JP6959563B2 - Glass composition for glass fiber, glass fiber and method for producing glass fiber - Google Patents
Glass composition for glass fiber, glass fiber and method for producing glass fiber Download PDFInfo
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- JP6959563B2 JP6959563B2 JP2016252648A JP2016252648A JP6959563B2 JP 6959563 B2 JP6959563 B2 JP 6959563B2 JP 2016252648 A JP2016252648 A JP 2016252648A JP 2016252648 A JP2016252648 A JP 2016252648A JP 6959563 B2 JP6959563 B2 JP 6959563B2
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
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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
- C03C13/001—Alkali-resistant fibres
- C03C13/002—Alkali-resistant fibres containing zirconium
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
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Description
本発明は、耐食性に優れたガラス繊維用ガラス組成物に関する。特にケイ酸カルシウム板やＧＲＣ（ガラス繊維強化コンクリート）等の補強材として、またバッテリーセパレータやアスベスト代替品等の耐食性が要求される材料として適したガラス繊維用ガラス組成物に関する。 The present invention relates to a glass composition for glass fibers having excellent corrosion resistance. In particular, the present invention relates to a glass composition for glass fiber, which is suitable as a reinforcing material such as a calcium silicate plate and GRC (glass fiber reinforced concrete), and as a material requiring corrosion resistance such as a battery separator and an asbestos substitute.
従来、ＧＲＣの補強材としては、特許文献１に記載されているようなＳｉＯ２−ＺｒＯ２−Ｒ２Ｏ（ＲはＬｉ、Ｎａ、Ｋの何れか）系のＺｒＯ２含有耐アルカリ性ガラス繊維が使用されている。 Conventionally, as a reinforcement of the GRC, SiO 2 -ZrO 2 -R 2 O , as described in Patent Document 1 (R is Li, Na, any of K) is based ZrO 2 containing alkali-resistant glass fibers in use.
このガラス繊維は、ケイ酸カルシウム板の補強材やバッテリーセパレータ等の耐食性材料としても使用されている。 This glass fiber is also used as a reinforcing material for a calcium silicate plate and a corrosion resistant material such as a battery separator.
ＧＲＣは、所定の長さに切断されたガラス繊維と、セメントと、骨材と、混和剤と、水等との混合物を型枠内にスプレーガンなどを使用して吹き付けることによって、板状に成形される建築用の構造材である。ＧＲＣに使用されるガラス繊維は、コンクリート中で何十年経過しても信頼性に足る強度を保持できることが求められる。 GRC is made into a plate by spraying a mixture of glass fiber, cement, aggregate, admixture, water, etc. cut to a predetermined length into a mold using a spray gun or the like. It is a structural material for construction that is molded. The glass fiber used for GRC is required to be able to maintain reliable strength even after decades in concrete.
前述のようなガラス繊維は、例えば、貴金属製のブッシング装置を使用して、溶融ガラスを連続的に成形、紡糸し、繊維形状にしたものである。尚、ブッシングの構造は、溶融ガラスを滞留させるために容器形状を有しており、その底部には鉛直方向に多数のノズルが配設されている。ガラス繊維は、紡糸温度（ガラスの粘度が約１０３ｄＰａ・ｓとなる温度、成形温度とも呼ばれる）付近の温度に調整された溶融ガラスをブッシング底部のノズルから繊維状に引き出すことで成形される。 The glass fiber as described above is obtained by continuously forming and spinning molten glass into a fiber shape using, for example, a bushing device made of a precious metal. The bushing structure has a container shape for retaining the molten glass, and a large number of nozzles are arranged in the vertical direction at the bottom thereof. Glass fibers are formed by pulling out the spinning temperature molten glass which is adjusted to a temperature of (the temperature at which the viscosity of the glass is about 10 3 dPa · s, the molding temperature also called) near the nozzle of the bushing bottom fibrous ..
特許文献１には、耐アルカリ性向上の観点からガラス組成中にＺｒＯ２を多量に含有させたガラス組成物が開示されている。しかし、ＺｒＯ２を多量に含有させるとガラスの紡糸温度が高くなってしまう。ガラスの紡糸温度が高いと、貴金属製のブッシング装置の損傷が激しくなり、ブッシングの交換頻度が高くなって、ガラス繊維の生産コストが高くなる。またＺｒＯ２を多量に含有させると液相温度が上昇し、紡糸温度と液相温度の差が小さくなり易い。紡糸温度と液相温度の差が小さいと、ブッシング底部のノズルにおいてガラスが失透しやすくなり、ガラス繊維の連続生産が難しいという問題がある。 Patent Document 1 discloses a glass composition containing a large amount of ZrO 2 in the glass composition from the viewpoint of improving alkali resistance. However, if a large amount of ZrO 2 is contained, the spinning temperature of the glass becomes high. When the glass spinning temperature is high, the precious metal bushing device is severely damaged, the bushing is frequently replaced, and the production cost of glass fiber is high. Further , when a large amount of ZrO 2 is contained, the liquidus temperature rises, and the difference between the spinning temperature and the liquidus temperature tends to be small. If the difference between the spinning temperature and the liquid phase temperature is small, the glass tends to be devitrified at the nozzle at the bottom of the bushing, and there is a problem that continuous production of glass fibers is difficult.
また特許文献２には、ＺｒＯ２を低減させつつ、一定量のＴｉＯ２を含有することによって耐アルカリ性を維持したガラス組成物が開示されている。しかし特許文献２に記載のガラス繊維も、ガラスの紡糸温度は高いままである。 Further, Patent Document 2 discloses a glass composition that maintains alkali resistance by containing a certain amount of TiO 2 while reducing ZrO 2. However, the glass fiber described in Patent Document 2 also has a high glass spinning temperature.
また特許文献３には、ＺｒＯ２を低減させつつ、一定量のＢ２Ｏ３を含有することによって紡糸温度を低下させたガラス組成物が開示されている。しかし特許文献３に記載のガラス繊維は、ガラスの紡糸温度と液相温度の差が小さく、連続生産が難しいという問題がある。 Further, Patent Document 3 discloses a glass composition in which the spinning temperature is lowered by containing a certain amount of B 2 O 3 while reducing ZrO 2. However, the glass fiber described in Patent Document 3 has a problem that the difference between the spinning temperature of the glass and the liquid phase temperature is small, and continuous production is difficult.
このように、優れた耐アルカリ性を有し、生産性に優れたガラス繊維用ガラス組成物を得ることは困難であった。 As described above, it has been difficult to obtain a glass composition for glass fibers having excellent alkali resistance and excellent productivity.
本発明は、上記事情に鑑みなされたものであり、優れた耐アルカリ性を有し、しかも生産性に優れたガラス繊維用ガラス組成物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 an object of the present invention is to provide a glass composition for glass fibers having excellent alkali resistance and excellent productivity.
