CN102718406B - The glass fiber with low dielectric constant that a kind of wire-drawing temperature is low - Google Patents
The glass fiber with low dielectric constant that a kind of wire-drawing temperature is low Download PDFInfo
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 84
- 238000005491 wire drawing Methods 0.000 title claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 238000005352 clarification Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract description 11
- 229910004298 SiO 2 Inorganic materials 0.000 abstract description 8
- 229910004261 CaF 2 Inorganic materials 0.000 abstract description 6
- 229910021193 La 2 O 3 Inorganic materials 0.000 abstract description 6
- 229910018068 Li 2 O Inorganic materials 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 5
- 229910052708 sodium Inorganic materials 0.000 abstract description 5
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 239000012779 reinforcing material Substances 0.000 abstract description 3
- 239000011521 glass Substances 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004031 devitrification Methods 0.000 description 7
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
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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
-
- 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
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
- C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
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- Engineering & Computer Science (AREA)
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Abstract
本发明公开了一种拉丝温度低的低介电常数玻璃纤维，其制备方法如下：原料组成以重量百分比表示：48wt％～55wt％的SiO2；12wt％～16wt％的Al2O3；22wt％～27wt％的B2O3；3～7wt％的CaO；0.5wt％～6wt％的La2O3；0～2wt％的CaF2；0～1wt％的Na2O、K2O和Li2O，Na2O、K2O和Li2O以任意比例混合；0～0.45wt％的MgO；0～0.45wt％的SO3；0～0.45wt％的TiO2；0～0.45wt％的Fe2O3；各种原料输送至混合仓中充分混合均匀，送入池窑，在1600℃温度下熔化、澄清、均化8h后，通过4000孔铂金漏板流出，在拉丝机带动下，即得到低介电常数玻璃纤维。本发明提供的玻璃纤维的耐水性优于E玻璃纤维和D玻璃纤维，而且与树脂附着力好、易于后续加工，特别适合作印刷电路板的增强材料。The invention discloses a glass fiber with low dielectric constant and low drawing temperature. The preparation method is as follows: the composition of raw materials is represented by weight percentage: 48wt%-55wt% of SiO 2 ; 12wt%-16wt% of Al 2 O 3 ; 22wt% %~27wt% of B 2 O 3 ; 3~7wt% of CaO; 0.5wt%~6wt% of La 2 O 3 ; 0~2wt% of CaF 2 ; 0~1wt% of Na 2 O, K 2 O and Li 2 O, Na 2 O, K 2 O and Li 2 O mixed in any proportion; 0-0.45wt% MgO; 0-0.45wt% SO 3 ; 0-0.45wt% TiO 2 ; 0-0.45wt% % Fe 2 O 3 ; all kinds of raw materials are transported to the mixing chamber, fully mixed evenly, sent to the pool kiln, melted, clarified and homogenized at 1600°C for 8 hours, and flow out through the 4000-hole platinum drain plate, driven by the wire drawing machine Next, the low dielectric constant glass fiber is obtained. The water resistance of the glass fiber provided by the invention is better than that of E glass fiber and D glass fiber, and it has good adhesion to resin and is easy for subsequent processing, and is especially suitable as a reinforcing material for printed circuit boards.
Description
技术领域 technical field
本发明涉及一种拉丝温度低的低介电常数和低介电损耗的玻璃纤维，它可用作印刷电路板的增强材料。The invention relates to a low dielectric constant and low dielectric loss glass fiber with low drawing temperature, which can be used as a reinforcing material for printed circuit boards.
背景技术 Background technique
近十几年来，由于电子信息产业的飞跃发展，印刷电路板向高密度与多层、超多层方向发展，要求覆铜板不仅充当基板，还要发展信号传输线功能、特性阻抗精度控制功能，并在多层板中充当内藏无源元件功能等。这就要求材料具有低的介电常数和介电损耗。这是因为材料的介电常数越小，则信号传播速度越快；在一定的传播频率下，材料的介质损耗越小，则传播损耗越小。印刷电路板通常由树脂和玻璃纤维组成。常规用于印刷电路板的树脂的介电性能是令人满意的，因而制约印刷电路板上述特性的关键，在于高质量、高品质的玻璃纤维材料。传统用于印刷电路板的E玻璃纤维的介电常数在7左右，不能满足电路板越来越快的处理速度的要求，因此开发较E玻璃具有更低的介电常数和介电损耗的玻璃纤维成为主要的研发方向。In the past ten years, due to the rapid development of the electronic information industry, printed circuit boards have developed in the direction of high density, multi-layer, and super-multi-layer. It acts as a built-in passive component function in a multilayer board, etc. This requires materials with low dielectric constant and dielectric loss. This is because the smaller the dielectric constant of the material, the faster the signal propagation speed; at a certain propagation frequency, the smaller the dielectric loss of the material, the smaller the propagation loss. Printed circuit boards are usually composed of resin and fiberglass. The dielectric properties of resins conventionally used for printed circuit boards are satisfactory, so the key to restricting the above characteristics of printed circuit boards lies in high-quality, high-quality glass fiber materials. The dielectric constant of E glass fiber traditionally used in printed circuit boards is around 7, which cannot meet the requirements of faster and faster processing speeds of circuit boards. Therefore, glass with lower dielectric constant and dielectric loss than E glass has been developed. Fiber has become the main research and development direction.
