WO1999001393A1 - Glass composition for fibers - Google Patents

Glass composition for fibers Download PDF

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Publication number
WO1999001393A1
WO1999001393A1 PCT/JP1998/002818 JP9802818W WO9901393A1 WO 1999001393 A1 WO1999001393 A1 WO 1999001393A1 JP 9802818 W JP9802818 W JP 9802818W WO 9901393 A1 WO9901393 A1 WO 9901393A1
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Prior art keywords
weight
glass
composition
glass composition
mgo
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PCT/JP1998/002818
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French (fr)
Japanese (ja)
Inventor
Masahiro Mori
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Nitto Boseki Co., Ltd.
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Application filed by Nitto Boseki Co., Ltd. filed Critical Nitto Boseki Co., Ltd.
Publication of WO1999001393A1 publication Critical patent/WO1999001393A1/en

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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

Definitions

  • the present invention relates to a glass composition which can be easily fiberized and has good acid resistance.
  • E-glass with the following composition occupies most of the glass fibers used for reinforcement of laminates and resins currently on the market.
  • Glass fibers produced from this E-glass have good mechanical properties such as tensile strength, electrical properties, physical properties such as water resistance, and excellent productivity due to excellent meltability of raw materials and spinnability of molten glass.
  • the composition is excellent both physically and economically.
  • An object of the present invention is to provide a composition for glass fiber which is more excellent in acid resistance than E glass and is easily fiberized.
  • compositions that meet the above-mentioned object, the present inventors have invented the following compositions.
  • the spinning temperature should be lower than 130 ° C. and the liquidus temperature should be lower than the spinning temperature by more than 55 ° C. in order to make the composition easy to fibrillate.
  • a study was made to satisfy complicated conditions to obtain an excellent composition, and the results are as follows.
  • the physical properties of the glass having the composition of the present invention are comparable to those of the conventional E glass.
  • the present invention is S i 0 2, B 2 0 3, A 12 0 3, C A_ ⁇ , R 2 0 (R is Na, K or the L i), the F 2 containing as essential components, the rate is S i 0 2 5 9 ⁇ 6 3 wt%, BsOa 0.
  • the present invention is S i 0 2, B 2 0 3, A 1 2 0 3, C aO, R 2 0 (R is Na, K or the L i), the F 2 containing as essential components, the rate is S i 0 2 5 9 to 63% by weight (preferably 59 to 62% by weight), B 2 0 3 0.
  • a preferred embodiment of the present invention is S i 0 2, B 2 0 3, A 1 2 0 3, C aO, the R 2 0, F 2 comprising as essential components, the ratio is S i 0 2 5 9 ⁇ 6 3% , B 2 0 3 1 ⁇ 4%, A "0 3 1 2 ⁇ 1 6%, C aO + MgO 2 0 ⁇ 2 5%, 0 ⁇ 4% MgO, N a 2 0 0. 1 ⁇ 1%, K 2 0 0. 1 ⁇ 1%, N a 2 0 + K 2 0 0. 2 ⁇ 1. 5%, c this is F 2 0.. 1 to textile glass composition excellent in acid resistance is 1% in the composition, S i 0 2 5 9% to below the acid resistance is not sufficient, liquidus temperature increases with the melting temperature above 6 3% increases, spinnability is poor.
  • B 2 0 3 is higher the melting temperature lower than 5% 0., acid resistance is deteriorated exceeds 4%.
  • the Al 2 O 3 is less than 11%, the liquidus temperature is high, and the spinnability is poor. If the Al 2 O 3 is more than 16%, the water resistance is improved but the melting temperature is too high.
  • the content of CaO + MgO is less than 20%, the melting temperature is too high, and if it is more than 26%, good acid resistance cannot be obtained, and the liquidus temperature is high, resulting in poor spinnability.
  • N a 2 0 + K 2 0+ L i 2 0 includes a melting temperature lower than 2% 0. becomes high, water resistance exceeds 5% 1., the minimum amount for the electric characteristics may deteriorate It is being considered.
  • F 2 is to improve the meltability of glass, 0.0 5% effect less Below, the small increase in the effect exceeds 1%.
  • T i 0 2, F e 2 0 3 which normally inevitably mixed as raw material impurities, S r 0 or the like and, Z r 0 degree 2 or the like is less than 1%, respectively to mix the erosion or the like of the refractory May be mixed.
  • the glass composition specified in the present invention excluding other components, The total amount of the components is preferably 99.0% by weight or more of the entire glass composition.
  • C To obtain the glass composition of the present invention, first, various raw materials ores are mixed so as to have the above-mentioned component composition. .
