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JPH10231142A - Corrosion-resistant glass fiber - Google Patents

Corrosion-resistant glass fiber

Info

Publication number
JPH10231142A
JPH10231142A JP5090997A JP5090997A JPH10231142A JP H10231142 A JPH10231142 A JP H10231142A JP 5090997 A JP5090997 A JP 5090997A JP 5090997 A JP5090997 A JP 5090997A JP H10231142 A JPH10231142 A JP H10231142A
Authority
JP
Japan
Prior art keywords
mol
glass
corrosion
glass fiber
temperature
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.)
Granted
Application number
JP5090997A
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Japanese (ja)
Other versions
JP3801293B2 (en
Inventor
Toru Kawamoto
徹 河本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Electric Glass Co Ltd
Original Assignee
Nippon Electric Glass Co Ltd
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Filing date
Publication date
Application filed by Nippon Electric Glass Co Ltd filed Critical Nippon Electric Glass Co Ltd
Priority to JP05090997A priority Critical patent/JP3801293B2/en
Publication of JPH10231142A publication Critical patent/JPH10231142A/en
Application granted granted Critical
Publication of JP3801293B2 publication Critical patent/JP3801293B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics

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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)

Abstract

PROBLEM TO BE SOLVED: To provide a corrosion-resistant glass fiber that contains a reduced amount of B2 O3 , contains no F2 , and is excellent in resistance to acid or water as well as excellent in devitrification behavior, and high in productivity. SOLUTION: This corrosion-resistant glass fiber contains 56-63mol% of SiO2 , 0.5-4.5mol% of TiO2 , 0-5mol% of MgO, 1-9mol% of TiO2 +MgO, 4.5-9mol% of Al2 O3 , 16-26mol% of CaO, where 0-7mol% of ΣRO=ZnO+SrO+BaO, 0-1.5mol% of Na2 O, 0-1.5mol% of K2 O, 0-1.5mol% of Li2 O where Na2 O+K2 O+ Li2 O<=3mol%, and 0.5-3mol% of B2 O3 , but not contains F2 .

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【産業上の利用分野】本発明は、Ｂ2 Ｏ3 を少量しか含
まず、Ｆ2 を含まないため、環境を汚染することがな
く、現在最も多く生産されているＥガラス繊維に比べて
耐酸性や耐水性に優れているため、ＦＲＰ、耐蝕ＦＲ
Ｐ、プリント基板用樹脂等の複合材料や、バッテリーセ
パレーター等の耐蝕性材料として適した耐蝕性ガラス繊
維に関するものである。The present invention contains only a small amount of B 2 O 3 and does not contain F 2 , so that it does not pollute the environment and has an acid resistance higher than that of E glass fiber which is currently most frequently produced. FRP, corrosion resistant FR due to excellent resistance and water resistance
The present invention relates to a corrosion-resistant glass fiber suitable as a corrosion-resistant material such as a composite material such as P, a resin for a printed circuit board, or a battery separator.

【０００２】[0002]

【従来の技術】従来、上記の用途に使用されているＢ2
Ｏ3 、Ｆ2 を含有しない繊維用ガラスとしては、ＵＳＰ
３，８４７，６２７、ＵＳＰ３，８７６，４８１、ＵＳ
Ｐ４，０２６，７１５に記載されているＳｉＯ2 −Ｔｉ
Ｏ2 −Ａｌ2 Ｏ3 −ＲＯ（ＲはＣａ等の２価金属）系の
ＥＣＲガラスが用いられている。2. Description of the Related Art Conventionally, B 2
As glass for fibers not containing O 3 and F 2 , USP
3,847,627, USP 3,876,481, US
SiO 2 —Ti described in P4,026,715
ECR glass based on O 2 —Al 2 O 3 —RO (R is a divalent metal such as Ca) is used.

【０００３】[0003]

【発明が解決しようとする課題】ＥＣＲガラスは、Ｂ2
Ｏ3 、Ｆ2 を含まず、Ｅガラスに比べ、耐酸性、耐水性
に優れている。The ECR glass is B 2
It does not contain O 3 and F 2 and has better acid resistance and water resistance than E glass.