本発明者は、鋭意検討の結果、ガラス繊維用ガラス組成物について、ＺｒＯ２を一定量以上含有させたガラス組成に、ＴｉＯ２及びＢ２Ｏ３を必須成分として含有させると、ガラスの紡糸温度を上げることなく液相温度を著しく低下させることが可能となり、ガラスの紡糸温度と液相温度の差を顕著に大きくできることを見出した。そして更に、ＺｒＯ２を一定量以上含有しているために、ＴｉＯ２及びＢ２Ｏ３を添加しても耐酸性、耐アルカリ性、耐水性に大きく影響しないことを見出した。 As a result of diligent studies, the present inventor has determined that the glass composition for glass fibers contains TiO 2 and B 2 O 3 as essential components in the glass composition containing a certain amount or more of ZrO 2 , and the glass spinning temperature. It has been found that the liquidus temperature can be remarkably lowered without raising the temperature, and the difference between the glass spinning temperature and the liquidus temperature can be remarkably increased. Furthermore, it was found that since ZrO 2 is contained in a certain amount or more, the addition of TiO 2 and B 2 O 3 does not significantly affect the acid resistance, alkali resistance, and water resistance.
すなわち、本発明のガラス繊維用ガラス組成物は、ガラス組成として、酸化物換算の質量％で、ＳｉＯ２ ５０〜６５％、Ａｌ２Ｏ３ ０〜５％、ＣａＯ ０〜１０％、Ｎａ２Ｏ １０〜２０％、Ｋ２Ｏ ０〜５％、ＺｒＯ２ １５超〜２０％、ＴｉＯ２ ０．１〜１０％、Ｂ２Ｏ３ ０．１〜１０％を含有することを特徴とする。 That is, the glass composition for glass fibers of the present invention has a glass composition of SiO 2 50 to 65%, Al 2 O 30 to 5%, Ca O 0 to 10%, and Na 2 O in terms of oxide mass%. It is characterized by containing 10 to 20%, K 2 O 0 to 5%, ZrO 2 15 to 20%, TiO 2 0.1 to 10%, and B 2 O 3 0.1 to 10%.
驚くべきことに、ＺｒＯ２を一定量以上含有させたガラス組成において、Ｂ２Ｏ３とＴｉＯ２の両方を含有させることによりＮａ、Ｚｒ、Ｓｉを含む結晶と、Ｋ、Ｚｒ、Ｓｉを含む結晶とが共晶状態になると考えられ、液相温度が著しく低下する。結果として、本発明のガラス繊維用ガラス組成物は、優れた耐アルカリ性を有しつつ、ガラスの紡糸温度と液相温度の差が大きく、生産性に優れるものとなった。 Surprisingly, in a glass composition containing a certain amount or more of ZrO 2 , crystals containing Na, Zr , and Si and crystals containing K, Zr, and Si by containing both B 2 O 3 and TiO 2 are contained. Is considered to be in a eutectic state, and the liquidus temperature drops significantly. As a result, the glass composition for glass fibers of the present invention has excellent alkali resistance, and the difference between the spinning temperature of the glass and the liquid phase temperature is large, resulting in excellent productivity.
本発明のガラス繊維用ガラス組成物は、紡糸温度と液相温度の差が１１５℃以上であることが好ましい。なお、「紡糸温度」とは、ガラスの粘度が１０３ｄＰａ・ｓとなる温度を意味する。このようにすることで、生産性に優れたガラス繊維用ガラス組成物とすることができる。 In the glass composition for glass fibers of the present invention, the difference between the spinning temperature and the liquid phase temperature is preferably 115 ° C. or more. Note that the "spinning temperature" means the temperature at which the viscosity of the glass is 10 3 dPa · s. By doing so, it is possible to obtain a glass composition for glass fibers having excellent productivity.
本発明のガラス繊維用ガラス組成物は、酸化物換算の質量比で、Ｂ２Ｏ３／ＴｉＯ２の値が０．０１〜９５であることが好ましい。このようにすることで、優れた耐アルカリ性を有しつつ、ガラスの紡糸温度と液相温度の差がより大きく、生産性に優れたガラス繊維用ガラス組成物とすることができる。 The glass composition for glass fibers of the present invention preferably has a B 2 O 3 / TiO 2 value of 0.01 to 95 in terms of oxide-equivalent mass ratio. By doing so, it is possible to obtain a glass composition for glass fibers having excellent alkali resistance, having a larger difference between the spinning temperature of the glass and the liquid phase temperature, and having excellent productivity.
本発明のガラス繊維用ガラス組成物は、Ｂ２Ｏ３＋ＴｉＯ２の含有量が１〜２０質量％であることが好ましい。ここで、「Ｂ２Ｏ３＋ＴｉＯ２」とは、Ｂ２Ｏ３及びＴｉＯ２の合量を意味している。このようにすることで、より確実に、優れた耐アルカリ性を有しつつ、ガラスの紡糸温度と液相温度の差がより大きく、生産性に優れたガラス繊維用ガラス組成物とすることができる。 The glass composition for glass fibers of the present invention preferably has a B 2 O 3 + TiO 2 content of 1 to 20% by mass. Here, "B 2 O 3 + TiO 2 " means the total amount of B 2 O 3 and TiO 2. By doing so, it is possible to obtain a glass composition for glass fibers having a larger difference between the spinning temperature and the liquid phase temperature of the glass and having excellent productivity while having more reliable and excellent alkali resistance. ..
本発明のガラス繊維用ガラス組成物は、Ｂ２Ｏ３の含有量が０．５〜７．８質量％であることが好ましい。このようにすることで、紡糸温度や液相温度を低下でき、耐アルカリ性に優れたガラス繊維用ガラス組成物とすることができる。 The glass composition for glass fibers of the present invention preferably has a B 2 O 3 content of 0.5 to 7.8% by mass. By doing so, the spinning temperature and the liquid phase temperature can be lowered, and a glass composition for glass fibers having excellent alkali resistance can be obtained.
本発明のガラス繊維用ガラス組成物は、Ｌｉ２Ｏの含有量が０〜０．２質量％であることが好ましい。このようにすることで、生産コストを低減させることができる。 The glass composition for glass fibers of the present invention preferably has a Li 2 O content of 0 to 0.2% by mass. By doing so, the production cost can be reduced.
本発明のガラス繊維用ガラス組成物は、Ｎａ２Ｏ＋Ｋ２Ｏの含有量が１０〜２０％であることが好ましい。ここで、「Ｎａ２Ｏ＋Ｋ２Ｏ」とは、Ｎａ２Ｏ及びＫ２Ｏの合量を意味している。このようにすることで、ガラスの粘度を低下させることができ、溶融性や成形性に優れたガラス繊維用ガラス組成物とすることができる。 The glass composition for glass fibers of the present invention preferably has a Na 2 O + K 2 O content of 10 to 20%. Here, "Na 2 O + K 2 O" means the total amount of Na 2 O and K 2 O. By doing so, the viscosity of the glass can be lowered, and a glass composition for glass fibers having excellent meltability and moldability can be obtained.