  • Silica sand, limestone, dolomite, clay, colemanite, fluorite, soda ash, etc. can be used as raw material ores.
  • the component that decreases volatilized by melting at high temperatures during spinning (such as B 2 0 3, F 2) , than the amount that is specified in the present invention, the excess amount Mix raw materials with raw ore.
  • the mixed raw materials are converted into glass fibers having the composition of the present invention by a known method.
  • the raw material is melted in a glass-melting furnace, passed through a spinning furnace called a pusher, and at a spinning temperature of about 1,200 ° C to 1,300, the molten glass flowing out of the nozzle at the bottom is rapidly drawn.
  • a glass fiber having a diameter of 3 to 2 ⁇ ⁇ ⁇ (a glass composition for a fiber of the present invention) is obtained.
  • the glass raw material was melted and spun into glass fiber with a diameter of 13 m.
  • Table 1 shows the glass fiber composition and test results.
  • Spinning temperature the temperature of the molten glass when the viscosity is 100.
  • Liquidus temperature the temperature above which no crystals are present in the glass.
  • Acid resistance% when glass fiber is immersed in 10% sulfuric acid at 80 ° C for 5 hours
  • Examples 1 to 4 are glass compositions of the present invention, and Comparative Example 1 is a conventional E glass fiber. Comparative Examples 2-5 are compositions outside the scope of the present invention, and Reference Examples are ECR glass fibers of acid-resistant glass.
  • the acid resistance is significantly improved, It also shows that it has the same acid resistance as ECR glass fiber used for applications requiring acid resistance.
  • Other characteristics of the glass of each embodiment can be equal to or higher than that of the E glass.
  • Comparative Examples 1 to 5 have compositions similar to the composition of the present invention, whereas Comparative Examples 2 to 4 have good acid resistance, but the spinning temperature is too high, and Comparative Example 5 has insufficient acid resistance and Not practical.
  • the glass composition of the present invention does not require any special components in the raw materials, and is composed of the same components as the fibers of the E glass composition. Although the raw material prices are low, the expensive ZnO and Ti are used. 0 2 required and the conventional acid-resistant glass, ECR glass (reference example) and it is found to have of Chasse of equivalent performance and spinning.
  • the glass fiber of the present invention suppresses the amount of Na 2 0 + K 20 to the minimum necessary content, and obtains Si 0 2 , B 2 0 3 , Al 2 0 3 , C 2 aO-, excellent acid resistance in combination with F 2 as an essential component, yet the spinning temperature 1 3 0 0 ° C or less, since the liquid phase temperature was successfully lowered 5 5 ° C or more than the spinning temperature, acid It has become possible to produce glass fibers with excellent properties.

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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

A glass composition for fibers, containing SiO2, B2O3, Al2O3, CaO, R2O (wherein R is Na, K or Li) or F2 as indispensable components in relative amounts of 59 to 63 % by weight of SiO2, 0.5 to 4 % by weight of B2O3, 11 to 16 % by weight of Al2O3, 20 to 26 % by weight of CaO+MgO, 0 to 4 % by weight of MgO, 0.2 to 1.5 % by weight of Na2O+K2O+Li2O (with the proviso that the relative amount of each of Na2O, K2O and Li2O is in the range of 0 to 1 % by weight), and 0.05 to 1.0 % by weight of F2. The composition is similar to a composition of E-glass and excellent in thermal resistance and spinnability.

Description

明 細 書 繊維用ガラス組成物 技術分野  Description Glass fiber composition for textiles Technical field
本発明は、 容易に繊維化することが可能で耐酸性の良好なガラス組成物に関す るものである。 背景技術  The present invention relates to a glass composition which can be easily fiberized and has good acid resistance. Background art
現在市販されている積層板や樹脂の補強等に使用されるガラス繊維は下記組成 の Eガラスがその大半を占めている。  E-glass with the following composition occupies most of the glass fibers used for reinforcement of laminates and resins currently on the market.