【０００４】ところで通常、ガラスを繊維化するために
は、所定割合に配合されたガラス原料を溶融して、均質
なガラスとした後、多数のノズルを底部に形成したブッ
シングに溶融ガラスを供給し、ブッシングのノズルから
ガラスを引き出すことによって繊維化する方法が採られ
る。[0004] Usually, in order to fiberize glass, a glass material blended in a predetermined ratio is melted to form a homogeneous glass, and then the molten glass is supplied to a bushing having a number of nozzles formed at the bottom. A method is employed in which the glass is drawn out from a bushing nozzle to produce a fiber.

【０００５】この場合、ガラスの失透温度が、ガラスを
繊維化する際の温度である紡糸温度を越えると、ガラス
融液中に失透物が生じ、ノズル付近で糸切れが起こり易
くなるため、失透温度は、紡糸温度より低い温度である
ことが繊維化の条件であり、その差（ΔＴ）が大きいほ
ど、紡糸性が良好となるが、ＥＣＲガラスは、失透温度
が１１５０℃以上であり、また紡糸温度に相当する１０
3 温度が１２００℃前後であるため、ΔＴが約５０℃と
なり、紡糸時にブッシングノズルの部分で失透が生じ易
く生産が困難であった。[0005] In this case, if the devitrification temperature of the glass exceeds the spinning temperature, which is the temperature at which the glass is fiberized, a devitrified substance is generated in the glass melt, and thread breakage is likely to occur near the nozzle. The fiberization condition is that the devitrification temperature is lower than the spinning temperature. The larger the difference (ΔT), the better the spinnability. However, the ECR glass has a devitrification temperature of 1150 ° C. or higher. And 10 corresponding to the spinning temperature.
(3) Since the temperature was around 1200 ° C., ΔT was about 50 ° C., and devitrification was likely to occur at the bushing nozzle during spinning, making production difficult.

【０００６】このようなガラスのΔＴを大きくするため
には、紡糸温度を高くすれば良いが、紡糸温度が１２５
０℃以上の高温になると、ブッシングの温度調整が困難
となり、バッチの溶融性も悪化するため、やはり生産性
が低下する。In order to increase the ΔT of such a glass, the spinning temperature may be increased.
At a high temperature of 0 ° C. or higher, it becomes difficult to adjust the temperature of the bushing, and the meltability of the batch deteriorates, so that the productivity also decreases.

【０００７】本発明は、上記事情に鑑みなされたもので
あり、Ｂ2 Ｏ3 、を少量しか含まず、Ｆ2 フリーであ
り、耐酸性、耐水性にすぐれているのみならず、失透性
に優れ、高い生産性を有する耐蝕性ガラス繊維を提供す
ることを目的とするものである。The present invention has been made in view of the above circumstances, and contains only a small amount of B 2 O 3 , is F 2 free, is excellent in acid resistance and water resistance, and is devitrified. It is an object of the present invention to provide a corrosion-resistant glass fiber having excellent productivity and high productivity.

【０００８】[0008]

【課題を解決するための手段】本発明の耐蝕性ガラス繊
維は、モル％で、ＳｉＯ2 ５６〜６３％、ＴｉＯ
2０．５〜４．５％、ＭｇＯ ０〜５％、ＴｉＯ2 ＋Ｍ
ｇＯ １〜９％、Ａｌ2 Ｏ3 ４．５〜９％、ＣａＯ
１６〜２６％、ΣＲＯ＝ＺｎＯ＋ＳｒＯ＋ＢａＯ０〜７
％、Ｎａ2 Ｏ ０〜１．５％、Ｋ2 Ｏ ０〜１．５％、
Ｌｉ2 Ｏ ０〜１．５％ Ｎａ2 Ｏ＋Ｋ2 Ｏ＋Ｌｉ2 Ｏ
≦３％、Ｂ2 Ｏ3 ０．５〜３％を含有し、Ｆ2 を含ま
ないことを特徴とする。According to the present invention, the corrosion-resistant glass fiber of the present invention is composed of, in terms of mol%, 56 to 63% of SiO 2 and TiO.
2 0.5-4.5%, MgO 0-5%, TiO 2 + M
gO 1-9%, Al 2 O 3 4.5-9%, CaO
16-26%, ΣRO = ZnO + SrO + BaO0-7
%, Na 2 O 0~1.5%, K 2 O 0~1.5%,
Li 2 O 0-1.5% Na 2 O + K 2 O + Li 2 O
≦ 3%, containing 0.5 to 3% of B 2 O 3 and not containing F 2 .