本発明のガラス繊維用ガラス組成物は、紡糸温度が１２７０℃以下であることが好ましい。このようにすることで、低温で繊維化できるようになることから、溶融コストを低減できる上、ブッシング等の繊維化設備の長寿命化も図れるため、生産コストを低減することができる。 The glass composition for glass fibers of the present invention preferably has a spinning temperature of 1270 ° C. or lower. By doing so, it becomes possible to fiberize at a low temperature, so that the melting cost can be reduced, and the life of the fibrous equipment such as a bushing can be extended, so that the production cost can be reduced.
本発明のガラス繊維用ガラス組成物は、液相温度が１１５０℃以下であることが好ましい。このようにすることで、紡糸が容易になることから、生産性に優れたガラス繊維用ガラス組成物とすることができる。 The glass composition for glass fibers of the present invention preferably has a liquid phase temperature of 1150 ° C. or lower. By doing so, spinning becomes easy, so that a glass composition for glass fibers having excellent productivity can be obtained.
本発明のガラス繊維用ガラス組成物は、１０質量％のＮａＯＨ水溶液１００ｍｌ中に８０℃、９０時間の条件で浸漬した時のガラスの質量減少率が４％以下であることが好ましい。なお、評価には３００〜５００μｍの粒度に分級した比重×１質量分のガラスを用いた。このようにすることで、ケイ酸カルシウム板やＧＲＣ等の複合材料の補強材として信頼性の高いガラス繊維を得ることが容易になる。 The glass composition for glass fibers of the present invention preferably has a glass mass reduction rate of 4% or less when immersed in 100 ml of a 10 mass% NaOH aqueous solution at 80 ° C. for 90 hours. For the evaluation, glass having a specific gravity × 1 mass classified into a particle size of 300 to 500 μm was used. By doing so, it becomes easy to obtain highly reliable glass fiber as a reinforcing material for a composite material such as a calcium silicate plate or GRC.
本発明のガラス繊維用ガラス組成物は、１０質量％のＨＣｌ水溶液１００ｍｌ中に８０℃、９０時間の条件で浸漬した時のガラスの質量減少率が４％以下であることが好ましい。なお、評価には３００〜５００μｍの粒度に分級した比重×１質量分のガラスを用いた。このようにすることで、バッテリーセパレータ等の耐食性材料として信頼性が高いガラス繊維を得ることが容易になる。 The glass composition for glass fibers of the present invention preferably has a glass mass reduction rate of 4% or less when immersed in 100 ml of a 10 mass% HCl aqueous solution at 80 ° C. for 90 hours. For the evaluation, glass having a specific gravity × 1 mass classified into a particle size of 300 to 500 μm was used. By doing so, it becomes easy to obtain highly reliable glass fiber as a corrosion-resistant material such as a battery separator.
本発明のガラス繊維は、上記のガラス繊維用ガラス組成物からなることを特徴とする。 The glass fiber of the present invention is characterized by comprising the above-mentioned glass composition for glass fiber.
本発明のガラス繊維の製造方法は、ガラス組成として、酸化物換算の質量％で、ＳｉＯ２ ５０〜６５％、Ａｌ２Ｏ３ ０〜５％、ＣａＯ ０〜１０％、Ｎａ２Ｏ １０〜２０％、Ｋ２Ｏ ０〜５％、ＺｒＯ２ １５超〜２０％、ＴｉＯ２ ０．１〜１０％、Ｂ２Ｏ３ ０．１〜１０％となるように調合した原料バッチをガラス溶融炉で溶融し、得られた溶融ガラスをブッシングから連続的に引き出して繊維状に成形することを特徴とする。 The method for producing glass fiber of the present invention has a glass composition of SiO 2 50 to 65%, Al 2 O 30 to 5%, CaO 0 to 10%, and Na 2 O 10 to 20 in terms of oxide mass%. %, K 2 O 0 to 5%, ZrO 2 over 15 to 20%, TiO 2 0.1 to 10%, B 2 O 3 0.1 to 10%. It is characterized in that the molten glass obtained by melting is continuously pulled out from the bushing and formed into a fibrous form.
本発明のガラス繊維の製造方法は、得られるガラスの紡糸温度と液相温度の差が１１５℃以上となるように原料バッチを調合することが好ましい。 In the method for producing glass fibers of the present invention, it is preferable to prepare a raw material batch so that the difference between the spinning temperature and the liquidus temperature of the obtained glass is 115 ° C. or more.
本発明のガラス繊維の製造方法は、酸化物換算の質量比で、Ｂ２Ｏ３／ＴｉＯ２の値が０．０１〜９５となるように調合した原料バッチを用いることが好ましい。 In the method for producing glass fiber of the present invention, it is preferable to use a raw material batch prepared so that the value of B 2 O 3 / TiO 2 is 0.01 to 95 in terms of mass ratio in terms of oxide.
このようにすることで、溶融温度を上昇させることなく、ガラスの紡糸温度と液相温度の差をより大きくできるため、生産性を向上できる。 By doing so, the difference between the spinning temperature of the glass and the liquid phase temperature can be made larger without raising the melting temperature, so that the productivity can be improved.
以下、本発明のガラス繊維用ガラス組成物について説明する。なお、特段の記載がなければ、各成分の含有範囲の説明において、％表示は質量％を指す。 Hereinafter, the glass composition for glass fibers of the present invention will be described. Unless otherwise specified,% notation indicates mass% in the description of the content range of each component.
ＳｉＯ２は、ガラス骨格構造を形成する主要成分であり、ガラスの耐酸性を向上させる成分でもある。ＳｉＯ２の含有量は５０〜６５％、好ましくは５５〜６０％、より好ましくは５７〜６０％である。ＳｉＯ２の含有量が少なすぎると、ガラスの機械的強度が低下し易くなる上、ガラスの耐酸性が低下する。ＳｉＯ２の含有量が多すぎると、ガラスの粘度が高くなってガラスの溶融に必要なエネルギーが増大する。また貴金属製ブッシングの損傷が激しくなって交換頻度が高くなり、生産コストが高くなる。更に、ガラスの耐アルカリ性が低下する。 SiO 2 is a main component that forms a glass skeleton structure, and is also a component that improves the acid resistance of glass. The content of SiO 2 is 50 to 65%, preferably 55 to 60%, and more preferably 57 to 60%. If the content of SiO 2 is too small, the mechanical strength of the glass tends to decrease, and the acid resistance of the glass decreases. If the content of SiO 2 is too high, the viscosity of the glass increases and the energy required for melting the glass increases. In addition, the precious metal bushing is severely damaged, the frequency of replacement increases, and the production cost increases. Further, the alkali resistance of the glass is lowered.
