JPH0822764B2 - Glass composition for long fibers - Google Patents
Glass composition for long fibersInfo
- Publication number
- JPH0822764B2 JPH0822764B2 JP1170637A JP17063789A JPH0822764B2 JP H0822764 B2 JPH0822764 B2 JP H0822764B2 JP 1170637 A JP1170637 A JP 1170637A JP 17063789 A JP17063789 A JP 17063789A JP H0822764 B2 JPH0822764 B2 JP H0822764B2
- Authority
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- Japan
- Prior art keywords
- glass
- cao
- composition
- content
- 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
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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
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- 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
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、長繊維用ガラス組成物に関し、特に安価
で、製造工程において環境を害することのなくかつ紡糸
性に優れた長繊維用ガラス組成物に関するものである。TECHNICAL FIELD The present invention relates to a glass composition for long fibers, which is particularly inexpensive, does not harm the environment in the manufacturing process, and has excellent spinnability. It is about things.
［従来技術とその問題点］ 従来より長繊維として産業上用いられている代表的な
ガラス繊維としてＥガラスがある。Ｅガラスは、米国特
許第2,334,961号に記載されていて、その組成は重量％
で、SiO2 52〜56,Al2O3 12〜16,CaO 16〜19,MgO 3〜6,B
2O3 9〜11である。また、この基本的なＥガラスを改良
したものとして、621ガラスが知られている。621ガラス
は、上記ＥガラスのMgOをのぞきCaOの含有率を増加させ
た組成であり、米国特許第2,571,074号に記載されてい
る。621ガラスの組成は該特許によると、重量％で表示
して、SiO2 52〜56,Al2O3 12〜16,CaO 19〜25,B2O3 8〜
13である。これらのＥガラスおよび621ガラスは、SiO2
−Al2O3−CaO系の共融点組成を基本組成とし、製造とく
に溶融を容易にするために、SiO2の一部をB2O3にあるい
はCaOの一部をMgOにおきかえたものであり（「ガラスの
事典」作花済夫編集，朝倉書店,1985,P.28）、B2O3の含
有量は、上記特許にあるように８％以上であるのが一般
的であった。[Prior Art and its Problems] E-glass is a typical glass fiber that has been industrially used as a long fiber. E-glass is described in US Pat. No. 2,334,961 and its composition is wt%.
, SiO 2 52 ~ 56, Al 2 O 3 12 ~ 16, CaO 16 ~ 19, MgO 3 ~ 6, B
2 O 3 9-11. Further, 621 glass is known as an improved version of this basic E glass. The 621 glass has a composition in which the content of CaO other than MgO of the E glass is increased, and is described in US Pat. No. 2,571,074. According to the patent, the composition of the 621 glass is expressed as wt%, and SiO 2 52 to 56, Al 2 O 3 12 to 16, CaO 19 to 25, B 2 O 3 8 to
It is 13. These E-glass and 621-glass are SiO 2
-Al 2 O 3 -CaO based eutectic composition is used as a basic composition, and SiO 2 is partially replaced with B 2 O 3 or CaO is replaced with MgO in order to facilitate production, particularly melting. Yes ("Encyclopedia of Glass" edited by Masao Hana, Asakura Shoten, 1985, P.28), and the content of B 2 O 3 was generally 8% or more as stated in the above patent. .