【０００９】また本発明の耐蝕性ガラス繊維は、好まし
くはモル％で、ＳｉＯ2 ５７〜６２％、ＴｉＯ2 ０．
５〜４％、ＭｇＯ ０〜４％、ＴｉＯ2 ＋ＭｇＯ １〜
８％Ａｌ2 Ｏ3 ５〜８％、ＣａＯ １７〜２５％、Σ
ＲＯ＝ＺｎＯ＋ＳｒＯ＋ＢａＯ ０〜６％、Ｎａ2 Ｏ
０〜１％、Ｋ2 Ｏ ０〜１％、Ｌｉ2 Ｏ ０〜１％、Ｎ
ａ2 Ｏ＋Ｋ2 Ｏ＋Ｌｉ2 Ｏ≦１．５％、Ｂ2 Ｏ3 ０．
５〜２．５％を含有し、Ｆ2 を含まないことを特徴とす
る。Further, the corrosion-resistant glass fiber of the present invention is preferably composed of 57 to 62% of SiO 2 and 0.1% of TiO 2 in mol%.
5-4%, MgO 0-4%, TiO 2 + MgO 1
8% Al 2 O 3 5~8% , CaO 17~25%, Σ
RO = ZnO + SrO + BaO 0-6%, Na 2 O
0~1%, K 2 O 0~1% , Li 2 O 0~1%, N
a 2 O + K 2 O + Li 2 O ≦ 1.5%, B 2 O 30 .
Containing 5 to 2.5%, characterized in that it contains no F 2.

【００１０】[0010]

【作用】本発明の耐蝕性ガラス繊維は、Ｂ2 Ｏ3 を少量
しか含まず、酸に強いＳｉＯ2、ＴｉＯ2 をそれぞれ５
６〜６３％、０．５〜４．５％含有し、しかもアルカリ
金属酸化物含有量を３％以下に抑えているため、優れた
耐蝕性を有している。また、Ｂ2 Ｏ3 を少量しか含ま
ず、Ｆ2 を含まないため、製造時に周囲環境を汚染する
ことがない。さらにＴｉＯ2 ＋ＭｇＯを１〜９％含むた
め、これらがＢ2 Ｏ3 やＦ2 に代わってフラックスとな
り、バッチ溶融性を良好に維持する。The corrosion-resistant glass fiber of the present invention contains only a small amount of B 2 O 3 and contains acid-resistant SiO 2 and TiO 2 of 5% each.
Since it contains 6 to 63% and 0.5 to 4.5%, and the content of alkali metal oxide is suppressed to 3% or less, it has excellent corrosion resistance. Further, since it contains only a small amount of B 2 O 3 and does not contain F 2 , it does not pollute the surrounding environment during manufacturing. Further, since TiO 2 + MgO is contained in an amount of 1 to 9%, these become fluxes instead of B 2 O 3 and F 2 , and maintain good batch meltability.

【００１１】本発明の耐蝕性ガラス繊維では、ＣａＯが
２６％以下、ＴｉＯ2 ０．５〜４．５％、ＭｇＯ ０
〜４．５％であり、かつＢ2 Ｏ3 を０．５〜３％含むた
め、メインの失透相であるディオプサイド Ｃａ（Ｍ
ｇ，Ｔｉ）Ｓｉ2 Ｏ6 の晶出を抑制し、失透温度は１１
３０℃以下にできることを見いだした。また紡糸温度も
１１９５℃〜１２３０℃となるため、その差ΔＴ＞９０
℃となり紡糸性は向上する。In the corrosion-resistant glass fiber of the present invention, the content of CaO is 26% or less, the content of TiO 2 is 0.5 to 4.5%, and the content of MgO 0
Was to 4.5%, and because it contains B 2 O 3 0.5 to 3%, diopside Ca (M is a main ShitsuTorusho
g, Ti) The crystallization of Si 2 O 6 is suppressed, and the devitrification temperature is 11
It has been found that the temperature can be reduced to 30 ° C. or less. Further, since the spinning temperature is 1195 ° C to 1230 ° C, the difference ΔT> 90
° C and spinnability improves.

