JP3771073B2 - Glass fiber - Google Patents
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- JP3771073B2 JP3771073B2 JP05608999A JP5608999A JP3771073B2 JP 3771073 B2 JP3771073 B2 JP 3771073B2 JP 05608999 A JP05608999 A JP 05608999A JP 5608999 A JP5608999 A JP 5608999A JP 3771073 B2 JP3771073 B2 JP 3771073B2
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- 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
Description
【０００１】
【発明の属する技術分野】
この発明は、実質的にZnO、B2O3、F2といった揮発成分を含まず、化学的な耐久性に優れたガラス繊維、特にＦＲＰ、プリント配線基盤用樹脂等の複合材料の補強材として好適なガラス繊維に関する。
【０００２】
【従来の技術】
ガラス繊維を生産するためには、所定の割合に調合されたガラス原料を高温下で熔融し、均質なガラスとした後、多数のノズルを底部にもったブッシングにその熔融物を供給し、そのノズル先端よりガラスを連続的に引き出す方法が用いられている。
【０００３】
繊維化する場合、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失透物が生成し、ブッシングのノズル付近で糸切れが起こりやすくなるので生産性を悪化させる。このためガラスの失透温度は紡糸温度よりも低いことが繊維化の条件になる。
【０００４】
また生産性を向上させるために、紡糸温度と失透温度との差（△Ｔ）をより大きくすることが求められるが、ガラスの紡糸温度をあげることは、ブッシングの温度調節を難しくするとともに、ブッシングの寿命が短くなるので好ましくない。さらに原料を高温で熔解しなければならないので、それに要するエネルギー消費量も増加する。したがって、紡糸温度は少しでも低い方が望まれる。
【０００５】
産業上最も使用されているＥガラス繊維は、その組成物中に紡糸温度や失透温度を下げる役割をする成分としてB2O3、F2が用いられている。しかしながら、B2O3は原料が高価であること、またB2O3、F2は熔融行程で揮発しやすいので、周囲の環境汚染を招くことが問題として示唆されるようになり、B2O3、F2を含まない新しいガラス繊維が求められている。
【０００６】
このようなB2O3、F2を含有しないガラス繊維としては、米国特許第３，８４７，６２７号、同３，８７６，４８１号、同４，０２６，７１５号および同５，７８９，３２９号の各公報に開示されている。
【０００７】
ここで米国特許第３，８４７，６２７号および同４，０２６，７１５号公報に記載されているガラス繊維の組成は、B2O3、F2を含まないが、それに変わる融剤として二酸化チタン(TiO2)およびROとして酸化ストロンチウム(SrO)、BaO、ZnOが使用されている。また米国特許第３，８７６，４８１号公報に記載されているガラス繊維は、B2O3、F2に代わる融剤として一酸化リチウム(Li2O)、TiO2を含有している。
【０００８】
しかしながら、上記TiO2、Li2O、ZnOは積極的に導入するには原料が高価である。また、ZnOは熔融時に揮発し、窯の寿命を低下させる問題がある。さらに、TiO2はガラスを着色させるので、補強材として使用した場合外観が損なわれる場合がある。
【０００９】
米国特許第５，７８９，３２９号公報に記載されているガラス組成は、ZnO、B2O3、F2といった揮発成分を含まず、また耐酸性、耐水性といった化学的耐久性にも優れているが、実施例記載の紡糸温度に相当する１，０００ポイズ［Ｐ］の温度はどれも１，２４８℃以上の高温にあるため、生産性とブッシング寿命の低下が懸念される。
【００１０】
【発明が解決しようとする課題】
本発明は上記の背景を踏まえたものであり、揮発成分であるZnO、B2O3、F2を含まないことで環境汚染を防止し、化学的耐久性に優れ、高い生産性を有するガラス繊維を提供することを目的とする。
【００１１】
【課題を解決するための手段】