Ａｌ２Ｏ３は、ガラスの化学的耐久性や機械的強度を高める成分である。一方、Ａｌ２Ｏ３は、ガラスの粘度を高める成分でもある。Ａｌ２Ｏ３の含有量は０〜５％、好ましくは０〜３％、より好ましくは０〜１％である。Ａｌ２Ｏ３の含有量が多すぎるとガラスの粘度が高くなってガラスの溶融に必要なエネルギーが増大する。 Al 2 O 3 is a component that enhances the chemical durability and mechanical strength of glass. On the other hand, Al 2 O 3 is also a component that increases the viscosity of glass. The content of Al 2 O 3 is 0 to 5%, preferably 0 to 3%, and more preferably 0 to 1%. If the content of Al 2 O 3 is too high, the viscosity of the glass increases and the energy required for melting the glass increases.
ＣａＯは、ガラスの粘度を低下させる成分である。ＣａＯの含有量は０〜１０％、好ましくは０〜５％、より好ましくは０〜４％、さらに好ましくは０〜３％である。ＣａＯの含有量が多すぎるとガラス中にＺｒ、Ｓｉ、Ｎａ、Ｃａを含む結晶が析出しやすくなり、ガラスの液相温度が高くなり、紡糸温度と液相温度の差が小さくなって生産性が低下する。 CaO is a component that reduces the viscosity of glass. The CaO content is 0 to 10%, preferably 0 to 5%, more preferably 0 to 4%, and even more preferably 0 to 3%. If the CaO content is too high, crystals containing Zr, Si, Na, and Ca are likely to precipitate in the glass, the liquidus temperature of the glass becomes high, and the difference between the spinning temperature and the liquidus temperature becomes small, resulting in productivity. Decreases.
アルカリ金属酸化物であるＮａ２Ｏ及びＫ２Ｏはガラスの粘度を低下させ、ガラスの溶融性や成形性を高める成分である。一方、アルカリ金属酸化物は、多量に含有しすぎるとガラスの耐水性を低下させてしまう成分である。Ｎａ２Ｏ＋Ｋ２Ｏの量は１０〜２０％、好ましくは１０〜１８％、より好ましくは１２〜１８％、さらに好ましくは１５〜１７％である。Ｎａ２Ｏ＋Ｋ２Ｏの量が少なすぎると、ガラスの粘度が高くなってガラスの溶融に必要なエネルギーが増大する。また貴金属製ブッシングの損傷が激しくなって交換頻度が高くなり、生産コストが高くなる。Ｎａ２Ｏ＋Ｋ２Ｏの量が多すぎると、ガラスの耐水性が低下する。 Alkali metal oxides Na 2 O and K 2 O are components that reduce the viscosity of glass and enhance the meltability and moldability of glass. On the other hand, the alkali metal oxide is a component that lowers the water resistance of the glass if it is contained in an excessive amount. The amount of Na 2 O + K 2 O is 10 to 20%, preferably 10 to 18%, more preferably 12 to 18%, still more preferably 15 to 17%. If the amount of Na 2 O + K 2 O is too small, the viscosity of the glass increases and the energy required to melt the glass increases. In addition, the precious metal bushing is severely damaged, the frequency of replacement increases, and the production cost increases. If the amount of Na 2 O + K 2 O is too large, the water resistance of the glass will decrease.
Ｎａ２Ｏは、ガラスの粘度を低下させ、ガラスの溶融性や成形性を高める成分である。Ｎａ２Ｏの含有量は１０〜２０％、好ましくは１０〜１８％、より好ましくは１２〜１８％、最も好ましくは１２〜１７％である。Ｎａ２Ｏの含有量が少なすぎると、ガラスの粘度が高くなり、ガラスの溶融に必要なエネルギーが増大する。また貴金属製ブッシングの損傷が激しくなって交換頻度が高くなり、生産コストが高くなる。Ｎａ２Ｏの含有量が多すぎるとガラスの液相温度が高くなり、紡糸温度と液相温度の差が小さくなって生産性が低下する。また、ガラスの耐水性が低下する。 Na 2 O is a component that lowers the viscosity of glass and enhances the meltability and moldability of glass. The content of Na 2 O is 10 to 20%, preferably 10 to 18%, more preferably 12 to 18%, and most preferably 12 to 17%. If the Na 2 O content is too low, the viscosity of the glass will increase and the energy required to melt the glass will increase. In addition, the precious metal bushing is severely damaged, the frequency of replacement increases, and the production cost increases. If the Na 2 O content is too high, the liquidus temperature of the glass becomes high, and the difference between the spinning temperature and the liquidus temperature becomes small, resulting in a decrease in productivity. In addition, the water resistance of the glass is reduced.
Ｋ２Ｏは、ガラスの粘度を低下させることによって、ガラスの溶融性や成形性を高める成分である。Ｋ２Ｏの含有量は０〜５％、好ましくは０〜３％、最も好ましくは０〜２％である。Ｋ２Ｏの含有量が多すぎると、ガラスの耐水性が低下する。また、原料バッチが水分を吸収しやすくなり、原料粉末の凝集体（いわゆる「だま」）が形成されやすい。原料粉末の凝集体が形成されると原料バッチの溶解性が悪化し、ガラス繊維中に未溶解のジルコニアが残留しやすくなって好ましくない。 K 2 O is a component that enhances the meltability and moldability of glass by lowering the viscosity of the glass. The content of K 2 O is 0-5%, preferably 0-3%, the most preferably 0-2%. If the K 2 O content is too high, the water resistance of the glass will decrease. In addition, the raw material batch easily absorbs water, and agglomerates of raw material powder (so-called "dama") are easily formed. When agglomerates of the raw material powder are formed, the solubility of the raw material batch deteriorates, and undissolved zirconia tends to remain in the glass fiber, which is not preferable.
Ｌｉ２Ｏは少量の添加によって液相温度を大幅に下げ、紡糸温度と液相温度の差を大きくし、生産性を向上させる成分である。しかし、Ｌｉ２Ｏは原料コストが高いため、Ｌｉ２Ｏの含有量が多すぎると生産コストが増加する。さらに、リチウムバッテリーの需要増加に伴いリチウム原料の供給がショートする懸念が高まっているため、Ｌｉ２Ｏの含有量が多すぎると生産に必要なリチウム原料が確保できなくなる懸念がある。よってＬｉ２Ｏの含有量は０〜０．２％であることが好ましく、コスト及び供給の観点からは、Ｌｉ２Ｏを含有しないことが好ましい。ここで「Ｌｉ２Ｏを含有しない」とは、ガラス組成としてＬｉ２Ｏを積極的に含有させない、という意味であり、不可避的不純物まで排除するものではない。より具体的には、不純物を含めた含有量が質量％で０．０１％以下であることを指す。このようにすれば、原料供給不安、原料費の高騰等の問題を回避し易くなる。 Li 2 O is a component that significantly lowers the liquidus temperature by adding a small amount, increases the difference between the spinning temperature and the liquidus temperature, and improves productivity. However, since Li 2 O has a high raw material cost, if the content of Li 2 O is too large, the production cost increases. Furthermore, as the demand for lithium batteries increases, there is a growing concern that the supply of lithium raw materials will be short-circuited. Therefore, if the Li 2 O content is too high, there is a concern that the lithium raw materials required for production cannot be secured. Therefore, the content of Li 2 O is preferably 0 to 0.2%, and it is preferable not to contain Li 2 O from the viewpoint of cost and supply. Here, " does not contain Li 2 O" means that Li 2 O is not positively contained in the glass composition, and does not exclude unavoidable impurities. More specifically, it means that the content including impurities is 0.01% or less in mass%. In this way, it becomes easy to avoid problems such as insecurity of raw material supply and soaring raw material costs.