しかし、最近B2O3の原料が高価であること、およびB2
O3が溶融工程で蒸散しその結果ガラスに変質をおこしや
すいことが問題にされてきており、いくつかの低B2O3ガ
ラスが提案されている。たとえば、米国特許第4,166,74
7号には、重量％で、SiO2 54〜55,Al2O3 13〜14,B2O3
5.5〜6.8,CaO 22〜24,MgO 0.2〜0.5なる組成物が提案さ
れており、この組成では、B2O3を低くするためにMgOを
0.2〜0.5％添加している。しかし、実施例でみると、Mg
Oは原料から積極的に加えられているのではなく不純物
として入っているのみである。そのため、不純物として
加えられる量は0.2〜0.5％に限られMgOの効果が十分得
られない。また、特平公１−27008にある低B2O3繊維用
ガラス組成物は、B2O3を減少させた分CaOを増大させて
おり、失透が生じやすくかつ耐薬品性に問題がある。さ
らに、特平公１−27009にある低B2O3繊維用ガラス組成
物は、B2O3を減少させた分ZnOを加えている。しかし、Z
nOはその原料がB2O3よりも高価であるため、B2O3減少の
利点がなくなる。また、特開昭60−264345,特開昭61−1
55227,および特開昭62−162649にも低B2O3の繊維用組成
が記載されているが、これらにはいずれも融剤としてF2
が含まれている。しかしながら、F2は溶融工程で蒸散し
環境に害をおよぼすために組成に含有させることは好ま
しくない。また、特開昭48−37411には、F2に代わる融
剤としてLi2Oが記載されているが、Li2Oは原料が著しく
高価である。However, recently, the raw material of B 2 O 3 is expensive, and B 2 O 3 is expensive.
It has been a problem that O 3 evaporates in the melting process and, as a result, the glass is likely to deteriorate, and some low B 2 O 3 glasses have been proposed. For example, U.S. Pat.
No. 7 contains SiO 2 54-55, Al 2 O 3 13-14, B 2 O 3 in weight%.
A composition of 5.5 to 6.8, CaO 22 to 24, MgO 0.2 to 0.5 has been proposed, and in this composition, MgO is added to lower B 2 O 3.
0.2-0.5% is added. However, in the example, Mg
O is not added positively from the raw material but is only contained as an impurity. Therefore, the amount added as an impurity is limited to 0.2 to 0.5%, and the effect of MgO cannot be sufficiently obtained. Further, the glass composition for low B 2 O 3 fibers in Japanese Patent Publication No. 1-200808 increases CaO by the amount of B 2 O 3 decreased, and thus devitrification easily occurs and there is a problem in chemical resistance. . Furthermore, the glass composition for low B 2 O 3 fibers in Japanese Patent Publication No. 1-27009 has added ZnO in a reduced B 2 O 3 content. But Z
The raw material for nO is more expensive than B 2 O 3 , so the benefit of B 2 O 3 reduction is lost. Further, JP-A-60-264345, JP-A-61-1
55227, and JP-A-62-162649 also describe low B 2 O 3 composition for fibers, all of which contain F 2 as a fluxing agent.
It is included. However, it is not preferable to include F 2 in the composition because it evaporates in the melting process and harms the environment. Further, in Japanese Patent Laid-Open No. 483741/1978, Li 2 O is described as a flux instead of F 2 , but the raw material of Li 2 O is extremely expensive.
以上のように、従来より生産されている長繊維用ガラ
スは、融剤であるB2O3を８％以上含有するか、あるいは
同じく融剤であるF2を含有することによってガラスの溶
融を容易にしていた。しかし、B2O3は，原料が高価であ
りかつ溶融工程での蒸散が著しいという問題があり、ま
たF2は、溶融工程で大気中に蒸散し環境を汚染するとい
う問題がある。そのため、F2を含まずかつB2O3含有量を
減少させることが望ましいが、B2O3の減少によりガラス
の溶融が困難になるということにたいして、CaOのみの
増加で補うと失透が生じやすくなり紡糸が困難になる。
また、ZnOの添加で補うとかえって原価が高くなる。As described above, the glass for long fibers that has been conventionally produced contains 8% or more of B 2 O 3 which is a flux, or contains F 2 which is also a flux, to melt the glass. It was easy. However, B 2 O 3 has a problem that the raw material is expensive and the evaporation in the melting process is remarkable, and F 2 has a problem that it evaporates into the atmosphere in the melting process and pollutes the environment. Therefore, it is desirable to reduce the content of B 2 O 3 without containing F 2 , but it is difficult to melt the glass due to the decrease of B 2 O 3 , devitrification is compensated by increasing only CaO. It tends to occur and makes spinning difficult.