上記目的を達成するために、請求項１に記載の発明のガラス繊維は、モルパーセント（以下、単に「％」と表記する）で、SiO2：５６〜６３％、Al2O3：４〜９％、ZrO2：０．１〜３％、ただしSiO2+ZrO2-Al2O3≧５２％、MgO：１〜７％、CaO：２１〜２８％、Na2O：０〜１．５％、K2O：０〜１．５％、ただしNa2O+K2O≦１．５％を含有し、不純物として、TiO2、SrO、Fe2O3、ZnO、B2O3、F2を合計で０．３％以下の範囲で含有するものである。
【００１２】
請求項２に記載の発明のガラス繊維は、請求項１の発明の構成に加えて、紡糸温度が１，２４５℃以下で、かつ紡糸温度と失透温度の差が４０℃以上あるものである。
【００１３】
請求項３に記載の発明のガラス繊維は、モルパーセントで、SiO2：５８〜６１％、Al2O3：６〜７％、ZrO2：０．１〜２％、ただしSiO2+ZrO2-Al2O3≧５３％、MgO：３〜６％、CaO：２３〜２７％、Na2O：０〜１％、K2O：０〜１％、ただしNa2O+K2O≦１％を含有し、不純物として、TiO2、SrO、Fe2O3、ZnO、B2O3、F2を合計で０．３％以下の範囲で含有し、紡糸温度が１，２３５℃以下で、かつ紡糸温度と失透温度との差が５０℃以上あるものである。
【００１４】
【発明の実施の形態】
次に、この発明の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。SiO2は、ガラスの耐酸性を向上させる成分であり、５６％未満では上記作用が得られず、一方６３％より多い場合はガラスの高温での粘性が上がるため、紡糸温度が上昇し、またバッチの熔解性が悪化する。このため含有量は５６〜６３％であり、５８〜６１％が望ましい。
【００１５】
Al2O3は、ガラスの耐水性を改善し、また適量含有させることで失透性を改善させる成分である。４％未満の場合は、十分な作用が得られず、９％より多い場合は耐酸性、熔解性が悪化する。このため含有量は、４〜９％であり、６〜７％が望ましい。
【００１６】
ZrO2は、ガラスの化学的な耐久性を向上させ、ガラスの屈折率を増加させ、少量で紡糸温度、失透温度を低下させるのに特に効果を与える成分である。０．１％未満では、上記作用が得られず、一方３％より多い場合はガラスが失透しやすくなったり、熔解性が悪化する。そのため含有量は、０．１〜３％であり、好ましくは０．１〜２％である。
【００１７】
ここでSiO2、ZrO2、Al2O3は、ガラスの特性、特に酸に対する耐久性に影響を与える成分である。SiO2とZrO2は、耐酸性を向上させる成分であり、Al2O3は耐酸性を悪化させる成分であり、特にSiO2+ZrO2-Al2O3の値が５２％以上の場合に耐酸性が良好であることを見い出した。このため、SiO2+ZrO2-Al2O3≧５２％であり、好ましくはSiO2+ZrO2-Al2O3≧５３％以上である。
【００１８】
MgOは、高温粘性を下げる作用を発揮し、かつ紡糸性とバッチ熔解性を向上させる成分であり、１％未満では上記作用が得られない。一方、７％より多い場合はガラスが失透しやすくなり、生産性が低下する。このため含有量は、１〜７％であり、３〜６％が好ましく、５〜６％が望ましい。
【００１９】
CaOは、ガラスの耐水性や失透性を向上させるとともに、ガラスの粘度を低下させ、熔解性と紡糸性を向上させる成分である。２１％未満の場合、上記作用が得られない。２８％より多くなる場合はガラスが失透しやすくなるため、その含有量は２１〜２８％であり、２３〜２７％が望ましい。
【００２０】
Na2O、K2Oといったアルカリ金属酸化物は、ガラスの融剤であり、熔解性を向上させると共に、少量でも失透温度を低下させる効果を発揮する。しかし、これらのアルカリ金属酸化物の合計量が１．５％を超えると、化学的耐久性が悪化するので好ましくない。このため含有量は、Na2O：０〜１．５％、K2O：０〜１．５％、かつNa2O+K2O≦１．５％であり、好ましくはNa2O：０〜１％、K2O：０〜１％、かつNa2O+K2O≦１％である。
【００２１】
この発明においては、上記成分以外に、SrO、酸化マンガン(MnO)、酸化鉄II(FeO)、酸化鉄III(Fe2O3)、TiO2、B2O3、F2などが原料の不純物として、合計で０．５％以下の範囲で混入することがある。
【００２２】
またガラス清澄剤として三酸化硫黄(SO3)、酸化アンチモン(Sb2O3)を少量含むことがある。しかしながら清澄剤を除く他の成分は、ガラスを着色したり、また直接導入するには原料が高価であることから、安価なガラス繊維を提案することに対して好ましくない。さらにZnO、B2O3、F2は製造工程において揮発し、環境を汚染するので好ましくない。なお、この発明において、ZnO、B2O3、F2を実質的に含まないとは、不純物として含むことはあっても、意図的に含有させることはないという趣旨である。