针对这种情况，国内外做了不少研究，开发了一些低介电常数和低介电损耗的玻璃纤维。如典型的D玻璃纤维的组成是：SiO272-76％，Al2O30-5％，B2O320-25％，Na2O+K2O3-5％。其介电常数为4.1左右，介电损耗为8×10-4左右。但是D玻璃的SiO2含量高，导致拉丝温度高达1400℃左右，玻璃纤维增强层压板的钻孔性能差，不利于后续加工，耐水性也很差，容易引起纤维与树脂的剥离。法国的圣戈班维特罗特斯(Vetrotex)公司申请的专利02810477.3介绍了一种低介电常数玻璃纤维的典型组成为：SiO253％，Al2O315.8％，B2O319.6％，Na2O+K2O0.5％，CaO5.3％，MgO3.9％，P2O51.2％。相应的介电常数为4.9左右，拉丝温度在1350℃左右。日本日东纺织株式会社专利96194439.0介绍了一种低介电常数玻璃纤维的组成，SiO250-60％，Al2O310-20％，B2O320-30％，Na2O+K2O+Li2O0.5％，CaO0-5％，MgO0-4％，Ti2O0.5-4％。，介电常数在4.2-4.5左右，拉丝温度在1280℃以上。美国AGY控股公司的专利200780048402.7介绍了一种低介电常数玻璃纤维的组成如下：SiO252-60％，Al2O311-16％，B2O320-30％，，CaO4-8％。相应的介电常数4.5-5，介电损耗≤5×10-4，拉丝温度在1350℃左右。泰山玻璃纤维股份有限公司的专利200610166224.5提供了一种低介电常数玻璃纤维，其组成为：SiO250-60％，Al2O36-9.5％，B2O330.5-35％，CaO0-5％，ZnO0-5％，TiO20.5-5％，其中ZnO代替部分CaO、MgO的作用使介电常数降低。相应的介电常数3.9-4.4，介电损耗(4-8.5)×10-4，拉丝温度在1350℃左右。四川省玻纤集团有限公司的专利200910216020.1介绍了一种低介电常数玻璃纤维组成为：SiO250-60％，Al2O312-18％，B2O321-27％，CaO0-1.8％，MgO0.5-3.2％，ZnO0.5-3.2％，TiO20.4-4％，CaF20.5％-3％，CeO0.2％-0.6％。该组成的玻璃纤维介电常数为4.2-4.6，从熔化温度可以推测其拉丝温度也在1350℃左右。上述开发的玻璃纤维组成虽然在介电性能方面能满足使用要求，但是玻璃的熔融性能差，拉丝温度高(均在1280℃以上，大部分在1350℃左右)，导致拉丝作业困难，同时对窑炉温度要求苛刻，会降低池窑寿命，因此生成成本较高，难于大规模生产。In response to this situation, a lot of research has been done at home and abroad, and some glass fibers with low dielectric constant and low dielectric loss have been developed. For example, the composition of typical D glass fiber is: SiO 2 72-76%, Al 2 O 3 0-5%, B 2 O 3 20-25%, Na 2 O+K 2 O 3-5%. Its dielectric constant is about 4.1, and its dielectric loss is about 8×10 -4 . However, the high SiO2 content of D glass leads to a high drawing temperature of about 1400°C. The drilling performance of glass fiber reinforced laminates is poor, which is not conducive to subsequent processing. The water resistance is also poor, which easily causes the peeling of fibers and resins. The patent 02810477.3 applied by the Saint-Gobain Vetrotex (Vetrotex) company in France describes a typical composition of a low dielectric constant glass fiber: SiO 2 53%, Al 2 O 3 15.8%, B 2 O 3 19.6%, Na 2 O+K 2 O 0.5%, CaO 5.3%, MgO 3.9%, P 2 O 5 1.2%. The corresponding dielectric constant is about 4.9, and the drawing temperature is about 1350°C. Japan's Nitto Textile Co., Ltd. patent 96194439.0 introduces a low dielectric constant glass fiber composition, SiO 2 50-60%, Al 2 O 3 10-20%, B 2 O 3 20-30%, Na 2 O+ K 2 O+Li2O 0.5%, CaO 0-5%, MgO 0-4%, Ti 2 O 0.5-4%. , the dielectric constant is around 4.2-4.5, and the drawing temperature is above 1280°C. The patent 200780048402.7 of the American AGY Holding Company introduces a low dielectric constant glass fiber composition as follows: SiO 2 52-60%, Al 2 O 3 11-16%, B 2 O 3 20-30%,, CaO4-8 %. The corresponding dielectric constant is 4.5-5, the dielectric loss is ≤5×10 -4 , and the drawing temperature is around 1350°C. The patent 200610166224.5 of Taishan Glass Fiber