In addition, adding ZnO increases the cost.
本発明は、環境汚染物質であるF2を含まず、かつB2O3
の減少を原料の高価なZnOおよびLi2Oで補うことなく、
さらに失透が生じにくく紡糸性に優れた長繊維用ガラス
組成物を提供することを目的とする。The present invention does not contain F 2 which is an environmental pollutant, and B 2 O 3
, Without compensating for the decrease in the cost with expensive ZnO and Li 2 O as raw materials,
Further, it is an object of the present invention to provide a glass composition for long fibers which is less likely to cause devitrification and has excellent spinnability.
［発明の構成］ 本発明は、B2O3の減少による溶融性の悪化をMgOおよ
びCaOの含有量を最適化することにより補うことができ
ることを見いだしたものである。すなわち、元来、Ｅガ
ラスおよび上記各特許に記載のガラスは、SiO2−Al2O3
−CaO系の共融点組成を基本とし、SiO2の一部を融剤で
あるB2O3で置換している。したがって、B2O3の減少分を
単純にSiO2で補うとガラスの溶融性を悪化させる。ま
た、B2O3の減少分をAl2O3で補うと、ガラスの溶融性を
悪化させるとともにガラスが失透しやすくなる。CaOで
補う場合、CaO含有量が多くなりすぎると耐薬品性が悪
くなるとともにガラスが失透しやすくなる。そこで、Ca
Oの一部をMgOで置換すると耐薬品性の悪化が防げるとと
もに失透も生じないことを見いだした。ただ、もともと
共融点組成を基本としているため、組成のわずかなずれ
により液相温度が著しく上昇しガラスが失透しやすくな
ることがある。そのため、CaO、MgOおよびその合量を限
定することで最適組成範囲が得られることがわかった。[Structure of the Invention] The present invention has found that the deterioration of meltability due to the decrease of B 2 O 3 can be compensated by optimizing the contents of MgO and CaO. That is, originally, the E glass and the glasses described in the above patents are SiO 2 —Al 2 O 3
Basic to the eutectic composition of -CaO system, and replacing a part of SiO 2 in B 2 O 3 is flux. Therefore, simply compensating for the decrease in B 2 O 3 with SiO 2 deteriorates the meltability of the glass. Further, if the decrease of B 2 O 3 is supplemented with Al 2 O 3 , the meltability of the glass is deteriorated and the glass is easily devitrified. When supplementing with CaO, if the CaO content is too high, the chemical resistance deteriorates and the glass tends to devitrify. So Ca
It has been found that when a part of O is replaced with MgO, deterioration of chemical resistance can be prevented and devitrification does not occur. However, since it is originally based on the eutectic composition, a slight deviation of the composition may cause the liquidus temperature to remarkably rise and the glass to easily devitrify. Therefore, it was found that the optimum composition range can be obtained by limiting the amounts of CaO, MgO and their total amounts.
本発明の要旨は、重量％で表示してSiO2 54.5〜57,Al
2O3 13〜16,B2O3 5〜7.5,CaO 21〜23,MgO 0.6〜3,CaO＋
MgO 21.6〜24,Na2O 0〜1,K2O 0〜1,Na2O＋K2O 0〜1,TiO
2 0〜1,Fe2O3 0〜１からなり、実質的にLi2O,ZnOおよび
F2を含まず紡糸性に優れた長繊維用ガラス組成物であ
る。The gist of the present invention is to express SiO 2 54.5 to 57, Al in terms of% by weight.