【００２３】
【実施例】
以下、本発明のガラス繊維を実施例に基づいて詳細に説明する。
【００２４】
【表１】
【表２】
「表１」および「表２」に示した組成を有するガラスを調製し、紡糸温度、失透温度、耐水性および耐酸性を測定した。まず、「表１」および「表２」に示すガラス組成となるように、粘土、珪砂、石灰石、苦灰石、アルミナおよび酸化ジルコニウムを調合し、白金坩堝を用いて１，５００℃で６時間熔融した。熔融後、融液を金属プレート上に流し出し厚さ約５mmの板状に成形、徐冷し、特性測定用のガラスを得た。紡糸温度、すなわち１，０００Ｐに相当する温度は、通常の白金球引き上げ法により測定した。
【００２７】
また失透温度は、以下のように測定した。すなわち板状のガラスの一部を粉砕し、直径１，１９０〜１，６８０μmの粒状にしてからアルコールで洗浄した後、白金ボートに入れ、長さ方向に温度勾配のついた電気炉内に２時間保持した。電気炉から上記ボートを取り出して放冷した後、５０倍の偏光顕微鏡を用いて結晶の出現位置を直接観察し、その最高温度を失透温度とした。
【００２８】
耐酸性は、板状のガラスを粉砕し、直径４２０〜５９０μmの粒状にしてからアルコールで洗浄し、比重グラム精秤し、８０℃の１０％H2SO4溶液中に浸漬し、７２時間経過したところで重量減少率［％］を算出した。また耐酸性はこの重量減少率が小さいほど良いことを示す。
【００２９】
耐水性は、ＪＩＳ Ｒ３５０２に基づく方法でアルカリ溶出量を測定することで調べた。この量が少ないほど、耐水性の良いことを表している。
【００３０】
実施例１〜９の各試料は、いずれも耐酸性による重量減少率が０．７％以下、耐水性は０．００６mg以下、屈折率は１．５６５以上と良好な値を示した。また、紡糸温度を表す１，０００Ｐに相当する温度も１，２４５℃以下であり、ブッシングの温度制御性が容易に行える。さらに、紡糸温度と失透温度との差△Ｔが４０℃以上であるため、紡糸時に失透が生成しにくく、高い生産性を維持することができる。
【００３１】
比較例１は市販のＥガラスであり、耐酸性が悪く、環境を汚染するB2O3、F2が含まれている。また比較例２は米国特許第３，８４７，６２７号公報記載の実施例（Ｎｏ．２４）で、ZrO2が入っているものの、ZnO、TiO2を含み、かつ紡糸温度は低いが、失透温度が高いので、生産性を示唆する△Ｔが小さくなり、安定した生産は難しい。比較例３は、米国特許第５，７８９，３２９号公報記載の紡糸温度が最も低い実施例（Ｎｏ．５）であるが、紡糸温度は１，２４８℃と高く、ブッシングの温度制御性や寿命に問題がある。
【００３２】
以上のようにこの発明のガラス繊維は、優れた生産性、紡糸性を有し、化学的耐久性に優れ、ＦＲＰやプリント配線基盤等の補強材料として有用である。
【００３３】
【発明の効果】
請求項１では、不純物として、TiO2、SrO、Fe2O3、ZnO、B2O3、F2を合計で０．３％以下の範囲とし、SiO2、Al2O3、ZrO2、MgO、CaO、Na2O、K2Oの含有量を限定すると共に、SiO2+ZrO2-Al2O3およびアルカリ金属酸化物の合計量を限定することで、化学的な耐久性に優れたガラス繊維が得られる。
【００３４】
請求項２では、請求項１に記載される範囲内でも特に紡糸温度と△Ｔ（紡糸温度−失透温度）を限定することで、より紡糸性、生産性に優れたガラス繊維が得られる。
【００３５】
請求項３では、不純物として、TiO2、SrO、Fe2O3、ZnO、B2O3、F2を合計で０．３％以下の範囲とし、特にSiO2、Al2O3、MgOの組成範囲を限定することで、紡糸温度と△Ｔに優れ、さらに耐酸性、耐水性も良好なガラス繊維が得られる。[0001]
BACKGROUND OF THE INVENTION
This invention is substantially free of volatile components such as ZnO, B 2 O 3 , and F 2 , and is used as a reinforcing material for composite materials such as glass fibers having excellent chemical durability, particularly FRP and printed wiring board resins. It relates to a suitable glass fiber.