【００１２】次に本発明の耐蝕性ガラス繊維の構成成分
を上記のように限定した理由を説明する。Next, the reason why the constituent components of the corrosion-resistant glass fiber of the present invention are limited as described above will be described.

【００１３】ＳｉＯ2 はガラスの耐酸性を向上させる成
分であり、その含有量は５６〜６３モル％、好ましくは
５７〜６２モル％である。５６モル％より少ない場合
は、上記の作用が得られず、６３モル％より多い場合
は、高温粘度が上昇し、ガラスの溶融性や紡糸性が悪化
する。[0013] SiO 2 is a component for improving the acid resistance of glass, and its content is 56 to 63 mol%, preferably 57 to 62 mol%. When the amount is less than 56 mol%, the above effects cannot be obtained, and when the amount is more than 63 mol%, the high temperature viscosity increases, and the meltability and spinnability of the glass deteriorate.

【００１４】ＴｉＯ2 は、紡糸温度である粘度１０3 ポ
イズに相当する温度を低下させて、ブッシングの劣化を
抑える成分である。またＢ2 Ｏ3 、Ｆ2 に代わるフラッ
クスとしてバッチの溶融性を向上させると共に耐酸性を
向上させる成分であり、その含有量は、０．５〜４．５
モル％、好ましくは０．５〜４モル％である。０．５モ
ル％より少ない場合は、耐酸性が悪くなり、４．５モル
％より多い場合は、ガラスが失透しやすくなる。[0014] TiO 2 is to lower the temperature corresponding to a viscosity of 10 3 poise is spinning temperature, is a component to suppress the deterioration of the bushing. Further, it is a component that improves the meltability of the batch and improves the acid resistance as a flux instead of B 2 O 3 and F 2 , and its content is 0.5 to 4.5.
Mol%, preferably 0.5 to 4 mol%. When the amount is less than 0.5 mol%, the acid resistance is deteriorated, and when the amount is more than 4.5 mol%, the glass tends to be devitrified.

【００１５】ＭｇＯは、紡糸温度を低下させて、ブッシ
ングの劣化を抑えると共にＢ2 Ｏ3やＦ2 に代わるフラ
ックスとしてバッチの溶融性を向上させる成分であり、
その含有量は、０〜４．５モル％、好ましくは０〜４モ
ル％である。４．５モル％より多い場合は、ガラスが失
透しやすくなる。MgO is a component that lowers the spinning temperature, suppresses the deterioration of the bushing, and improves the meltability of the batch as a flux replacing B 2 O 3 and F 2 .
Its content is 0-4.5 mol%, preferably 0-4 mol%. If the content is more than 4.5 mol%, the glass tends to be devitrified.

【００１６】但し本発明では、ガラスバッチの溶融性
や、ガラス粘度を考慮して、ＴｉＯ2とＭｇＯを合量で
１〜９モル％、好ましくは１〜８モル％とする。この含
量が、１モル％より少ない場合は、バッチ溶融性が悪化
し、高温粘度が上昇する。一方、９モル％より多い場合
は、ガラスが失透しやすくなる。However, in the present invention, the total amount of TiO 2 and MgO is set to 1 to 9 mol%, preferably 1 to 8 mol% in consideration of the meltability of the glass batch and the glass viscosity. If this content is less than 1 mol%, the batch meltability deteriorates and the high temperature viscosity increases. On the other hand, when it is more than 9 mol%, the glass is apt to be devitrified.

【００１７】Ａｌ2 Ｏ3 は、ガラスの耐水性や失透性を
向上させると共に溶融性を向上させる成分であり、その
含有量は４．５〜９モル％、好ましくは５〜８モル％で
ある。４．５モル％より少ない場合は、上記の作用が得
られず、９モル％より多い場合は、耐酸性が悪くなる。Al 2 O 3 is a component that improves the water resistance and devitrification of the glass and also improves the melting property. Its content is 4.5 to 9 mol%, preferably 5 to 8 mol%. is there. When the amount is less than 4.5 mol%, the above effects cannot be obtained, and when the amount is more than 9 mol%, the acid resistance deteriorates.