Co., Ltd. provides a low dielectric constant glass fiber, the composition of which is: SiO 2 50-60%, Al 2 O 3 6-9.5%, B 2 O 3 30.5-35%, CaO0 -5%, ZnO 0-5%, TiO 2 0.5-5%, where ZnO replaces part of CaO and MgO to reduce the dielectric constant. The corresponding dielectric constant is 3.9-4.4, the dielectric loss is (4-8.5)×10 -4 , and the drawing temperature is about 1350°C. The patent 200910216020.1 of Sichuan Fiberglass Group Co., Ltd. introduces a low dielectric constant glass fiber composition: SiO 2 50-60%, Al 2 O 3 12-18%, B 2 O 3 21-27%, CaO0- 1.8%, MgO0.5-3.2%, ZnO0.5-3.2%, TiO2 0.4-4%, CaF20.5%-3%, CeO0.2%-0.6%. The glass fiber dielectric constant of this composition is 4.2-4.6, and it can be inferred from the melting temperature that its drawing temperature is also around 1350°C. Although the above-mentioned developed glass fiber composition can meet the requirements of use in terms of dielectric properties, the glass has poor melting properties and high drawing temperature (all above 1280°C, most of them are around 1350°C), which makes the drawing operation difficult, and at the same time, the kiln Strict furnace temperature requirements will reduce the life of the tank kiln, so the production cost is high and it is difficult to produce on a large scale.
发明内容 Contents of the invention
本发明的目的在于克服现有技术的不足，提供一种用于印刷电路板的低介电常数玻璃纤维。本发明提供的玻璃纤维具有低的介电常数和介电损耗，耐水性好，而拉丝温度在1250～1280℃之间，易于生产。The purpose of the present invention is to overcome the deficiencies of the prior art and provide a glass fiber with low dielectric constant for printed circuit boards. The glass fiber provided by the invention has low dielectric constant and dielectric loss, good water resistance, and the drawing temperature is between 1250-1280 DEG C, which is easy to produce.
一种拉丝温度低的低介电常数玻璃纤维，其制备方法如下：原料组成以重量百分比表示：48wt％～55wt％的SiO2；12wt％～16wt％的Al2O3；22wt％～27wt％的B2O3；3～7wt％的CaO；0.5wt％～6wt％的La2O3；0～2wt％的CaF2；0～1wt％的Na2O、K2O和Li2O，Na2O、K2O和Li2O以任意比例混合；0～0.45wt％的MgO；0～0.45wt％的SO3；0～0.45wt％的TiO2；0～0.45wt％的Fe2O3；各种原料输送至混合仓中充分混合均匀，送入池窑，在1600℃温度下熔化、澄清、均化8h后，通过4000孔铂金漏板流出，在拉丝机带动下，即得到低介电常数玻璃纤维。A low dielectric constant glass fiber with low drawing temperature, the preparation method of which is as follows: the composition of raw materials is represented by weight percentage: 48wt%-55wt% of SiO2 ; 12wt%-16wt% of Al2O3 ; 22wt %-27wt% 3~7wt% of CaO; 0.5wt%~6wt% of La 2 O 3 ; 0~ 2wt % of CaF 2 ; 0~1wt% of Na 2 O, K 2 O and Li 2 O, Na 2 O, K 2 O and Li 2 O mixed in any proportion; 0-0.45wt% MgO; 0-0.45wt% SO 3 ; 0-0.45wt% TiO 2 ; 0-0.45wt% Fe 2 O 3 ; Various raw materials are transported to the mixing chamber, fully mixed evenly, sent to the pool kiln, melted, clarified, and homogenized at 1600 °C for 8 hours, and flow out through the 4000-hole platinum drain plate, driven by the wire drawing machine, to obtain Low dielectric constant glass fiber.