ＺｒＯ２は、ガラスの耐アルカリ性、耐酸性及び耐水性を向上させる成分である。ＺｒＯ２の含有量は１５超〜２０％、好ましくは１５．５〜１９．５％、より好ましくは１６〜１９％、さらに好ましくは１６．５〜１８．５％、最も好ましくは１７〜１８％である。ＺｒＯ２の含有量が少なすぎるとガラス繊維用ガラス組成物の耐アルカリ性が低下し、その結果、ＧＲＣに求められる耐久性を実現できない。ＺｒＯ２の含有量が多すぎるとガラスの液相温度が高くなり、紡糸温度と液相温度の差が小さくなって生産性が低下する。 ZrO 2 is a component that improves the alkali resistance, acid resistance, and water resistance of glass. The content of ZrO 2 is more than 15 to 20%, preferably 15.5 to 19.5%, more preferably 16 to 19%, further preferably 16.5 to 18.5%, and most preferably 17 to 18%. Is. If the content of ZrO 2 is too small, the alkali resistance of the glass composition for glass fibers is lowered, and as a result, the durability required for GRC cannot be realized. If the content of ZrO 2 is too large, the liquidus temperature of the glass becomes high, the difference between the spinning temperature and the liquidus temperature becomes small, and the productivity decreases.
ＴｉＯ２は、ガラスの耐水性と耐アルカリ性を向上させると共に、紡糸温度を下げ、液相温度を大幅に低下させる成分である。ＴｉＯ２の含有量は、０．１〜１０％、好ましくは１〜９％、より好ましくは２〜８％である。ＴｉＯ２の含有量が少なすぎると、ガラスの耐水性と耐アルカリ性が低下する上、紡糸温度が上昇して生産コストが高くなる。ＴｉＯ２の含有量が多すぎると、ガラス中にＴｉＯ２を含む結晶が析出しやすくなって液相温度が大幅に上昇する。その結果、紡糸温度と液相温度の差が小さくなって生産性が低下する。 TiO 2 is a component that improves the water resistance and alkali resistance of glass, lowers the spinning temperature, and significantly lowers the liquidus temperature. The content of TiO 2 is 0.1 to 10%, preferably 1 to 9%, and more preferably 2 to 8%. If the content of TiO 2 is too small, the water resistance and alkali resistance of the glass are lowered, and the spinning temperature is raised, resulting in a high production cost. If the content of TiO 2 is too large, crystals containing TiO 2 are likely to precipitate in the glass, and the liquidus temperature rises significantly. As a result, the difference between the spinning temperature and the liquid phase temperature becomes small, and the productivity decreases.
Ｂ２Ｏ３は紡糸温度を下げ、液相温度を大幅に低下させる成分である。Ｂ２Ｏ３の含有量は、０．１〜１０％、好ましくは１〜９％、より好ましくは１〜７．８％である。Ｂ２Ｏ３の含有量が少なすぎると、紡糸温度が上昇し、紡糸温度と液相温度の差が小さくなって生産性が低下する。また、Ｂ２Ｏ３の含有量が多すぎると、ガラスの耐アルカリ性が低下する。 B 2 O 3 is a component that lowers the spinning temperature and significantly lowers the liquidus temperature. The content of B 2 O 3 is 0.1 to 10%, preferably 1 to 9%, and more preferably 1 to 7.8%. If the content of B 2 O 3 is too small, the spinning temperature rises, the difference between the spinning temperature and the liquid phase temperature becomes small, and the productivity decreases. Further, if the content of B 2 O 3 is too large, the alkali resistance of the glass is lowered.
本発明のガラス繊維用ガラス組成物は、Ｂ２Ｏ３とＴｉＯ２を必須成分として含有する。上述したとおり、ＺｒＯ２を一定量以上含有させたガラス組成において、Ｂ２Ｏ３とＴｉＯ２の両方を含有させることによりＮａ、Ｚｒ、Ｓｉを含む結晶と、Ｋ、Ｚｒ、Ｓｉを含む結晶とが共晶状態になると考えられ、液相温度が著しく低下するためである。Ｂ２Ｏ３／ＴｉＯ２の値は、共晶点を決定付ける指標かつガラスの耐アルカリ性を管理する指標として重要である。Ｂ２Ｏ３／ＴｉＯ２の値は、０．０１〜９５、好ましくは０．０２〜９２、より好ましくは０．０５〜９０、更に好ましくは０．１０〜８５、特に好ましくは０．１２〜８０である。Ｂ２Ｏ３／ＴｉＯ２の値が小さすぎると液相温度が上昇し、生産性が低下する。また、Ｂ２Ｏ３／ＴｉＯ２の値が大きすぎると、耐アルカリ性が低下する。 The glass composition for glass fibers of the present invention contains B 2 O 3 and TiO 2 as essential components. As described above, in a glass composition containing a certain amount or more of ZrO 2 , a crystal containing Na, Zr , and Si and a crystal containing K, Zr , and Si are formed by containing both B 2 O 3 and TiO 2. Is considered to be in a eutectic state, and the liquidus temperature drops significantly. The value of B 2 O 3 / TiO 2 is important as an index for determining the eutectic point and an index for controlling the alkali resistance of the glass. The value of B 2 O 3 / TiO 2 is 0.01 to 95, preferably 0.02 to 92, more preferably 0.05 to 90, still more preferably 0.10 to 85, and particularly preferably 0.12 to 0.12. It is 80. If the value of B 2 O 3 / TiO 2 is too small, the liquidus temperature rises and the productivity decreases. Further, if the value of B 2 O 3 / TiO 2 is too large, the alkali resistance is lowered.