含有成分 重量％ (以後％は重量％を表す）  Ingredients wt% (% means wt% hereinafter)
S i 02 5 2〜 5 6 S i 0 2 5 2 to 5 6
B2 03 5〜 1 0 B 2 0 3 5 to 10
AA 1122 003 1 2〜1 6 AA 11 22 00 3 1 2 to 16
C a 0 1 6〜 2 5  C a 0 1 6 to 2 5
MgO 0〜 6  MgO 0-6
N a 2 0 + K2 0 0〜 2 N a 2 0 + K 2 0 0~ 2
T i O 2 0〜 1  T i O 2 0-1
FF ee22 003 0〜 0 FF ee22 00 3 0〜0
F2 0 1 F 2 0 1
この Eガラスから製造したガラス繊維は引張強度などの機械的特性、 電気特性、 耐水性等の物性が良く、 また原料の溶融性、 溶融ガラスの紡糸性に優れているた め生産性が良いという物性的にも、 経済的にも優れた組成である。  Glass fibers produced from this E-glass have good mechanical properties such as tensile strength, electrical properties, physical properties such as water resistance, and excellent productivity due to excellent meltability of raw materials and spinnability of molten glass. The composition is excellent both physically and economically.
し力、しな力 ら、 耐酸性が極めて低いという欠点を持っている。 このため耐酸性 を要する用途には Eガラスは用いられなかった。 発明の開示 It has the drawback of extremely low acid resistance. For this reason, E glass was not used for applications requiring acid resistance. Disclosure of the invention
本発明は、 Eガラスより耐酸性に優れ、 繊維化が容易なガラス繊維用組成を提 供しょうとするものである。  An object of the present invention is to provide a composition for glass fiber which is more excellent in acid resistance than E glass and is easily fiberized.
本発明者は、 前記目的に合致する組成を種々検討した結果、 次の組成を発明す るに至った。  As a result of various studies on compositions that meet the above-mentioned object, the present inventors have invented the following compositions.
本発明を具体的に説明すれば、 繊維化が容易な組成とするために紡糸温度を 1 3 0 0 °C以下、 液相温度を紡糸温度より 5 5°C以上低くなるよう、 しかも耐酸 性が優れた組成となるよう複雑な条件を満たすよう検討され、 その結果は以下の ようであり本発明の組成を有するガラスの物性は従来の Eガラスに比べて遜色が ないものである。  To explain the present invention specifically, the spinning temperature should be lower than 130 ° C. and the liquidus temperature should be lower than the spinning temperature by more than 55 ° C. in order to make the composition easy to fibrillate. A study was made to satisfy complicated conditions to obtain an excellent composition, and the results are as follows. The physical properties of the glass having the composition of the present invention are comparable to those of the conventional E glass.
本発明は S i 02 、 B 2 03 、 A 12 03 、 C a〇、 R2 0 (Rは Na、 Kま たは L i) 、 F2 を必須成分として含み、 その割合が S i 02 5 9〜6 3重量％、 BsOa 0. 5〜4重量％、 A 1203 1 1〜1 6重量％、 C a O + Mg 0 2 0 〜2 6重量％、 MgO 0〜4重量％、 N a 2 0 0〜 1重量％、 K2 0 0〜 1重量％、 L i 2 0 0〜 1重量％、 N a 2 0 + K2 0 + L i 2 0 0. 2〜 1. 5重量％、 F 2 0. 0 5〜1. 0重量％である耐酸性に優れた繊維用ガラス 組成物である。 発明を実施するための最良の形態 The present invention is S i 0 2, B 2 0 3, A 12 0 3, C A_〇, R 2 0 (R is Na, K or the L i), the F 2 containing as essential components, the rate is S i 0 2 5 9~6 3 wt%, BsOa 0. 5~4 wt%, A 1 2 0 3 1 1~1 6 wt%, C a O + Mg 0 2 0 ~2 6 wt%, MgO 0 to 4 wt%, N a 2 0 0~ 1 wt%, K 2 0 0~ 1 wt%, L i 2 0 0~ 1 wt%, N a 2 0 + K 2 0 + L i 2 0 0. 2~ It is a glass composition for fibers having excellent acid resistance of 1.5% by weight and F 2 0.05 to 1.0% by weight. BEST MODE FOR CARRYING OUT THE INVENTION