[0002]
[Prior art]
In order to produce glass fibers, glass raw materials prepared at a predetermined ratio are melted at a high temperature to form homogeneous glass, and then the melt is supplied to a bushing having a number of nozzles at the bottom. A method of continuously pulling out glass from the nozzle tip is used.
[0003]
When fiberizing, the devitrification temperature of the glass exceeds the spinning temperature, which is the temperature at which the glass is fiberized, and devitrified material is generated, and yarn breakage is likely to occur near the bushing nozzle, thus reducing productivity. Let For this reason, the devitrification temperature of the glass is lower than the spinning temperature as a condition for fiberization.
[0004]
Moreover, in order to improve productivity, it is required to increase the difference between the spinning temperature and the devitrification temperature (ΔT), but increasing the spinning temperature of the glass makes it difficult to adjust the temperature of the bushing, This is not preferable because the life of the bushing is shortened. Furthermore, since the raw material must be melted at a high temperature, the energy consumption required for it is also increased. Therefore, it is desirable that the spinning temperature is as low as possible.
[0005]
The E glass fiber most used in the industry uses B 2 O 3 and F 2 as components that lower the spinning temperature and devitrification temperature in the composition. However, B 2 O 3 is that the raw material is expensive, since the B 2 O 3, F 2 is easy to volatilize melting process, now can cause the surrounding environment pollution are suggested as problems, B 2 There is a need for new glass fibers that do not contain O 3 and F 2 .
[0006]
Examples of such glass fibers not containing B 2 O 3 and F 2 include US Pat. Nos. 3,847,627, 3,876,481, 4,026,715, and 5,789,329. It is disclosed in each publication.
[0007]
Here, the composition of the glass fiber described in US Pat. Nos. 3,847,627 and 4,026,715 does not contain B 2 O 3 and F 2 , but titanium dioxide is used as a flux instead of it. Strontium oxide (SrO), BaO, and ZnO are used as (TiO 2 ) and RO. Further, the glass fiber described in US Pat. No. 3,876,481 contains lithium monoxide (Li 2 O) and TiO 2 as fluxes in place of B 2 O 3 and F 2 .
[0008]
However, the raw materials of TiO 2 , Li 2 O, and ZnO are expensive to actively introduce. In addition, ZnO volatilizes during melting and has a problem of reducing the life of the kiln. Furthermore, since TiO 2 colors the glass, the appearance may be impaired when used as a reinforcing material.
[0009]
The glass composition described in US Pat. No. 5,789,329 does not contain volatile components such as ZnO, B 2 O 3 and F 2 , and is excellent in chemical durability such as acid resistance and water resistance. However, since the temperature of 1,000 poise [P] corresponding to the spinning temperature described in the examples is all at a high temperature of 1,248 ° C. or more, there is a concern that the productivity and the bushing life are lowered.
[0010]
[Problems to be solved by the invention]
The present invention is based on the background described above, and does not contain ZnO, B 2 O 3 , and F 2 as volatile components, thereby preventing environmental pollution, excellent chemical durability, and high productivity. The object is to provide fibers.