Ｂ２Ｏ３とＴｉＯ２の相互作用をより確実に得るために、Ｂ２Ｏ３とＴｉＯ２を含有させる際には、Ｂ２Ｏ３とＴｉＯ２の合量を一定範囲に規制することが好ましい。このようにすることで、液相温度を著しく低下させ、生産性を向上させることができる。そのため、Ｂ２Ｏ３＋ＴｉＯ２の値は、１〜２０％であり、好ましくは２〜１９％、より好ましくは３〜１８％、更に好ましくは４〜１８％、５〜１７％、６〜１６％、６．５〜１５％、特に好ましくは７〜１３％である。Ｂ２Ｏ３＋ＴｉＯ２の値が小さすぎると紡糸温度と液相温度が高くなり、生産性が低下する。Ｂ２Ｏ３＋ＴｉＯ２の値が大きすぎると生産コストが増加する。 In order to obtain the interaction between B 2 O 3 and TiO 2 more reliably, when B 2 O 3 and TiO 2 are contained, the total amount of B 2 O 3 and TiO 2 may be regulated within a certain range. preferable. By doing so, the liquidus temperature can be remarkably lowered and the productivity can be improved. Therefore, the value of B 2 O 3 + TiO 2 is 1 to 20%, preferably 2 to 19%, more preferably 3 to 18%, still more preferably 4 to 18%, 5 to 17%, 6 to 16. %, 6.5 to 15%, particularly preferably 7 to 13%. If the value of B 2 O 3 + TiO 2 is too small, the spinning temperature and the liquidus temperature will rise, and the productivity will decrease. If the value of B 2 O 3 + TiO 2 is too large, the production cost will increase.
本発明のガラス繊維用ガラス組成物は、上記した成分（ＳｉＯ２、Ａｌ２Ｏ３、ＣａＯ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｌｉ２Ｏ、ＺｒＯ２、ＴｉＯ２及びＢ２Ｏ３）以外の成分を含みうる。ただし上記した成分の含有量が合量で９８％以上、特に９９％以上となるように組成を調節することが望ましい。その理由は、これらの成分の合量が９８％未満の場合、意図しない異種成分の混入によって耐アルカリ性、耐酸性、耐水性が低下して製品としての特性が低下したり、紡糸温度と液相温度の差が小さくなって生産性が低下したりする等の不都合が生じ易い。 The glass composition for glass fibers of the present invention has other than the above-mentioned components (SiO 2 , Al 2 O 3 , CaO, Na 2 O, K 2 O, Li 2 O, ZrO 2, TiO 2 and B 2 O 3 ). May contain ingredients. However, it is desirable to adjust the composition so that the total content of the above-mentioned components is 98% or more, particularly 99% or more. The reason is that when the total amount of these components is less than 98%, the alkali resistance, acid resistance, and water resistance are lowered due to unintended mixing of different kinds of components, and the characteristics of the product are deteriorated, or the spinning temperature and liquid phase are deteriorated. Inconveniences such as a decrease in productivity due to a small temperature difference are likely to occur.
上記した成分以外の成分として、例えばＨ２、ＣＯ２、ＣＯ、Ｈ２Ｏ、Ｈｅ、Ｎｅ、Ａｒ、Ｎ２等の微量成分をそれぞれ０．１％まで含有してもよい。また、ガラス中にＰｔ、Ｒｈ、Ａｕ等の貴金属元素を５００ｐｐｍまで添加してもよい。 As a component other than the above-mentioned components, for example , trace components such as H 2 , CO 2 , CO, H 2 O, He, Ne, Ar, and N 2 may be contained up to 0.1% each. Further, noble metal elements such as Pt, Rh and Au may be added to the glass up to 500 ppm.
さらに耐アルカリ性、耐酸性、耐水性、液相温度の改善のために、ＭｇＯ、ＳｒＯ、ＢａＯ、ＺｎＯ、Ｐ２Ｏ５、Ｆｅ２Ｏ３、Ｃｒ２Ｏ３、Ｓｂ２Ｏ３、ＳＯ３、ＭｎＯ、ＳｎＯ２、ＣｅＯ２、Ｃｌ２、Ｌａ２Ｏ３、ＷＯ３、Ｎｂ２Ｏ５、Ｙ２Ｏ３等を合量で２％まで含有してもよい。 Further, in order to improve alkali resistance, acid resistance, water resistance, and liquid phase temperature, MgO, SrO, BaO, ZnO, P 2 O 5 , Fe 2 O 3 , Cr 2 O 3 , Sb 2 O 3 , SO 3 , MnO, SnO 2 , CeO 2 , Cl 2 , La 2 O 3 , WO 3 , Nb 2 O 5 , Y 2 O 3 and the like may be contained up to 2% in total.
本発明のガラス繊維用ガラス組成物は、３００〜５００μｍの粒度に分級された比重×１重量分のガラスを１０質量％のＮａＯＨ水溶液１００ｍｌ中に８０℃、９０時間浸漬した時のガラスの重量減少率が４％以下、好ましくは３．９％以下、より好ましくは３．８％以下、更に好ましくは３．６％以下、特に３％以下である。この耐アルカリ性試験によるガラスの重量減少率が多いと、ケイ酸カルシウム板やＧＲＣ等の複合材料の補強材としての信頼性が低くなる。 The glass composition for glass fibers of the present invention reduces the weight of glass when a glass having a specific gravity × 1 weight, which is classified into a particle size of 300 to 500 μm, is immersed in 100 ml of a 10 mass% NaOH aqueous solution at 80 ° C. for 90 hours. The rate is 4% or less, preferably 3.9% or less, more preferably 3.8% or less, still more preferably 3.6% or less, and particularly 3% or less. If the weight reduction rate of the glass by this alkali resistance test is large, the reliability as a reinforcing material of a composite material such as a calcium silicate plate or GRC becomes low.
本発明のガラス繊維用ガラス組成物は、３００〜５００μｍの粒度に分級された比重×１重量分のガラスを１０質量％のＨＣｌ水溶液１００ｍｌ中に８０℃、９０時間浸漬した時のガラスの重量減少率が４％以下、好ましくは３％以下、より好ましくは２％以下、更に好ましくは１．５％以下、特に１％以下である。この耐酸性試験によるガラスの重量減少率が多いと、バッテリーセパレータ等の耐食性材料としての信頼性が低下する。 The glass composition for glass fibers of the present invention reduces the weight of glass when a glass having a specific gravity × 1 weight, which is classified into a particle size of 300 to 500 μm, is immersed in 100 ml of a 10 mass% HCl aqueous solution at 80 ° C. for 90 hours. The rate is 4% or less, preferably 3% or less, more preferably 2% or less, still more preferably 1.5% or less, and particularly 1% or less. If the weight reduction rate of the glass by this acid resistance test is large, the reliability as a corrosion resistant material such as a battery separator is lowered.
本発明のガラス繊維用ガラス組成物は、耐水性試験として、ＪＩＳ Ｒ３５０２（１９９５）に準拠した方法で測定したアルカリ溶出量が０．４０ｍｇ以下、好ましくは０．３５ｍｇ以下、更に好ましくは０．３０ｍｇ以下、特に好ましくは０．３０ｍｇ未満である。アルカリ溶出量が多いと、オートクレーブ処理中にガラスからアルカリ成分が溶出して、ガラスが劣化しやすくなる。 The glass composition for glass fibers of the present invention has an alkali elution amount of 0.40 mg or less, preferably 0.35 mg or less, more preferably 0.30 mg, as measured by a method according to JIS R3502 (1995) as a water resistance test. Hereinafter, it is particularly preferably less than 0.30 mg. If the amount of alkali eluted is large, the alkali component is eluted from the glass during the autoclave treatment, and the glass is liable to deteriorate.