本発明は S i 02 、 B 2 03 、 A 12 03 、 C aO、 R2 0 (Rは Na、 Kま たは L i) 、 F2 を必須成分として含み、 その割合が S i 02 5 9〜6 3重量％ (好ましくは 5 9〜 6 2重量％) 、 B 2 03 0. 5〜 4重量％ (好ましくは 1〜 4重量％、 特に好ましくは 1〜 2重量％) 、 A 12 03 1 1 -1 6重量％ (好ま しくは 1 2〜 1 6重量％、 特に好ましくは 1 2〜 1 5重量％) 、 C a O+MgO 2 0 -2 6重量％ (好ましくは 2 0〜 2 5重量％、 特に好ましくは 2 2〜 2 5重 量％) 、 MgO 0〜4重量％ (特に好ましくは 0. 5〜3重量％) 、 Na2 0 0〜 1重量％ (好ましくは 0. 1〜 1重量％、 特に好ましくは 0. 1〜 0. 5重 量％) 、 K2 0 0〜 1重量％ (好ましくは 0. 1〜 1重量％、 特に好ましく は 0. 1〜 0. 5重量％) 、 L i 2 0 0〜 1重量％ (好ましくは 0. 1 ~ 1 重量％、 特に好ましくは 0. 1〜0. 5重量％) 、 N a 2 0 + K2 O + L i 2 0 0. 2〜 1. 5重量％ (特に好ましくは 0. 2〜 1. 0重量％) 、 F 2 0. 0 5 〜 1. 0重量％ (好ましくは 0. 1〜し 0重量％、 特に好ましくは 0. 1〜 0. 6重量％) である耐酸性に優れた繊維用ガラス組成物である。 The present invention is S i 0 2, B 2 0 3, A 1 2 0 3, C aO, R 2 0 (R is Na, K or the L i), the F 2 containing as essential components, the rate is S i 0 2 5 9 to 63% by weight (preferably 59 to 62% by weight), B 2 0 3 0. 5 to 4% by weight (preferably 1 to 4% by weight, particularly preferably 1 to 2% by weight) ), A 1 2 0 3 1 1 -1 6 % by weight (preferred properly 1 2-1 6% by weight, particularly preferably 1 2-1 5 wt%), C a O + MgO 2 0 -2 6 wt% (preferably 2 0-2 5 wt%, particularly preferably 2 2-2 5 by weight%), MgO 0 to 4% by weight (particularly preferably 0.5 to 3 wt%), Na 2 0 0 to 1 weight % (Preferably 0.1 to 1% by weight, particularly preferably 0.1 to 0.5% by weight), K 2 0 0 to 1% by weight (preferably 0.1 to 1% by weight, particularly preferably Is 0.1 to 0.5% by weight), L i 200 0 to 1% by weight (preferably 0.1 to 1% by weight, particularly preferably 0.1 to 0.5% by weight), Na 20 + K 2 O + L i 2 0 0. 2~ 1. 5 wt% (particularly preferably 0.2 to 1.0 wt%), F 2 0. 0 5 ~ 1. 0 wt% (preferably 0. 1 to 0% by weight, particularly preferably 0.1 to 0.6% by weight).
本発明の好ましい態様は S i 02 、 B 2 03 、 A 12 03 、 C aO、 R2 0、 F2 を必須成分として含み、 その割合が S i 02 5 9〜6 3%、 B2 03 1〜4 %、 A " 03 1 2〜1 6%、 C aO+MgO 2 0〜2 5 %、 MgO 0〜4 %、 N a 2 0 0. 1〜1 %、 K2 0 0. 1〜 1 %、 N a 20 + K20 0. 2 〜1. 5%、 F2 0. 1〜 1 %である耐酸性に優れた繊維用ガラス組成物である c この組成において、 S i 02 が 5 9 %を下回ると耐酸性が十分でなく、 6 3 % を上回ると溶融温度が高くなると共に液相温度も高くなり、 紡糸性が悪くなる。 A preferred embodiment of the present invention is S i 0 2, B 2 0 3, A 1 2 0 3, C aO, the R 2 0, F 2 comprising as essential components, the ratio is S i 0 2 5 9~6 3% , B 2 0 3 1~4%, A "0 3 1 2~1 6%, C aO + MgO 2 0~2 5%, 0~4% MgO, N a 2 0 0. 1~1%, K 2 0 0. 1~ 1%, N a 2 0 + K 2 0 0. 2 ~1. 5%, c this is F 2 0.. 1 to textile glass composition excellent in acid resistance is 1% in the composition, S i 0 2 5 9% to below the acid resistance is not sufficient, liquidus temperature increases with the melting temperature above 6 3% increases, spinnability is poor.
B 2 03 が 0. 5%を下回ると溶融温度が高くなり、 4 %を上回ると耐酸性が 悪くなる。 B 2 0 3 is higher the melting temperature lower than 5% 0., acid resistance is deteriorated exceeds 4%.
A l 2 03 は 1 1 %を下回ると液相温度が高く紡糸性が悪くなり、 1 6%を上 回ると耐水性はよくなるが溶融温度が高くなりすぎる。 If the Al 2 O 3 is less than 11%, the liquidus temperature is high, and the spinnability is poor. If the Al 2 O 3 is more than 16%, the water resistance is improved but the melting temperature is too high.