本发明中，各组分成分如上的限定理由如下：In the present invention, the above-mentioned limitation reason of each component composition is as follows:
在所述玻璃纤维中，SiO2是形成玻璃及玻璃纤维的骨架氧化物之一，当SiO2不足48wt％时，玻璃纤维的耐水性降低，介电常数偏大；当SiO2超过53wt％时，玻璃纤维的高温粘度大，拉丝温度高。因此本发明中，SiO2含量为48wt％～53wt％，In the glass fiber, SiO2 is one of the skeleton oxides that form glass and glass fiber. When SiO2 is less than 48wt%, the water resistance of glass fiber decreases and the dielectric constant is too large; when SiO2 exceeds 53wt%. , the high temperature viscosity of glass fiber is high, and the drawing temperature is high. Therefore in the present invention, SiO 2 content is 48wt%～53wt%,
Al2O3也是形成玻璃的骨架氧化物之一，当Al2O3不足12wt％时，玻璃纤维的耐水性降低，介电常数偏大；当Al2O3超过16wt％时，玻璃纤维的高温粘度大，拉丝温度高。因此本发明中，Al2O3含量为12wt％～16wt％，Al 2 O 3 is also one of the skeleton oxides that form glass. When Al 2 O 3 is less than 12wt%, the water resistance of glass fiber decreases and the dielectric constant is too large; when Al 2 O 3 exceeds 16wt%, the glass fiber High temperature viscosity, high drawing temperature. Therefore in the present invention, the content of Al 2 O 3 is 12wt%～16wt%,
B2O3也是形成玻璃的骨架氧化物之一，当B2O3不足22wt％时，玻璃纤维的高温粘度大，拉丝温度高，介电常数高；当B2O3超过27wt％时，玻璃纤维的耐水性降低。因此本发明中，B2O3的含量为22wt％～27wt％。B 2 O 3 is also one of the skeleton oxides that form glass. When B 2 O 3 is less than 22wt%, the high-temperature viscosity of glass fiber is high, the drawing temperature is high, and the dielectric constant is high; when B 2 O 3 exceeds 27wt%, The water resistance of glass fiber is reduced. Therefore, in the present invention, the content of B 2 O 3 is 22wt%-27wt%.
CaO是玻璃网络调整体，添加CaO可以降低玻璃纤维的熔制温度，提高玻璃纤维的耐水性；但是，当CaO超过6wt％时，玻璃纤维的介电常数会增大。因此本发明中，CaO含量为3～6wt％。CaO is a glass network regulator, adding CaO can reduce the melting temperature of glass fiber and improve the water resistance of glass fiber; however, when CaO exceeds 6wt%, the dielectric constant of glass fiber will increase. Therefore, in the present invention, the CaO content is 3-6 wt%.
La2O3的引入可以显著降低玻璃纤维的高温粘度，降低其失透温度的上限，大大增加失透温度上限和拉丝温度之差，从而改善玻璃纤维的工艺性和操作性。La2O3添加量不足0.5wt％时，工艺性和操作性改善不明显；La2O3添加量超过6wt％时，玻璃纤维的介电常数会增大。因此，本发明中，La2O3含量为0.5wt％～6wt％。The introduction of La 2 O 3 can significantly reduce the high-temperature viscosity of glass fiber, reduce the upper limit of devitrification temperature, and greatly increase the difference between the upper limit of devitrification temperature and drawing temperature, thereby improving the processability and operability of glass fiber. When the amount of La 2 O 3 added is less than 0.5wt%, the manufacturability and operability are not significantly improved; when the amount of La 2 O 3 added exceeds 6wt%, the dielectric constant of the glass fiber will increase. Therefore, in the present invention, the content of La 2 O 3 is 0.5wt%˜6wt%.