本発明のガラス繊維用ガラス組成物は、紡糸温度が１２７０℃以下、好ましくは１２６５℃以下、更に好ましくは１２６０℃以下、特に好ましくは１２５０℃以下である。紡糸温度が高すぎると、高温で紡糸を行う必要があることから、溶融コストが高くなるだけではなく、貴金属製ブッシングの損傷が激しくなり、交換頻度が高くなって生産コストが高くなる。 The glass composition for glass fibers of the present invention has a spinning temperature of 1270 ° C. or lower, preferably 1265 ° C. or lower, more preferably 1260 ° C. or lower, and particularly preferably 1250 ° C. or lower. If the spinning temperature is too high, it is necessary to spin at a high temperature, which not only increases the melting cost, but also severely damages the precious metal bushing, increases the frequency of replacement, and increases the production cost.
本発明のガラス繊維用ガラス組成物は、液相温度が１１５０℃以下、好ましくは１１４０℃以下、更に好ましくは１１３０℃以下、特に好ましくは１１２０℃以下である。液相温度が高すぎると、失透しやすくなり、生産性が低下する。 The glass composition for glass fibers of the present invention has a liquid phase temperature of 1150 ° C. or lower, preferably 1140 ° C. or lower, more preferably 1130 ° C. or lower, and particularly preferably 1120 ° C. or lower. If the liquidus temperature is too high, devitrification is likely to occur and productivity is reduced.
本発明のガラス繊維用ガラス組成物は、紡糸温度と液相温度の差が１１５℃以上、好ましくは１２０℃以上、より好ましくは１３０℃以上、更に好ましくは１４０℃以上、特に好ましくは１５０℃以上である。紡糸温度と液相温度の差が小さいと、生産性が低下する。 In the glass composition for glass fibers of the present invention, the difference between the spinning temperature and the liquid phase temperature is 115 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, still more preferably 140 ° C. or higher, and particularly preferably 150 ° C. or higher. Is. If the difference between the spinning temperature and the liquid phase temperature is small, the productivity will decrease.
次に本発明のガラス繊維を製造する方法を、ダイレクトメルト法（ＤＭ法）を例にして説明する。なお本発明は下記の方法に制限されるものではなく、例えばマーブル状に成形した繊維用ガラス材料をブッシング装置で再溶融し紡糸する、いわゆる間接成形法（ＭＭ法：マーブルメルト法）を採用することもできる。この方法は少量多品種生産に向いている。 Next, the method for producing the glass fiber of the present invention will be described by taking the direct melt method (DM method) as an example. The present invention is not limited to the following methods, and employs, for example, a so-called indirect forming method (MM method: marble melting method) in which a glass material for fibers molded into a marble shape is remelted and spun by a bushing device. You can also do it. This method is suitable for low-volume, high-mix production.
まず酸化物換算の質量％で、ＳｉＯ２ ５０〜６５％、Ａｌ２Ｏ３ ０〜５％、ＣａＯ ０〜１０％、Ｎａ２Ｏ １０〜２０％、Ｋ２Ｏ ０〜５％、ＺｒＯ２ １５超〜２０％、ＴｉＯ２ ０．１〜１０％、Ｂ２Ｏ３ ０．１〜１０％を含有するガラスとなるようにガラス原料を調合する。なおガラス原料の一部又は全部にガラスカレットを使用してもよい。各成分の含有量を上記の通りとした理由は既述の通りであり、ここでは説明を省略する。 First, in terms of oxide-equivalent mass%, SiO 2 50 to 65%, Al 2 O 30 to 5%, CaO 0 to 10%, Na 2 O 10 to 20%, K 2 O 0 to 5%, ZrO 2 15 The glass raw material is prepared so as to be a glass containing ultra to 20%, TiO 2 0.1 to 10%, and B 2 O 3 0.1 to 10%. A glass cullet may be used for a part or all of the glass raw material. The reason why the content of each component is set as described above is as described above, and the description thereof will be omitted here.
次いで、調合した原料バッチをガラス溶融炉に投入し、ガラス化し、溶融、均質化する。溶融温度は１４００〜１６００℃程度が好適である。 Next, the prepared raw material batch is put into a glass melting furnace, vitrified, melted, and homogenized. The melting temperature is preferably about 1400 to 1600 ° C.
続いて溶融ガラスを紡糸してガラス繊維に成形する。詳述すると、溶融ガラスをブッシングに供給する。ブッシングに供給された溶融ガラスは、その底面に設けられた多数のブッシングノズルからフィラメント状に連続的に引き出される。このようにして引き出されたモノフィラメントに各種処理剤を塗布し、所定本数毎に集束することによってガラス繊維を得る。 Subsequently, the molten glass is spun and formed into glass fibers. More specifically, the molten glass is supplied to the bushing. The molten glass supplied to the bushing is continuously drawn out in a filament shape from a large number of bushing nozzles provided on the bottom surface thereof. Various treatment agents are applied to the monofilaments drawn out in this manner, and the glass fibers are obtained by focusing the monofilaments in predetermined numbers.
このようにして成形された本発明のガラス繊維は、チョップドストランド、ヤーン、ロービング等に加工され、種々の用途に供される。 The glass fiber of the present invention thus formed is processed into chopped strands, yarns, rovings and the like, and is used for various purposes.
尚、チョップドストランドとは、ガラスモノフィラメントを集束したガラス繊維（ストランド）を所定長の長さに切断したものである。ヤーンとは、ストランドに撚りをかけたものである。ロービングとは、ストランドを複数本合糸し、円筒状に巻き取ったものである。 The chopped strand is obtained by cutting a glass fiber (strand) in which glass monofilaments are focused into a predetermined length. A yarn is a twist of a strand. Robbing is a combination of a plurality of strands and winding them into a cylindrical shape.
以下、実施例に基づいて、本発明を詳細に説明する。表１は本発明の実施例（Ｎｏ．１〜８）及び比較例Ｎｏ．９をそれぞれ示している。 Hereinafter, the present invention will be described in detail based on Examples. Table 1 shows Examples (No. 1 to 8) and Comparative Example No. 1 of the present invention. 9 are shown respectively.
表の各試料は、次のようにして作製した。 Each sample in the table was prepared as follows.