2 O 3 13 to 16, B 2 O 3 5 to 7.5, CaO 21 to 23, MgO 0.6 to 3, CaO +
MgO 21.6~24, Na 2 O 0~1, K 2 O 0~1, Na 2 O + K 2 O 0~1, TiO
20 to 1 , Fe 2 O 3 0 to 1 and substantially consists of Li 2 O, ZnO and
A glass composition for long fibers, which does not contain F 2 and has excellent spinnability.
本発明の長繊維用ガラス組成物に関し、その各ガラス
成分の作用効果および組成範囲限定の理由を以下に述べ
る。Regarding the glass composition for long fibers of the present invention, the effect of each glass component and the reason for limiting the composition range will be described below.
SiO2は、基本系の構成成分がガラスの骨格を形成す
る。SiO2の含有量が、54.5％より少ないと耐薬品性が悪
化し、57％を越えると溶融しにくくなるとともに失透し
やすくなる。Al2O3は、基本系の構成成分でガラスの骨
格を形成する。Al2O3の含有量が、13％よりすくないと
液相温度が上昇しガラスが失透しやすくなり、16％を越
えるとガラス融液の粘度が上昇し溶融および紡糸が困難
になる。B2O3は、融剤として作用しガラス融液の粘度を
下げて溶融および紡糸を容易にする。B2O3の含有量が５
％より少ないと、ガラス融液の粘度が上昇し溶融および
紡糸が困難になる。しかし、7.5％をこえると、原料コ
ストが高くなるとともに融液からの蒸散が増大しガラス
の変質が生じる。CaOは、基本系の構成成分であるとと
もに融剤として作用する。CaOの含有量が21％より少な
いと、ガラス融液の粘度が上昇するため溶融および紡糸
が困難になる。CaO含有量が23％を越えると、失透しや
すくなるとともに耐薬品性が悪くなる。MgOは、失透を
制御するとともに融剤として作用するが、0.6％より少
ないとその効果がなく、３％を越えると失透しやすくな
る。CaOとMgOの合量が21.6％より少ないとガラス融液の
粘度が上昇し、24％より多いと失透しやすくなる。Na
2O,K2O,TiO2およびFe2O3は、原料からの不純物としてそ
れぞれ1.0％以下は含有してもよい。ただし、Na2Oおよ
びK2Oは、含有量が多いとガラスの電気特性を悪化させ
るので1.0％を上限とする。また、TiO2およびFe2O3は、
含有量が1.0％を越えると、ガラスが着色するので、1.0
％を上限とする。In SiO 2 , the constituents of the basic system form the skeleton of glass. If the SiO 2 content is less than 54.5%, the chemical resistance deteriorates, and if it exceeds 57%, it becomes difficult to melt and devitrification easily occurs. Al 2 O 3 is a constituent of the basic system and forms the skeleton of glass. If the Al 2 O 3 content is less than 13%, the liquidus temperature rises and the glass tends to devitrify, while if it exceeds 16%, the viscosity of the glass melt increases and melting and spinning become difficult. B 2 O 3 acts as a flux and reduces the viscosity of the glass melt to facilitate melting and spinning. B 2 O 3 content is 5
If it is less than%, the viscosity of the glass melt increases and melting and spinning become difficult. However, if it exceeds 7.5%, the raw material cost becomes high and the evaporation from the melt increases, so that the glass is deteriorated. CaO is a constituent of the basic system and acts as a flux. If the content of CaO is less than 21%, the viscosity of the glass melt increases and melting and spinning become difficult. When the CaO content exceeds 23%, devitrification is likely to occur and the chemical resistance becomes poor. MgO controls devitrification and acts as a flux, but if it is less than 0.6%, it has no effect, and if it exceeds 3%, devitrification tends to occur. If the total amount of CaO and MgO is less than 21.6%, the viscosity of the glass melt increases, and if it exceeds 24%, devitrification is likely to occur. Na
2 O, K 2 O, TiO 2 and Fe 2 O 3 may be contained as impurities from raw materials in an amount of 1.0% or less. However, if the content of Na 2 O and K 2 O is large, the electrical characteristics of the glass deteriorate, so the upper limit is 1.0%. In addition, TiO 2 and Fe 2 O 3 are
If the content exceeds 1.0%, the glass will be colored, so 1.0
% Is the upper limit.