C aO + MgOは、 2 0 %を下回ると溶融温度が高くなりすぎ、 2 6 %を上回 るとよい耐酸性が得られないと共に液相温度が高く紡糸性が悪くなる。  If the content of CaO + MgO is less than 20%, the melting temperature is too high, and if it is more than 26%, good acid resistance cannot be obtained, and the liquidus temperature is high, resulting in poor spinnability.
MgOは、 4 %を上回ると液相温度が高く紡糸性が悪くなる。  If MgO exceeds 4%, the liquidus temperature is high and spinnability deteriorates.
N a 2 0 + K2 0+ L i 2 0は、 0. 2 %を下回ると溶融温度が高くなり、 1. 5%を上回ると耐水性、 電気特性が悪くなるため最小限の配合量になるよう 検討されている。 N a 2 0 + K 2 0+ L i 2 0 includes a melting temperature lower than 2% 0. becomes high, water resistance exceeds 5% 1., the minimum amount for the electric characteristics may deteriorate It is being considered.
F2 は、 ガラスの溶融性を改良するものであるが、 0. 0 5 %を下回ると効果 が少なく、 1 %を上回っても効果の増加は少ない。 F 2 is is to improve the meltability of glass, 0.0 5% effect less Below, the small increase in the effect exceeds 1%.
その他の成分として、 原料不純物として通常必然的に混入する T i 02 、 F e 2 03 、 S r 0等や、 耐火物の浸蝕等から混入する Z r 02 等がそれぞれ 1 %以下程度混入することがある。 Other components, T i 0 2, F e 2 0 3 which normally inevitably mixed as raw material impurities, S r 0 or the like and, Z r 0 degree 2 or the like is less than 1%, respectively to mix the erosion or the like of the refractory May be mixed.
しかしながら、 その他の成分を除いた、 本発明で特定されているガラス組成物 成分の合計量は、 ガラス組成物全体の 9 9 . 0重量％以上であることが好ましい c 本発明のガラス組成物を得るには、 まず、 上記成分組成となるよう、 各種原料 鉱石を混合する。 However, the glass composition specified in the present invention, excluding other components, The total amount of the components is preferably 99.0% by weight or more of the entire glass composition. C To obtain the glass composition of the present invention, first, various raw materials ores are mixed so as to have the above-mentioned component composition. .
原料鉱石としては、 けい砂、 石灰石、 ドロマイ ト、 クレー、 コレマナイ ト、 蛍 石、 ソ一ダ灰などが使用できる。  Silica sand, limestone, dolomite, clay, colemanite, fluorite, soda ash, etc. can be used as raw material ores.
この原料配合の段階で、 紡糸の際の高温での溶融により揮発して減少する成分 ( B 2 03 、 F 2 など） については、 本発明で特定されている量よりも、 余分の 量の原料鉱石を入れて原料を調合する。 At the stage of the raw material formulation, the component that decreases volatilized by melting at high temperatures during spinning (such as B 2 0 3, F 2) , than the amount that is specified in the present invention, the excess amount Mix raw materials with raw ore.
そして、 混合された原料を公知の方法で、 本発明の組成を有するガラス繊維と する。  Then, the mixed raw materials are converted into glass fibers having the composition of the present invention by a known method.
例えば、 その原料をガラス溶融炉で溶融し、 プッシングと呼ばれる紡糸炉部分 に流し、 紡糸温度約 1， 2 0 0 °C〜 1， 3 0 0 で、 底面のノズルから流れ出す 溶融ガラスを急速に延伸し直径が 3〜2 δ ^ πιのガラス繊維 （本発明の繊維用ガ ラス組成物） を得る。 実施例  For example, the raw material is melted in a glass-melting furnace, passed through a spinning furnace called a pusher, and at a spinning temperature of about 1,200 ° C to 1,300, the molten glass flowing out of the nozzle at the bottom is rapidly drawn. A glass fiber having a diameter of 3 to 2 δ ^ πι (a glass composition for a fiber of the present invention) is obtained. Example
ガラス原料を溶融、 直径 1 3 mのガラス繊維を紡糸した。 ガラス繊維の組成 と試験結果を表 1に示す。  The glass raw material was melted and spun into glass fiber with a diameter of 13 m. Table 1 shows the glass fiber composition and test results.
表中の言葉の意味を以下に示す。  The meaning of the words in the table is shown below.
紡糸温度：粘度 1 0 0 0ボイズのときの溶融ガラスの温度。  Spinning temperature: the temperature of the molten glass when the viscosity is 100.
液相温度：その温度以上ではガラス中に結晶が存在しない温度。  Liquidus temperature: the temperature above which no crystals are present in the glass.