【００１８】ＣａＯはガラスの耐水性、失透性を向上さ
せると共にガラスの粘度を低下させて溶融性を向上させ
る成分であり、その含有量は１６〜２６モル％、好まし
くは１７〜２５モル％である。１６モルより少ない場合
や、２６モル％より多い場合は、ガラスが失透しやすく
なる。CaO is a component which improves the water resistance and devitrification of the glass and lowers the viscosity of the glass to improve the melting property, and its content is 16 to 26 mol%, preferably 17 to 25 mol%. It is. If the amount is less than 16 mol or more than 26 mol%, the glass tends to be devitrified.

【００１９】ＺｎＯ、ＳｒＯ、ＢａＯは失透性を改善す
る成分であり、その含有量は合計でΣＲＯ＝０〜７モル
％、好ましくは０〜６モル％である。７モル％を越える
とバッチの溶融性が悪化する。ZnO, SrO and BaO are components for improving the devitrification, and the total content thereof is ΣRO = 0 to 7 mol%, preferably 0 to 6 mol%. If it exceeds 7 mol%, the meltability of the batch deteriorates.

【００２０】Ｌｉ2 Ｏ、Ｎａ2 Ｏ、Ｋ2 Ｏといったアリ
カリ金属酸化物は、ガラスの粘度を低下させると共に、
フラックス剤としてバッチの溶融性を向上させる成分で
あり、Ｌｉ2 Ｏは、０〜１．５モル％、Ｎａ2 Ｏは、０
〜１．５モル％、Ｋ2 Ｏは、０〜１．５モル％、Ｌｉ2
Ｏ＋Ｎａ2 Ｏ＋Ｋ2 Ｏ≦３モル％であり、好ましくはＬ
ｉ2 Ｏは、０〜１モル％、Ｎａ2 Ｏは、０〜１モル％、
Ｋ2 Ｏは、０〜１モル％、Ｌｉ2 Ｏ＋Ｎａ2 Ｏ＋Ｋ2 Ｏ
≦１．５モル％である。これらの合量が、３モル％を越
えると、ガラスの耐水性が悪くなり、ＦＲＰ使用時に強
度が大幅に低下する。Alkali metal oxides such as Li 2 O, Na 2 O and K 2 O reduce the viscosity of glass and
It is a component that improves the meltability of the batch as a fluxing agent. Li 2 O is 0 to 1.5 mol%, and Na 2 O is 0
To 1.5 mol%, K 2 O is 0 to 1.5 mol%, Li 2
O + Na 2 O + K 2 O ≦ 3 mol%, preferably L
i 2 O is 0 to 1 mol%, Na 2 O is 0 to 1 mol%,
K 2 O is 0 to 1 mol%, Li 2 O + Na 2 O + K 2 O
≤ 1.5 mol%. If the total amount exceeds 3 mol%, the water resistance of the glass deteriorates, and the strength is greatly reduced when FRP is used.

【００２１】Ｂ2 Ｏ3 はガラスの溶融性を向上させるフ
ラックスとしての役割を果たすと共に、失透性を大幅に
改善する役割を有する。その含有量は０．５〜３モル
％、好ましくは０．５〜２．５モル％である。０．５モ
ル％より少ない場合は、上記の作用が得られず、３モル
％を越えると、耐酸性が悪化すると共に、高温溶融時の
揮発が増大し、製造時に周辺環境を害する。B 2 O 3 plays a role as a flux for improving the melting property of the glass, and also has a role for greatly improving the devitrification. Its content is 0.5-3 mol%, preferably 0.5-2.5 mol%. When the amount is less than 0.5 mol%, the above-mentioned effects cannot be obtained. When the amount exceeds 3 mol%, the acid resistance is deteriorated, and the volatilization at the time of high-temperature melting is increased, thereby harming the surrounding environment during production.