[0011]
[Means for Solving the Problems]
In order to achieve the above object, the glass fiber of the invention according to claim 1 is SiO 2 : 56 to 63%, Al 2 O 3 : 4 to 4 in mole percent (hereinafter, simply referred to as “%”). 9%, ZrO 2 : 0.1 to 3%, but SiO 2 + ZrO 2 —Al 2 O 3 ≧ 52%, MgO: 1 to 7%, CaO: 21 to 28%, Na 2 O: 0 to 1. 5%, K 2 O: 0 to 1.5%, but containing Na 2 O + K 2 O ≦ 1.5%, and as impurities, TiO 2 , SrO, Fe 2 O 3 , ZnO, B 2 O 3 , F 2 in a total range of 0.3 % or less.
[0012]
The glass fiber of the invention according to claim 2 has a spinning temperature of 1,245 ° C. or less and a difference between the spinning temperature and the devitrification temperature of 40 ° C. or more in addition to the configuration of the invention of claim 1. .
[0013]
The glass fiber of the invention according to claim 3 is, in mole percent, SiO 2 : 58 to 61%, Al 2 O 3 : 6 to 7%, ZrO 2 : 0.1 to 2 %, provided that SiO 2 + ZrO 2 -Al 2 O 3 ≧ 53%, MgO: 3 to 6%, CaO: 23 to 27%, Na 2 O: 0 to 1%, K 2 O: 0 to 1%, provided that Na 2 O + K 2 O ≦ Containing 1%, TiO 2 , SrO, Fe 2 O 3 , ZnO, B 2 O 3 , and F 2 are contained in a total range of 0.3 % or less, and the spinning temperature is 1,235 ° C. or less In addition, the difference between the spinning temperature and the devitrification temperature is 50 ° C. or more .
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Next, the reason why the constituent components of the glass fiber of the present invention are limited as described above will be described. SiO 2 is a component that improves the acid resistance of the glass, and if it is less than 56%, the above action cannot be obtained. On the other hand, if it exceeds 63%, the viscosity of the glass at a high temperature increases, so that the spinning temperature rises. Batch meltability deteriorates. For this reason, content is 56 to 63%, and 58 to 61% is desirable.
[0015]
Al 2 O 3 is a component that improves the water resistance of glass and improves devitrification by containing an appropriate amount. When it is less than 4%, sufficient action cannot be obtained, and when it is more than 9%, acid resistance and meltability deteriorate. For this reason, content is 4 to 9%, and 6 to 7% is desirable.
[0016]
ZrO 2 is a component that is particularly effective for improving the chemical durability of glass, increasing the refractive index of glass, and lowering the spinning temperature and devitrification temperature with a small amount. If it is less than 0.1%, the above-mentioned action cannot be obtained. On the other hand, if it exceeds 3%, the glass tends to be devitrified or the meltability is deteriorated. Therefore, the content is 0.1 to 3%, preferably 0.1 to 2%.
[0017]
Here, SiO 2 , ZrO 2 , and Al 2 O 3 are components that affect the properties of the glass, particularly the durability against acid. SiO 2 and ZrO 2 are components that improve acid resistance, and Al 2 O 3 is a component that deteriorates acid resistance, especially when the value of SiO 2 + ZrO 2 -Al 2 O 3 is 52% or more. It was found that the acid resistance was good. For this reason, SiO 2 + ZrO 2 —Al 2 O 3 ≧ 52%, preferably SiO 2 + ZrO 2 —Al 2 O 3 ≧ 53%.
[0018]
MgO is a component that exerts the effect of lowering the high temperature viscosity and improves the spinnability and batch meltability, and the above effect cannot be obtained at less than 1%. On the other hand, when it is more than 7%, the glass tends to be devitrified and the productivity is lowered. For this reason, content is 1 to 7%, 3 to 6% is preferable and 5 to 6% is desirable.
[0019]
CaO is a component that improves the water resistance and devitrification of the glass, lowers the viscosity of the glass, and improves the meltability and spinnability. When it is less than 21%, the above-mentioned action cannot be obtained. If it exceeds 28%, the glass tends to devitrify, so its content is 21-28%, preferably 23-27%.