耐酸性％：ガラス繊維を、 8 0 °Cの 1 0 %硫酸中に 5時間浸潰したときの  Acid resistance%: when glass fiber is immersed in 10% sulfuric acid at 80 ° C for 5 hours
重量減少率。  Weight loss rate.
([浸漬前の重量ー浸漬後の重量] / [浸漬前の重量] ) X 1 0 0 (%) 実施例 1 一 4は本発明のガラス組成であり、 比較例 1は従来の Eガラス繊維、 比較例 2— 5は本発明の範囲外の組成、 参考例は耐酸性ガラスの E C Rガラス繊 維である。  ([Weight before immersion−weight after immersion] / [weight before immersion]) X 100 (%) Examples 1 to 4 are glass compositions of the present invention, and Comparative Example 1 is a conventional E glass fiber. Comparative Examples 2-5 are compositions outside the scope of the present invention, and Reference Examples are ECR glass fibers of acid-resistant glass.
比較例 1の Eガラス繊維と本発明を比較すると耐酸性は大幅に改善されており、 また耐酸性の必要な用途に使用される E C Rガラス繊維と同等の耐酸性を有する ことがわかる。 また各実施例のガラスの他の特性は Eガラスと同等乃至それ以上 でめる。 When the E glass fiber of Comparative Example 1 is compared with the present invention, the acid resistance is significantly improved, It also shows that it has the same acid resistance as ECR glass fiber used for applications requiring acid resistance. Other characteristics of the glass of each embodiment can be equal to or higher than that of the E glass.
比較例 1 一 5は本発明の組成と類似の組成であるが、 比較例 2— 4は、 耐酸性 はよいものの紡糸温度が高くなりすぎ、 比較例 5は耐酸性が不十分でありいずれ も実用的ではない。  Comparative Examples 1 to 5 have compositions similar to the composition of the present invention, whereas Comparative Examples 2 to 4 have good acid resistance, but the spinning temperature is too high, and Comparative Example 5 has insufficient acid resistance and Not practical.
本発明のガラス組成物は、 原料に特殊な成分を必要とせず、 Eガラス組成の繊 維と同様の成分からなっており、 原料価格が安いにもかかわらず、 高価な Z n O と T i 0 2 を必須とした従来の耐酸性ガラス、 E C Rガラス （参考例） と同等の 性能と紡糸のしゃすさを有していることがわかる。 The glass composition of the present invention does not require any special components in the raw materials, and is composed of the same components as the fibers of the E glass composition. Although the raw material prices are low, the expensive ZnO and Ti are used. 0 2 required and the conventional acid-resistant glass, ECR glass (reference example) and it is found to have of Chasse of equivalent performance and spinning.
表 1 組成 実施例 参考例 w t 0 vo Table 1 Composition Example Reference Example w t 0 vo
1 2 3 4 1 2 3 4 5  1 2 3 4 1 2 3 4 5
S i 02 J CO9. Q 0 UVJ.0 fi1 ? fiク 4 fin n fiク n ϋθ. V 59.0S i 0 2 J CO9. Q 0 UVJ.0 fi1? Fi 4 n fin n fi n ϋθ. V 59.0
B2 03 0， ) 1 π 1 A リ霧 *τ 1 π 1 f) 一B 2 0 3 0,) 1 π 1 A fog * τ 1 π 1 f) one
A I 2 03 10， \J 119 Πj 114 *τ. O Q π n 1R u* 0 R 14 0 14 π 12.0AI 2 0 3 10, \ J 119 Πj 114 * τ. OQ π n 1R u * 0 R 14 0 14 π 12.0
C a 0 22.0 22.0 20.0 19.0 22.3 19.0 20.0 19.0 22.0 21.6C a 0 22.0 22.0 20.0 19.0 22.3 19.0 20.0 19.0 22.0 21.6
Mg 0 0.5 1.0 2.0 3.5 0.8 1.2 0.7 0.0 0.4 2.7Mg 0 0.5 1.0 2.0 3.5 0.8 1.2 0.7 0.0 0.4 2.7
T i 02 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 2.1T i 0 2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 2.1
Na2 0 0.5 0.5 0.6 0.6 0.4 0.5 0.5 0.5 0.5 0.3 2 0 πク Λ U, L 0 1 υ. U. L u. Λ U.0 L Π Na 2 0 0.5 0.5 0.6 0.6 0.4 0.5 0.5 0.5 0.5 0.3 2 0 π Λ U, L 0 1 υ. U.L u.Λ U.0 L Π
U.9 L U. 0.1 U.9 L U. 0.1
F e Λ ク Λ Λ ク n F e Λ n n n
2 03 U. U.ク 2 0 3 UU
C 9 u. Λ ク Λ ク  C 9 u.