【００２２】表１にＢ2 Ｏ3 導入による液相温度に対す
る効果を示す。ＣａＯ置換、Ｂ2 Ｏ3 ２％導入によ
り、液相温度は１１５０℃から１０９０℃へと大幅に低
下する。Table 1 shows the effect of the introduction of B 2 O 3 on the liquidus temperature. The liquidus temperature is greatly reduced from 1150 ° C. to 1090 ° C. by the CaO substitution and the introduction of 2% of B 2 O 3 .

【００２３】[0023]

【表１】 [Table 1]

【００２４】本発明においては、上記成分以外にも１０
モル％以下の範囲内で、ＭｎＯ、ＭｎＯ2 、ＦｅＯ、Ｆ
ｅ2 Ｏ3 、Ｐ2 Ｏ5 等の成分を添加しても良い。しかし
ながらこれらの添加成分の合計が、１０モル％を越える
と、紡糸性が悪くなるため好ましくない。さらにＦ2
は、製造工程において環境を汚染するため含有しないこ
とが望ましい。In the present invention, in addition to the above components, 10
MnO, MnO 2 , FeO, F
Components such as e 2 O 3 and P 2 O 5 may be added. However, if the total amount of these additional components exceeds 10 mol%, spinnability deteriorates, which is not preferable. Further F 2
Is not contained because it pollutes the environment in the manufacturing process.

【００２５】[0025]

【実施例】以下、本発明の耐蝕性ガラス繊維を実施例に
基づいて詳細に説明する。EXAMPLES Hereinafter, the corrosion-resistant glass fiber of the present invention will be described in detail with reference to examples.

【００２６】表２、３は、本発明の実施例（試料Ｎｏ．
１〜１１）及び比較例（試料Ｎｏ．１２〜１４）の各試
料のガラス組成と特性を示すものである。Tables 2 and 3 show Examples of the present invention (Sample Nos.
1 shows the glass composition and characteristics of each sample of Comparative Examples (Sample Nos. 12 to 14).

【００２７】[0027]

【表２】 [Table 2]

【００２８】[0028]

【表３】 [Table 3]

【００２９】表１〜３に示した各試料は、次のようにし
て調製した。Each sample shown in Tables 1 to 3 was prepared as follows.

【００３０】先ず各表に示す組成となるようにガラス原
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、融液をグラファイト板状に流しだし、厚
さ５ｍｍの板状に変形して、以下の測定に供するガラス
試料を得た。First, a glass raw material was prepared so as to have the composition shown in each table, and was melted at 1500 ° C. for 4 hours using a platinum crucible. After melting, the melt was poured into a graphite plate and deformed into a plate having a thickness of 5 mm to obtain a glass sample to be used for the following measurement.

【００３１】耐酸性は、板状ガラス試料を粉砕し、直径
２９７〜５００μｍの粒度のガラスを比重グラム精秤
し、これを１０％ＨＣｌ溶液１００ｍｌ中に浸漬し、８
０℃、９６時間の条件で震盪した後、その重量減少率を
測定した。この重量減少率が小さい程、耐酸性が良いこ
とを示している。For acid resistance, a sheet glass sample was pulverized, glass having a particle size of 297 to 500 μm in diameter was precisely weighed in gram specific gravity, and immersed in 100 ml of 10% HCl solution.
After shaking at 0 ° C. for 96 hours, the weight loss rate was measured. The smaller the weight loss rate, the better the acid resistance.

【００３２】耐水性は、ＪＩＳ Ｒ３５０２の方法に基
づいてアルカリ溶出量（ｍｇ）を測定することによって
判定した。アルカリ溶出量が少ない程、耐水性がよいこ
とを示している。The water resistance was determined by measuring the alkali elution amount (mg) based on the method of JIS R3502. The smaller the alkali elution amount, the better the water resistance.

【００３３】粘度１０3 ポイズに相当する温度は、通常
の白金球引き上げ法によって測定したものであり、また
失透温度は、ガラス試料の一部を直径２９７〜５００μ
ｍの粉末にしてから、白金ボートにいれ、温度勾配を有
する電気炉内に１６時間保持した後、放冷し、顕微鏡で
失透出現位置を観察することによって測定したものであ
る。The temperature corresponding to a viscosity of 10 3 poise was measured by a usual platinum ball pulling-up method, and the devitrification temperature was determined by measuring a part of a glass sample with a diameter of 297 to 500 μm.
The powder was placed in a platinum boat, kept in an electric furnace having a temperature gradient for 16 hours, allowed to cool, and measured by observing a devitrification appearance position with a microscope.