[0020]
Alkali metal oxides such as Na 2 O and K 2 O are glass fluxes, improving the meltability and exhibiting the effect of reducing the devitrification temperature even with a small amount. However, if the total amount of these alkali metal oxides exceeds 1.5%, the chemical durability deteriorates, which is not preferable. For this reason, the content is Na 2 O: 0 to 1.5%, K 2 O: 0 to 1.5%, and Na 2 O + K 2 O ≦ 1.5%, preferably Na 2 O: 0 to 1%, K 2 O: 0 to 1%, and Na 2 O + K 2 O ≦ 1%.
[0021]
In this invention, in addition to the above components, impurities such as SrO, manganese oxide (MnO), iron oxide II (FeO), iron oxide III (Fe 2 O 3 ), TiO 2 , B 2 O 3 , and F 2 are raw materials. As a result, it may be mixed within a total range of 0.5% or less.
[0022]
Moreover, it may contain a small amount of sulfur trioxide (SO 3 ) and antimony oxide (Sb 2 O 3 ) as a glass fining agent. However, the other components other than the fining agent are not preferable for proposing inexpensive glass fibers because the raw materials are expensive for coloring glass or for direct introduction. Furthermore, ZnO, B 2 O 3 and F 2 are not preferable because they volatilize in the manufacturing process and contaminate the environment. In the present invention, the fact that ZnO, B 2 O 3 , and F 2 are not substantially contained means that they are not intentionally contained even though they are contained as impurities.
[0023]
【Example】
Hereinafter, the glass fiber of this invention is demonstrated in detail based on an Example.
[0024]
[Table 1]
[Table 2]
Glasses having the compositions shown in “Table 1” and “Table 2” were prepared, and spinning temperature, devitrification temperature, water resistance and acid resistance were measured. First, clay, silica sand, limestone, dolomite, alumina and zirconium oxide were prepared so that the glass compositions shown in “Table 1” and “Table 2” were obtained, and then used at a temperature of 1,500 ° C. for 6 hours using a platinum crucible. Melted. After melting, the melt was poured onto a metal plate, formed into a plate having a thickness of about 5 mm, and slowly cooled to obtain a glass for measuring properties. The spinning temperature, that is, the temperature corresponding to 1,000 P, was measured by an ordinary platinum ball pulling method.
[0027]
The devitrification temperature was measured as follows. That is, a part of the plate-like glass is pulverized, made into granules having a diameter of 1,190 to 1,680 μm, washed with alcohol, put into a platinum boat, and placed in an electric furnace with a temperature gradient in the length direction. Held for hours. After the boat was taken out from the electric furnace and allowed to cool, the appearance position of the crystal was directly observed using a 50 × polarization microscope, and the maximum temperature was defined as the devitrification temperature.
[0028]
Acid resistance is obtained by pulverizing plate-like glass, granulating it into a particle having a diameter of 420 to 590 μm, washing with alcohol, precisely weighing a specific gravity, and immersing in a 10% H 2 SO 4 solution at 80 ° C. for 72 hours. The weight reduction rate [%] was calculated. Moreover, it shows that acid resistance is so good that this weight reduction rate is small.
[0029]
The water resistance was examined by measuring the alkali elution amount by a method based on JIS R3502. The smaller the amount, the better the water resistance.
[0030]
Each of the samples of Examples 1 to 9 showed good values such that the weight loss rate due to acid resistance was 0.7% or less, the water resistance was 0.006 mg or less, and the refractive index was 1.565 or more. Further, the temperature corresponding to 1,000 P representing the spinning temperature is 1,245 ° C. or less, and the bushing temperature controllability can be easily performed. Furthermore, since the difference ΔT between the spinning temperature and the devitrification temperature is 40 ° C. or more, devitrification is not easily generated during spinning, and high productivity can be maintained.