CaF2在玻璃纤维中的主要作用是助熔剂，能够降低玻璃纤维的高温粘度。CaF2含量不足0.5wt％时，助熔作用不明显；CaF2含量超过3wt％时，会加剧玻璃纤维的挥发和对耐火材料的侵蚀，而且得到的玻璃纤维易于分相。因此本发明中，CaF2的含量为0.5wt％～3wt％。The main role of CaF 2 in glass fiber is as a flux, which can reduce the high temperature viscosity of glass fiber. When the content of CaF 2 is less than 0.5wt%, the fluxing effect is not obvious; when the content of CaF 2 exceeds 3wt%, it will intensify the volatilization of glass fibers and the erosion of refractory materials, and the obtained glass fibers are easy to phase separation. Therefore, in the present invention, the content of CaF 2 is 0.5wt%-3wt%.
在本发明提供的玻璃纤维中，Na2O、K2O和Li2O等碱金属氧化物能够降低玻璃纤维的介电损耗，但是其含量超过1wt％时，玻璃纤维的介电损耗大，耐水性变差，因此，本发明中，Na2O、K2O和Li2O总含量为0～1wt％。In the glass fiber provided by the present invention, alkali metal oxides such as Na 2 O, K 2 O and Li 2 O can reduce the dielectric loss of the glass fiber, but when its content exceeds 1 wt%, the dielectric loss of the glass fiber is large, Water resistance becomes poor, therefore, in the present invention, the total content of Na 2 O, K 2 O and Li 2 O is 0-1 wt%.
在本发明提供的玻璃纤维中，MgO作为玻璃原料中的杂质引入，其含量过高时，不利于降低玻璃纤维的介电常数和介电损耗，还会增加玻璃纤维的分相倾向。在本发明中，所述MgO的含量为0～0.45wt％。In the glass fiber provided by the present invention, MgO is introduced as an impurity in the glass raw material. When the content is too high, it is not conducive to reducing the dielectric constant and dielectric loss of the glass fiber, and it will also increase the phase separation tendency of the glass fiber. In the present invention, the content of MgO is 0-0.45wt%.
在本发明提供的玻璃纤维中，SO3作为玻璃原料中的杂质引入，其含量过高时，不利于降低玻璃纤维的介电损耗。在本发明中，所述SO3的含量为0～0.45wt％。In the glass fiber provided by the present invention, SO 3 is introduced as an impurity in the glass raw material, and when its content is too high, it is not conducive to reducing the dielectric loss of the glass fiber. In the present invention, the content of SO 3 is 0-0.45wt%.
在本发明提供的玻璃纤维中，TiO2作为玻璃原料中的杂质引入，其含量过高时，不利于降低玻璃纤维的介电常数；含量过低，会大幅度增加玻璃纤维原料的成本。在本发明中，所述TiO2的含量为0～0.45wt％。In the glass fiber provided by the present invention, TiO2 is introduced as an impurity in the glass raw material. When the content is too high, it is not conducive to reducing the dielectric constant of the glass fiber; if the content is too low, the cost of the glass fiber raw material will be greatly increased. In the present invention, the content of TiO 2 is 0-0.45wt%.
在所述玻璃纤维中，Fe2O3作为玻璃原料中的杂质引入，其含量过高，不利于降低玻璃纤维的介电常数和介电损耗；含量过低，原料成本会升高。在本发明中，Fe2O3的含量为0～0.45wt％。In the glass fiber, Fe 2 O 3 is introduced as an impurity in the glass raw material. If the content is too high, it is not conducive to reducing the dielectric constant and dielectric loss of the glass fiber; if the content is too low, the raw material cost will increase. In the present invention, the content of Fe 2 O 3 is 0-0.45wt%.
本发明对所述玻璃纤维的制备方法没有特殊限制，可以按照以下方法制备：The present invention does not have special limitation to the preparation method of described glass fiber, can prepare according to the following method:
按照实际配方计算好各原料的添加量，准确称量后将各种原料输送至混合仓中充分混合均匀，再经窑头料仓送入池窑，在1400℃～1650℃温度下熔化、澄清、均化后，通过铂金漏板流出，在拉丝机带动下，即得到低介电常数玻璃纤维。Calculate the addition amount of each raw material according to the actual formula, and after accurate weighing, transport the various raw materials to the mixing bin to mix them evenly, and then send them to the pool kiln through the kiln head bin, where they are melted and clarified at a temperature of 1400°C to 1650°C , After homogenization, it flows out through the platinum bushing, and is driven by the wire drawing machine to obtain glass fibers with low dielectric constant.