U. L 0.2 U. L 0.2
Z n 0 2.0Z n 0 2.0
F2 0.6 0.6 0.7 0.5 0.6 0.7 0.7 0.5 0.5 試験結果 ϋ¾糸'皿度 1255 1261 1287 1278 1201 1332 1318 1319 1252 1250 液相温度 1184 1180 1192 1215 1065 1284 1260 1259 1139 1160 耐酸性 0.8 0.6 0.4 0.4 28.7 0.4 0.7 0.5 8.9 0.6 F 2 0.6 0.6 0.7 0.5 0.6 0.7 0.7 0.5 0.5 Test result ϋ¾ Thread thickness 1255 1261 1287 1278 1201 1332 1318 1319 1252 1250 Liquidus temperature 1184 1180 1192 1215 1065 1284 1260 1259 1139 1160 Acid resistance 0.8 0.6 0.4 0.4 28.7 0.4 0.7 0.5 8.9 0.6
産業上の利用可能性 Industrial applicability
以上説明したように、 本発明のガラス繊維は、 Na2 0 + K2 0の量を必要最 小限度の含有量に抑え、 S i 02 、 B2 03 、 A l 2 03 、 C aO、 F2 を必須 成分として組合わせて耐酸性に優れ、 しかも紡糸温度を 1 3 0 0 °C以下、 液相温 度を紡糸温度より 5 5°C以上低くすることに成功したので、 耐酸性に優れたガラ ス繊維の生産が可能になつた。 As described above, the glass fiber of the present invention suppresses the amount of Na 2 0 + K 20 to the minimum necessary content, and obtains Si 0 2 , B 2 0 3 , Al 2 0 3 , C 2 aO-, excellent acid resistance in combination with F 2 as an essential component, yet the spinning temperature 1 3 0 0 ° C or less, since the liquid phase temperature was successfully lowered 5 5 ° C or more than the spinning temperature, acid It has become possible to produce glass fibers with excellent properties.
また、 高価で入手に不安のある B 2 03 を減少させたので原料価格も安くなる という経済的な効果もある。 In addition, there is also the economic effect of raw material prices also be cheaper because reduced the B 2 0 3 with anxiety to get expensive.

Claims

請 求 の 範 囲 The scope of the claims
1. S i 02 、 B 2 03 、 A 1 03 、 C a 0、 R2 0 (Rは N a、 Kまたは L i ) . F2 を必須成分として含み、 その割合が S i 02 5 9〜6 3重量％、 B 2 03 0. 5〜4重量％、 A 1 03 1 1〜1 6重量％、 C a O+MgO 2 0〜2 6重量％、 MgO 0〜4重量％、 Na2 0 + K2 O + L i 2 0 0. 2 〜1. 5重量％ (ただし、 Na2 0、 K2 0及び L i 2 0の含有量は、 それぞれ、 0〜1重量％の範囲内） 、 F 2 0. 0 5〜1. 0重量％である繊維用ガラス組成 物。 1. S i 0 2, B 2 0 3, A 1 0 3, C a 0, R 2 0 (R is N a, K or L i) comprising as. F 2 essential components, the ratio is S i 0 2 5 9 to 6 3% by weight, B 2 0 3 0.5 to 4% by weight, A 10 3 1 1 to 16% by weight, CaO + MgO 2 0 to 26% by weight, MgO 0 to 4 wt%, Na 2 0 + K 2 O + L i 2 0 0. 2 ~1. 5 wt% (provided that the content of Na 2 0, K 2 0 and L i 2 0, respectively, 0-1 weight %), And F 2 0.05 to 1.0% by weight.
2. S i 02 力く 5 9〜 6 3重量％、 B 2 03 が 1〜 4重量％、 A 12 03 が 1 2〜 1 6重量％、 C aO + MgOが 2 0〜2 5重量％、 MgOが0〜4重量％、 N a 0が 0. 1〜1重量％、 K2 0が 0. 1〜 1重量％、 N a 2 0 + K2 0が 0. 2〜1. 5重量％、 F2 が 0. 1〜 1重量％である繊維用ガラス組成物。 2. S i 0 2 Chikaraku 5 9-6 3 wt%, B 2 0 3 is 1-4 wt%, A 1 2 0 3 1 2-1 6 wt%, C aO + MgO is 2 0-2 5 wt%, MgO 0 to 4 wt%, N a 0 is from 0.1 to 1 wt%, K 2 0 is from 0.1 to 1 wt%, N a 2 0 + K 2 0 is from 0.2 to 1 . 5 wt%, F 2 fibers glass composition is from 0.1 to 1 wt%.