[0031]
Comparative Example 1 is a commercially available E glass, which has poor acid resistance and contains B 2 O 3 and F 2 that pollute the environment. Comparative Example 2 is an example (No. 24) described in US Pat. No. 3,847,627, which contains ZrO 2 but contains ZnO and TiO 2 and has a low spinning temperature. Since the temperature is high, ΔT suggesting productivity is small, and stable production is difficult. Comparative Example 3 is an example (No. 5) having the lowest spinning temperature described in US Pat. No. 5,789,329, but the spinning temperature is as high as 1,248 ° C., and the temperature controllability and life of bushing are high. There is a problem.
[0032]
As described above, the glass fiber of the present invention has excellent productivity and spinnability, is excellent in chemical durability, and is useful as a reinforcing material for FRP, printed wiring board and the like.
[0033]
【The invention's effect】
In claim 1, TiO 2 , SrO, Fe 2 O 3 , ZnO, B 2 O 3 , and F 2 are added in a total range of 0.3 % or less, and SiO 2 , Al 2 O 3 , ZrO 2 , Excellent chemical durability by limiting the content of MgO, CaO, Na 2 O, K 2 O and limiting the total amount of SiO 2 + ZrO 2 -Al 2 O 3 and alkali metal oxides Glass fiber is obtained.
[0034]
In claim 2, even within the range described in claim 1, by limiting the spinning temperature and ΔT (spinning temperature-devitrification temperature), a glass fiber with better spinnability and productivity can be obtained.
[0035]
In claim 3, as impurities, TiO 2 , SrO, Fe 2 O 3 , ZnO, B 2 O 3 , and F 2 are added in a total range of 0.3 % or less, particularly SiO 2 , Al 2 O 3 , MgO. By limiting the composition range, a glass fiber excellent in spinning temperature and ΔT, and having good acid resistance and water resistance can be obtained.
Claims (3)
二酸化ケイ素(SiO2)：５６〜６３％、
酸化アルミニウム(Al2O3)：４〜９％、
酸化ジルコニウム(ZrO2)：０．１〜３％、
ただし、SiO2+ZrO2-Al2O3≧５２％、
酸化マグネシウム(MgO)：１〜７％、
酸化カルシウム(CaO)：２１〜２８％、
一酸化ナトリウム(Na2O)：０〜１．５％、
酸化カリウム(K2O)：０〜１．５％、
ただし、Na2O+K2O≦１．５％
を含有し、不純物として、二酸化チタン(TiO2)、酸化ストロンチウム(SrO)、酸化鉄III(Fe2O3)、酸化亜鉛(ZnO)、三酸化二ホウ素(B2O3)、フッ素(F2)を合計で０．３％以下の範囲で含有するガラス繊維。In mole percent,
Silicon dioxide (SiO 2 ): 56 to 63%,
Aluminum oxide (Al 2 O 3 ): 4-9%
Zirconium oxide (ZrO 2 ): 0.1 to 3%,
However, SiO 2 + ZrO 2 —Al 2 O 3 ≧ 52%,
Magnesium oxide (MgO): 1-7%
Calcium oxide (CaO): 21-28%,
Sodium monoxide (Na 2 O): 0 to 1.5%,
Potassium oxide (K 2 O): 0 to 1.5%,
However, Na 2 O + K 2 O ≦ 1.5%
As impurities, titanium dioxide (TiO 2 ), strontium oxide (SrO), iron oxide III (Fe 2 O 3 ), zinc oxide (ZnO), diboron trioxide (B 2 O 3 ), fluorine (F 2 ) A glass fiber containing 0.3 % or less in total.
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| DE10161791A1 (en) * | 2001-12-07 | 2003-06-26 | Dbw Fiber Neuhaus Gmbh | Continuous glass fiber with improved thermal resistance |
| US7285508B2 (en) | 2003-08-29 | 2007-10-23 | Nippon Sheet Glass Company, Limited | Glass flake |
| JP2013047184A (en) * | 2005-07-05 | 2013-03-07 | Nippon Electric Glass Co Ltd | Glass fiber composition, glass fiber, and glass fiber-containing composite material |
| JP5442181B2 (en) | 2005-07-05 | 2014-03-12 | 日本電気硝子株式会社 | Glass fiber composition, glass fiber and glass fiber-containing composite material |
| TW202402702A (en) * | 2022-03-30 | 2024-01-16 | 日商日本板硝子股份有限公司 | Glass fiber |
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