【００３４】表２、３から明らかなように実施例である
Ｎｏ．１〜１１の各試料は、いずれも耐酸性試験による
重量減少率が１．２％以下であり、アルカリ溶出量は、
０．００６ｍｇ以下であり、良好な値を示した。また粘
度１０3 ポイズに相当する温度も１２３０℃以下であ
り、ΔＴが１００℃以上であるため、ブッシングの温度
コントロール、繊維化が容易であることが理解できた。As is clear from Tables 2 and 3, the No. 1 of the embodiment was used. Each of the samples 1 to 11 had a weight loss rate of 1.2% or less in the acid resistance test, and the alkali elution amount was
It was 0.006 mg or less, showing a good value. Further, the temperature corresponding to a viscosity of 10 3 poise was 1230 ° C. or less, and ΔT was 100 ° C. or more, so that it was understood that the bushing temperature control and fiberization were easy.

【００３５】それに対し、比較例であるＮｏ．１２の試
料は、耐酸性試験による重量減少率が４０％と非常に多
かった。またＮｏ．１３の試料は、ΔＴが６０℃であ
り、失透し易く紡糸が困難であり、Ｎｏ．１４の試料
は、粘度１０3 ポイズに相当する温度が１２５０℃であ
るため、ブッシングの温度コントロールが困難であると
考えられる。On the other hand, the comparative example No. Twelve samples had a very large weight loss rate of 40% in the acid resistance test. No. Sample No. 13 had a ΔT of 60 ° C., was easily devitrified, and was difficult to spin. Since the temperature of the sample No. 14 corresponding to the viscosity of 10 3 poise is 1250 ° C., it is considered that the temperature control of the bushing is difficult.

【００３６】[0036]

【発明の効果】以上のように本発明の耐蝕性ガラス繊維
は優れた生産性、紡糸性を有し、しかも耐酸性、耐水性
に優れているため、耐蝕ＦＲＰやプリント基板用樹脂等
の複合材料の補強材として、またバッテッリーセパレー
タ等の耐蝕性材料として有用である。As described above, the corrosion-resistant glass fiber of the present invention has excellent productivity and spinnability, and is excellent in acid resistance and water resistance. It is useful as a reinforcing material for the material and as a corrosion-resistant material such as a battery separator.

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】モル％で、ＳｉＯ2 ５６〜６３％、Ｔｉ
Ｏ2 ０．５〜４．５％、ＭｇＯ ０〜５％、ＴｉＯ2
＋ＭｇＯ １〜９％、Ａｌ2 Ｏ3 ４．５〜９％、Ｃａ
Ｏ １６〜２６％、ΣＲＯ＝ＺｎＯ＋ＳｒＯ＋ＢａＯ
０〜７％、Ｎａ2 Ｏ ０〜１．５％、Ｋ2 Ｏ ０〜１．
５％、Ｌｉ2 Ｏ ０〜１．５％、Ｎａ2 Ｏ＋Ｋ2 Ｏ＋Ｌ
ｉ2 Ｏ≦３％、Ｂ2 Ｏ3 ０．５〜３％を含有し、Ｆ2
を含まないことを特徴とする耐蝕性ガラス繊維。(1) In terms of mol%, SiO 2 is 56 to 63% and Ti is
O 2 0.5 to 4.5%, MgO 0 to 5%, TiO 2
+ MgO 1-9%, Al 2 O 3 4.5-9%, Ca
O 16-26%, ΣRO = ZnO + SrO + BaO
0~7%, Na 2 O 0~1.5% , K 2 O 0~1.
5%, Li 2 O 0-1.5%, Na 2 O + K 2 O + L
i 2 O ≦ 3%, B 2 O 3 0.5-3%, F 2
Corrosion resistant glass fiber characterized by not containing. 【請求項２】モル％で、ＳｉＯ2 ５７〜６２％、Ｔｉ
Ｏ2 ０．５〜４％、ＭｇＯ ０〜４％、ＴｉＯ2 ＋Ｍ
ｇＯ １〜８％、Ａｌ2 Ｏ3 ５〜８％、ＣａＯ １７
〜２５％、ΣＲＯ＝ＺｎＯ＋ＳｒＯ＋ＢａＯ ０〜６
％、Ｎａ2 Ｏ０〜１％、Ｋ2 Ｏ ０〜１％、Ｌｉ2 Ｏ
０〜１％、Ｎａ2 Ｏ＋Ｋ2 Ｏ＋Ｌｉ2Ｏ≦１．５％、Ｂ2
Ｏ3 ０．５〜２．５％を含有し、Ｆ2 を含まないこ
とを特徴とする耐蝕性ガラス繊維。2. Molar%, SiO 2 57-62%, Ti
O 2 0.5-4%, MgO 0-4%, TiO 2 + M
gO 1-8%, Al 2 O 3 5-8%, CaO 17
２５RO = ZnO + SrO + BaO 0-6
%, Na 2 O0~1%, K 2 O 0~1%, Li 2 O
0-1%, Na 2 O + K 2 O + Li 2 O ≦ 1.5%, B 2
O 3 containing 0.5 to 2.5% corrosion resistant glass fiber characterized by not containing F 2.
JP05090997A 1997-02-18 1997-02-18 Corrosion resistant glass fiber Expired - Fee Related JP3801293B2 (en)