3. S i 02 が 5 9〜6 2重量％である請求項 1に記載の繊維用ガラス組成物 c 3. S i 0 2 5 9-6 2 Fiber glass composition according to claim 1 by weight% c
4. B 2 03 が 1〜2重量％である請求項 1に記載の繊維用ガラス組成物。4. B 2 0 3 fiber glass composition according to claim 1 which is 1 to 2 wt%.
5. A 12 03 が 1 2〜1 5重量％である請求項 1に記載の繊維用ガラス組成 物。 5. A 1 2 0 3 fibers glass composition according to claim 1 which is 1 2 to 1 5% by weight.
6. C aO+MgOが 2 2〜2 5重量％である請求項 1に記載の繊維用ガラス 組成物。  6. The glass composition for fibers according to claim 1, wherein the content of CaO + MgO is 22 to 25% by weight.
7. 80が0. 5〜3重量％である請求項 1に記載の繊維用ガラス組成物。7. The glass composition for fibers according to claim 1, wherein 7.80 is 0.5 to 3% by weight.
8. Na2 0 + K2 O + L i 2 0が 0. 2〜1. 0重量％である請求項 1に記 載の繊維用ガラス組成物。 8. Na 2 0 + K 2 O + L i 2 0 is 0.2 to 1.0 fiber glass composition for serial placement in claim 1 by weight.
9. F2 が 0. 1〜0. 6重量％である請求項 1に記載の繊維用ガラス組成物 c 9. F 2 is 0.1 to 0.6% by weight fiber glass composition for c according to claim 1,
PCT/JP1998/002818 1997-07-04 1998-06-24 Glass composition for fibers WO1999001393A1 (en)

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WO2001032576A1 (en) 1999-11-04 2001-05-10 Saint Gobain Vetrotex France S.A. Glass yarns, composite thereof, method for making same and reinforcing glass composition
EP1496026A1 (en) * 2003-07-07 2005-01-12 Johns Manville International, Inc. Low boron e-glass composition
FR2867776A1 (en) * 2004-03-17 2005-09-23 Saint Gobain Vetrotex GLASS YARNS FOR REINFORCING ORGANIC AND / OR INORGANIC MATERIALS
WO2008142347A2 (en) * 2007-05-23 2008-11-27 Saint-Gobain Technical Fabrics Europe Glass yarns suitable for reinforcing organic and/or inorganic materials
JP2012519144A (en) * 2009-03-02 2012-08-23 巨石集▲団▼有限公司 New glass fiber composition
WO2016068303A1 (en) * 2014-10-30 2016-05-06 旭ファイバーグラス株式会社 Transparent abs resin composition
KR101748496B1 (en) 2015-11-09 2017-06-19 주식회사 케이씨씨 Batch Composition for Preparing Long Glass Fiber Using Anorthite
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JPS62162649A (en) * 1986-01-08 1987-07-18 Nippon Sheet Glass Co Ltd Glass composition for fiber

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US7022634B2 (en) 2003-07-07 2006-04-04 Johns Manville Low boron E-glass composition
EP1496026A1 (en) * 2003-07-07 2005-01-12 Johns Manville International, Inc. Low boron e-glass composition
JP2005029465A (en) * 2003-07-07 2005-02-03 Johns Manville Internatl Inc E-glass composition containing low boron
US7811954B2 (en) 2004-03-17 2010-10-12 Saint-Gobain Technical Fabrics Europe Glass yarn for reinforcing organic and/or inorganic materials
WO2005093227A3 (en) * 2004-03-17 2005-11-24 Saint Gobain Vetrotex Glass yarn for reinforcing organic and/ or inorganic materials
WO2005093227A2 (en) * 2004-03-17 2005-10-06 Saint-Gobain Vetrotex France S.A. Glass yarn for reinforcing organic and/ or inorganic materials
CN1934043A (en) * 2004-03-17 2007-03-21 法国圣戈班韦特罗特斯有限公司 Glass yarn for reinforcing organic and/ or inorganic materials
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WO2008142347A2 (en) * 2007-05-23 2008-11-27 Saint-Gobain Technical Fabrics Europe Glass yarns suitable for reinforcing organic and/or inorganic materials
WO2008142347A3 (en) * 2007-05-23 2009-02-19 Saint Gobain Technical Fabrics Glass yarns suitable for reinforcing organic and/or inorganic materials
JP2012519144A (en) * 2009-03-02 2012-08-23 巨石集▲団▼有限公司 New glass fiber composition
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