まず、表中のガラス組成になるように、天然原料、化成原料等の各種ガラス原料を秤量、混合して、原料バッチを作製した。次に、この原料バッチを白金ロジウム合金製坩堝に投入した後、間接加熱電気炉内で１５５０℃、５時間加熱して、溶融ガラスを得た。尚、均質な溶融ガラスを得るために、加熱時に、耐熱性撹拌棒を用いて、溶融ガラスを複数回攪拌した。続いて、得られた溶融ガラスを耐火性鋳型内に流し出し、板状のガラスを成形した後、徐冷炉内で徐冷処理（１０１３ｄＰａ・ｓにおける温度より３０〜５０℃高い温度で３０分間加熱した後、徐冷点〜歪点の温度域を１℃／分で降温）を行った。得られた各試料につき、紡糸温度、液相温度、耐酸性、耐アルカリ性、アルカリ溶出量を測定した。 First, various glass raw materials such as natural raw materials and chemical raw materials were weighed and mixed so as to have the glass composition shown in the table to prepare a raw material batch. Next, this raw material batch was put into a platinum rhodium alloy crucible and then heated at 1550 ° C. for 5 hours in an indirect heating electric furnace to obtain molten glass. In order to obtain a homogeneous molten glass, the molten glass was stirred a plurality of times using a heat-resistant stirring rod during heating. Subsequently, the obtained molten glass was poured into a refractory mold to form a plate-shaped glass, and then a slow cooling treatment was performed in a slow cooling furnace (at a temperature 30 to 50 ° C. higher than the temperature at 10 13 dPa · s for 30 minutes. After heating, the temperature range from the slow cooling point to the strain point was lowered at 1 ° C./min). For each of the obtained samples, the spinning temperature, liquid phase temperature, acid resistance, alkali resistance, and alkali elution amount were measured.
紡糸温度の測定は次のようにして行った。まず、上記した板状ガラス試料を適正な寸法に破砕し、なるべく気泡が巻き込まれないようにアルミナ製坩堝に投入した。続いてアルミナ製坩堝を加熱して、融液状態とし、白金球引き上げ法によって複数の温度におけるガラスの粘度を求めた。その後、得られた複数の計測値から粘度曲線を作成し、その内挿によって１０３ｄＰａ・ｓとなる温度を算出した。 The spinning temperature was measured as follows. First, the above-mentioned plate-shaped glass sample was crushed to an appropriate size and put into an alumina crucible so as not to involve air bubbles as much as possible. Subsequently, the alumina crucible was heated to a melted state, and the viscosities of the glass at a plurality of temperatures were determined by the platinum ball pulling method. Then, to create the viscosity curve from a plurality of measurement values obtained were calculated temperature by the interpolation becomes 10 3 dPa · s.
液相温度の測定は次のようにして行った。まず、上記した板状ガラス試料を粉砕し、３００〜５００μｍの範囲の粒度となるように調整し、耐火性の容器に適切な嵩密度を有する状態に充填した。続いてこの耐火性容器を、最高温度を１３５０℃に設定した間接加熱型の温度勾配炉内に入れて静置し、１６時間大気雰囲気中で加熱操作を行った。その後、温度勾配炉から、耐火性容器ごと試験体を取り出し、室温まで冷却後、偏光顕微鏡によって液相温度を特定した。 The liquidus temperature was measured as follows. First, the above-mentioned plate-shaped glass sample was crushed, adjusted to have a particle size in the range of 300 to 500 μm, and filled in a refractory container in a state having an appropriate bulk density. Subsequently, this refractory container was placed in an indirect heating type temperature gradient furnace in which the maximum temperature was set to 1350 ° C. and allowed to stand, and the heating operation was performed in the atmosphere for 16 hours. Then, the test piece was taken out from the temperature gradient furnace together with the fire-resistant container, cooled to room temperature, and then the liquidus temperature was specified by a polarizing microscope.
紡糸温度と液相温度の差は両者の値から算出した。 The difference between the spinning temperature and the liquid phase temperature was calculated from both values.
耐酸性は次のようにして測定した。まず、上記した板状ガラス試料を粉砕し、直径３００〜５００μｍの粒度のガラスを比重×１質量分だけ精秤し、続いて１０質量％ＨＣｌ溶液１００ｍｌ中に浸漬して、８０℃、９０時間の条件で振とうした。その後、ガラス試料の質量減少率を測定した。この値が小さいほど耐酸性に優れていることになる。 Acid resistance was measured as follows. First, the above-mentioned plate-shaped glass sample is crushed, glass having a particle size of 300 to 500 μm in diameter is precisely weighed by a specific gravity × 1 mass, and then immersed in 100 ml of a 10 mass% HCl solution at 80 ° C. for 90 hours. I shook it under the conditions of. Then, the mass reduction rate of the glass sample was measured. The smaller this value is, the better the acid resistance is.
耐アルカリ性は次のようにして測定した。まず、上記した板状ガラス試料を粉砕し、直径３００〜５００μｍの粒度のガラスを比重×１質量分だけ精秤し、続いて１０質量％ＮａＯＨ溶液１００ｍｌ中に浸漬して、８０℃、９０時間の条件で振とうした。その後、ガラス試料の質量減少率を測定した。この値が小さいほど耐アルカリ性に優れていることになる。 Alkali resistance was measured as follows. First, the above-mentioned plate-shaped glass sample is crushed, glass having a particle size of 300 to 500 μm in diameter is precisely weighed by a specific gravity × 1 mass, and then immersed in 100 ml of a 10 mass% NaOH solution at 80 ° C. for 90 hours. I shook it under the conditions of. Then, the mass reduction rate of the glass sample was measured. The smaller this value is, the better the alkali resistance is.
耐水性を示すアルカリ溶出量は、ＪＩＳ Ｒ３５０２（１９９５）に準拠した方法で測定した。この値が小さいほど耐水性に優れていることになる。 The amount of alkali elution showing water resistance was measured by a method according to JIS R3502 (1995). The smaller this value is, the better the water resistance is.
表１から明らかなように、実施例であるＮｏ．１〜８は、紡糸温度が１２７０℃以下、紡糸温度と液相温度の差が１１５℃以上、耐アルカリ性や耐酸性の指標となる質量減少率がいずれも４％以下、アルカリ溶出量が０．４０ｍｇ以下であった。 As is clear from Table 1, No. 1 of Examples. In Nos. 1 to 8, the spinning temperature is 1270 ° C. or lower, the difference between the spinning temperature and the liquid phase temperature is 115 ° C. or higher, the mass reduction rate, which is an index of alkali resistance and acid resistance, is 4% or less, and the amount of alkali elution is 0. It was 40 mg or less.
それに対し、比較例であるＮｏ．９は、紡糸温度と液相温度の差が１１５℃未満であり、安定した生産が難しい。 On the other hand, No. In No. 9, the difference between the spinning temperature and the liquid phase temperature is less than 115 ° C., which makes stable production difficult.
本発明のガラス繊維は、ケイ酸カルシウム板の補強材やバッテリーセパレータ等の耐食性材料として好適である。 The glass fiber of the present invention is suitable as a corrosion-resistant material such as a reinforcing material for a calcium silicate plate and a battery separator.
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