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JP3801293B2 JP3801293B2 (en) 2006-07-26

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Publication number Priority date Publication date Assignee Title
US6818575B2 (en) 2000-09-06 2004-11-16 Ppg Industries Ohio, Inc. Glass fiber forming compositions
FR2867775A1 (en) * 2004-03-17 2005-09-23 Saint Gobain Vetrotex GLASS YARNS FOR REINFORCING ORGANIC AND / OR INORGANIC MATERIALS
US6962886B2 (en) * 1999-05-28 2005-11-08 Ppg Industries Ohio, Inc. Glass Fiber forming compositions
WO2009154062A1 (en) * 2008-06-18 2009-12-23 日本板硝子株式会社 Scale‑like glass and covered scale‑like glass
WO2023276619A1 (en) * 2021-06-29 2023-01-05 日東紡績株式会社 Glass composition for glass fibers, glass fiber, and glass fiber-reinforced resin molded article

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6962886B2 (en) * 1999-05-28 2005-11-08 Ppg Industries Ohio, Inc. Glass Fiber forming compositions
US7144836B2 (en) 1999-05-28 2006-12-05 Ppg Industries Ohio, Inc. Glass fiber forming compositions
US7153799B2 (en) 1999-05-28 2006-12-26 Ppg Industries Ohio, Inc. Glass fiber forming compositions
US6818575B2 (en) 2000-09-06 2004-11-16 Ppg Industries Ohio, Inc. Glass fiber forming compositions
FR2867775A1 (en) * 2004-03-17 2005-09-23 Saint Gobain Vetrotex GLASS YARNS FOR REINFORCING ORGANIC AND / OR INORGANIC MATERIALS
WO2005092808A1 (en) * 2004-03-17 2005-10-06 Saint-Gobain Vetrotex France S.A. Glass yarn for reinforcing organic and/ or inorganic materials
JP2007529402A (en) * 2004-03-17 2007-10-25 サン−ゴバン ベトロテックス フランス ソシエテ アノニム Glass strand capable of strengthening organic and / or inorganic materials
US7781355B2 (en) 2004-03-17 2010-08-24 Saint-Gobain Technical Fabrics Europe Glass yarn for reinforcing organic and/or inorganic materials
EP1753700B1 (en) 2004-03-17 2017-08-09 OCV Intellectual Capital, LLC Glass yarn for reinforcing organic and/ or inorganic materials
WO2009154062A1 (en) * 2008-06-18 2009-12-23 日本板硝子株式会社 Scale‑like glass and covered scale‑like glass
WO2023276619A1 (en) * 2021-06-29 2023-01-05 日東紡績株式会社 Glass composition for glass fibers, glass fiber, and glass fiber-reinforced resin molded article

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