiO 2 <0.6%, Fe 2 O 3 <0.6%. The glass of the present invention has a low content of B 2 O 3 and F, a low incidence of thread breakage, a low liquidus temperature, and has performance equivalent to E-glass in terms of strength, weather resistance, etc. The invention is of industrial interest. Molten glass having the composition shown in Table A below was drawn out from the bushing to produce a glass fiber bundle (glass fiber thickness: 10 μm, number of bundled fibers: 800). Table B below shows the occurrence of thread breakage and the liquidus temperature. In the table, ~ indicates the glass composition of the present invention, and indicates E.
- Glass composition, V is “The Manufacturing
Technology of Continuous Glass Fiber” No. 30
The composition of glass in the first column of the page is from the table of this publication.
The glass composition of is the glass composition of this publication table.
【表】【table】
【表】【table】
【表】
特開昭48−37411号（以下引例(ロ)という）第１
表３の組成を有する硝子と本発明実施例の組成
を有する硝子とを夫々溶融し同一条件で溶融硝子
をブツシングから引出し硝子繊維束を製造した
（硝子繊維の太さ10μ、集束本数800本）１ブツシ
ング、１日当りの糸切れ発生件数の３日間の平均
値及び糸切れ発生の減少に伴なう（引例(ロ)の発明
を100として）生産量の増加割合は次の通りであ
つた。[Table] JP-A-48-37411 (hereinafter referred to as reference (b)) No. 1
Glass having the composition shown in Table 3 and glass having the composition according to the example of the present invention were each melted, and the molten glass was drawn out from a bushing under the same conditions to produce a glass fiber bundle (glass fiber thickness 10μ, number of bundled fibers 800). The three-day average of the number of yarn breakages per bushing per day and the rate of increase in production due to the decrease in the number of yarn breakages (with the invention in reference (b) as 100) were as follows.
Claims (1)
び／又はK2O）、B2O3、Ｆ、TiO2、Fe2O3、を必
須成分として含み且つSiO253.0〜53.9％、
Al2O314.5〜17.0％、CaO＋MgO21.0〜24.0％、
MgO0.1〜5.0％、Na2O＋K2O0.4〜0.9％、
B2O35.8〜7.2％、F0.2〜1.0％、TiO2＜0.6％、
Fe2O3＜0.6％である繊維用の硝子組成物。1 Contains SiO 2 , Al 2 O 3 , CaO, MgO, R 2 O (Na 2 O and/or K 2 O), B 2 O 3 , F, TiO 2 , Fe 2 O 3 as essential components, and contains SiO 2 53.0~53.9%,
Al 2 O 3 14.5-17.0%, CaO + MgO2 1.0-24.0%,
MgO0.1-5.0%, Na2O + K2O0.4-0.9 %,
B2O3 5.8-7.2 %, F0.2-1.0%, TiO2 <0.6%,
A glass composition for fibers having Fe 2 O 3 <0.6%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7787680A JPS573737A (en) | 1980-06-11 | 1980-06-11 | Glass composition for filament |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7787680A JPS573737A (en) | 1980-06-11 | 1980-06-11 | Glass composition for filament |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS573737A JPS573737A (en) | 1982-01-09 |
| JPH0336773B2 true JPH0336773B2 (en) | 1991-06-03 |
Family
ID=13646255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7787680A Granted JPS573737A (en) | 1980-06-11 | 1980-06-11 | Glass composition for filament |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS573737A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4521523A (en) * | 1982-10-18 | 1985-06-04 | Owens-Corning Fiberglas Corporation | Methods of introducing fluorine into glasses |
| JPS60264345A (en) * | 1984-06-12 | 1985-12-27 | Nippon Sheet Glass Co Ltd | Glass composition for fiber |
| CN115818966A (en) * | 2019-09-25 | 2023-03-21 | 巨石集团有限公司 | Electronic-grade glass fiber composition, glass fiber thereof and electronic cloth |
-
1980
- 1980-06-11 JP JP7787680A patent/JPS573737A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS573737A (en) | 1982-01-09 |
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