［実施例］ 次に本発明を実施例に基ずいてさらに詳しく説明す
る。次表は本発明の実施例および比較例の各試料のガラ
ス組成と特性を示すものである。EXAMPLES Next, the present invention will be described in more detail based on examples. The following table shows the glass composition and characteristics of each sample of the examples and comparative examples of the present invention.
表に示したNo.1〜７の試料は、次のように調製した。
まず、表に示す組成にあわせてガラス原料を調合し白金
坩堝を用いて1500℃で４時間溶融した。溶融後、融液を
カーボン板上に流しだし、アニールして以下の測定に供
するガラス試料を得た。ガラスの粘度を白金球引き上げ
法にて測定した。紡糸温度は103ポイズに相当する温
度、溶融温度は102ポイズに相当する温度である。ま
た、白金ボートに297〜500μｍの粉末をいれ温度勾配炉
に16時間保持した後の失透観察により液相温度を測定し
た。耐薬品性試験として、粉末法による耐酸性試験を実
施した。297〜500μｍの粉末を80℃,10％硫酸に入れ16
時間保持した後、重量減少率を測定した。 The samples Nos. 1 to 7 shown in the table were prepared as follows.
First, a glass raw material was prepared according to the composition shown in the table and melted at 1500 ° C. for 4 hours using a platinum crucible. After melting, the melt was poured onto a carbon plate and annealed to obtain a glass sample to be used in the following measurement. The viscosity of the glass was measured by the platinum ball pull-up method. The spinning temperature is a temperature corresponding to 10 3 poise, and the melting temperature is a temperature corresponding to 10 2 poise. The liquid phase temperature was measured by devitrification observation after placing 297 to 500 μm powder in a platinum boat and holding it in a temperature gradient furnace for 16 hours. As a chemical resistance test, an acid resistance test by the powder method was carried out. Put 297-500μm powder in 80%, 10% sulfuric acid 16
After holding for a period of time, the weight loss rate was measured.
表から明らかなように本発明の実施例であるNo.1〜６
は、いずれも、紡糸温度が1220℃以下、溶融温度が1420
℃以下であり、紡糸性および溶融性に優れていることが
わかる。また、液相温度が1100℃以下であり、失透が生
じにくいことがわかる。一方、比較例は、CaO含有量が
大きいため液相温度が高く紡糸性が悪い。さらにSiO2含
有量が少ないため耐酸性試験で重量減少率が大きく耐薬
品性に劣ることがわかる。As is apparent from the table, Nos. 1 to 6 which are examples of the present invention
Both have a spinning temperature of 1220 ° C or lower and a melting temperature of 1420 ° C.
It can be seen that the temperature is not higher than 0 ° C and the spinnability and meltability are excellent. Further, it can be seen that the liquidus temperature is 1100 ° C. or lower, and devitrification is unlikely to occur. On the other hand, in the comparative example, since the CaO content is large, the liquidus temperature is high and the spinnability is poor. Furthermore, since the content of SiO 2 is small, the weight loss rate is large in the acid resistance test and the chemical resistance is poor.
［発明の効果］ 以上のように本発明によると、紡糸性および溶融性を
損なうことなくB2O3含有量を低くした長繊維用ガラス組
成物を得ることができる。本発明の長繊維用ガラス組成
物は、B2O3含有量を低くしたことにより溶融工程でのB2
O3蒸散に伴うガラスの変質を防ぐことができるため品質
が向上し、さらに低B2O3であるとともにLi2OやZnOを含
まないため安価な製品の供給が可能である。また、本発
明のガラス組成物は、耐薬品性にも優れており、F2を含
有しないため、製造工程で環境を汚染することがない。[Effect of the Invention] As described above, according to the present invention, a glass composition for long fibers having a low B 2 O 3 content can be obtained without impairing spinnability and meltability. The glass composition for long fibers of the present invention has a B 2 O 3 content of B 2 in the melting step due to a low content.
Since it is possible to prevent the glass from being deteriorated due to O 3 evaporation, the quality is improved, and since it is low in B 2 O 3 and does not contain Li 2 O or ZnO, it is possible to supply an inexpensive product. Further, the glass composition of the present invention has excellent chemical resistance and does not contain F 2 and therefore does not pollute the environment in the manufacturing process.
Claims (1)
2O3 5〜7.5,CaO 21〜23,MgO 0.6〜3,CaO＋MgO 21.6〜2
4,Na2O 0〜1,K2O 0〜1,Na2O＋K2O 0〜1,TiO2 0〜1,Fe2O
3 0〜１からなり、実質的にLi2O,ZnOおよびF2を含まず
紡糸性に優れた長繊維用ガラス組成物。1. SiO 2 54.5-57, Al 2 O 3 13-16, B in wt%
2 O 3 5 ~ 7.5, CaO 21 ~ 23, MgO 0.6 ~ 3, CaO + MgO 21.6 ~ 2
4, Na 2 O 0 to 1, K 2 O 0 to 1, Na 2 O + K 2 O 0 to 1, TiO 2 0 to 1, Fe 2 O
A glass composition for long fibers, which is composed of 30 to 1 and is substantially free of Li 2 O, ZnO and F 2 and has excellent spinnability.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1170637A JPH0822764B2 (en) | 1989-06-30 | 1989-06-30 | Glass composition for long fibers |
| FR9008240A FR2650268B1 (en) | 1989-06-30 | 1990-06-29 | GLASS FOR GLASS FIBERS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1170637A JPH0822764B2 (en) | 1989-06-30 | 1989-06-30 | Glass composition for long fibers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0337136A JPH0337136A (en) | 1991-02-18 |
| JPH0822764B2 true JPH0822764B2 (en) | 1996-03-06 |
Family
ID=15908569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1170637A Expired - Lifetime JPH0822764B2 (en) | 1989-06-30 | 1989-06-30 | Glass composition for long fibers |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0822764B2 (en) |
| FR (1) | FR2650268B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976619A (en) * | 2012-11-15 | 2013-03-20 | 安徽工程大学 | Glass fiber used for automobile bumper |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2717464B1 (en) * | 1994-03-15 | 1996-05-24 | Vetrotex France Sa | Glass fibers intended for the reinforcement of organic and composite materials obtained. |
| US7022634B2 (en) | 2003-07-07 | 2006-04-04 | Johns Manville | Low boron E-glass composition |
| JP2017226582A (en) * | 2016-06-23 | 2017-12-28 | 日本電気硝子株式会社 | Manufacturing method of glass fiber |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3687850A (en) * | 1970-03-27 | 1972-08-29 | Johns Manville | High temperature insulating fiber |
| JPS4837411A (en) * | 1971-09-16 | 1973-06-02 | ||
| JPS5777042A (en) * | 1980-10-31 | 1982-05-14 | Asahi Fiber Glass Co Ltd | Glass composition for filament |
| JPS63225552A (en) * | 1987-03-13 | 1988-09-20 | Nitto Boseki Co Ltd | Glass composition absorbing ultraviolet ray for fiber |
-
1989
- 1989-06-30 JP JP1170637A patent/JPH0822764B2/en not_active Expired - Lifetime
-
1990
- 1990-06-29 FR FR9008240A patent/FR2650268B1/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976619A (en) * | 2012-11-15 | 2013-03-20 | 安徽工程大学 | Glass fiber used for automobile bumper |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2650268B1 (en) | 1992-10-09 |
| FR2650268A1 (en) | 1991-02-01 |
| JPH0337136A (en) | 1991-02-18 |
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