采用本发明组成和重量百分比例制备的玻璃纤维，室温下，频率为1MHz时介电常数为4.5～5.0，介电损耗为5～9×10-4。The glass fiber prepared by using the composition and weight percentage of the present invention has a dielectric constant of 4.5-5.0 and a dielectric loss of 5-9×10 -4 at a frequency of 1 MHz at room temperature.
与现有技术相比，本发明具有下列特点和有益效果：(1)本发明提供的玻璃纤维具有后低的介电常数和介电损耗，室温下，频率为1MHz时介电常数为4.1～4.6，介电损耗为5～9×10-4。(2)本发明提供的玻璃纤维的拉丝温度在1250～1280℃之间，低于其它发明的1350℃左右的拉丝温度，而且本发明提供的玻璃纤维的拉丝温度与失透上限温度之差均大于100℃，部分甚至高于200℃，非常有利于拉丝作业，易于生产。(3)本发明提供的玻璃纤维的耐水性优于E玻璃纤维和D玻璃纤维，而且与树脂附着力好、易于后续加工，特别适合作印刷电路板的增强材料。Compared with the prior art, the present invention has the following characteristics and beneficial effects: (1) the glass fibers provided by the present invention have low dielectric constant and dielectric loss, and at room temperature, the dielectric constant is 4.1～2 when the frequency is 1MHz. 4.6, the dielectric loss is 5 to 9×10 -4 . (2) The drawing temperature of the glass fiber provided by the present invention is between 1250 and 1280°C, which is lower than the drawing temperature of about 1350°C in other inventions, and the difference between the drawing temperature and the devitrification upper limit temperature of the glass fiber provided by the present invention is even It is higher than 100°C, and some are even higher than 200°C, which is very conducive to wire drawing and easy to produce. (3) The water resistance of the glass fiber provided by the present invention is better than that of E glass fiber and D glass fiber, and it has good adhesion to resin and is easy for subsequent processing, and is especially suitable as a reinforcing material for printed circuit boards.
具体实施方式 detailed description
以下结合具体实施例，对本发明进行详细说明。The present invention will be described in detail below in conjunction with specific embodiments.
实施例1～7Examples 1-7
按照表1所示的配方、按照以下方法制备玻璃纤维：According to the formula shown in table 1, glass fiber is prepared according to the following method:
按照实际配方计算好各原料的添加量，准确称量后将各种原料输送至混合仓中充分混合均匀，再经窑头料仓送入池窑，在1600℃温度下熔化、澄清、均化8h后，通过4000孔铂金漏板流出，在拉丝机带动下(拉丝机线速度约1000m/min)，即得到低介电常数玻璃纤维。Calculate the addition amount of each raw material according to the actual formula, and after accurate weighing, transport all kinds of raw materials to the mixing bin to mix them evenly, and then send them to the pool kiln through the kiln head bin for melting, clarification and homogenization at 1600°C After 8 hours, it flows out through the 4000-hole platinum plug plate, and is driven by the wire drawing machine (the line speed of the wire drawing machine is about 1000m/min), and the low dielectric constant glass fiber is obtained.
对所述玻璃纤维进行性能测试，结果参见表1，表1为本发明实施例及比较例提供的玻璃纤维的配方及性能。Performance tests were performed on the glass fibers, and the results are shown in Table 1. Table 1 shows the formulations and properties of the glass fibers provided in the examples and comparative examples of the present invention.
对所述玻璃纤维进行性能测试。所述介电常数和介电损耗按照以下方法测定：Performance tests were performed on the glass fibers. Described dielectric constant and dielectric loss are measured according to the following method:
将各种原料按照配方要求制成配合料，混合均匀后装入铂金坩埚在1550℃到1600℃保温8小时，得到均匀、澄清的玻璃液；将所述玻璃液倒在预热的不锈钢模具上，置于马弗炉内退火后制成玻璃片，将所述玻璃片经切割、研磨、抛光后制成厚约1.5mm、长约4mm、宽约3mm的矩形片，在所述矩形片涂上银电极后进行介电常数及介电损耗的测量；Various raw materials are made into batches according to the formula requirements, mixed evenly, put into a platinum crucible and kept at 1550°C to 1600°C for 8 hours to obtain a uniform and clear glass liquid; pour the glass liquid onto a preheated stainless steel mold , placed in a muffle furnace and annealed to make a glass sheet, the glass sheet is cut, ground, and polished to make a rectangular sheet with a thickness of about 1.5 mm, a length of about 4 mm, and a width of about 3 mm. After the silver electrode is applied, the dielectric constant and dielectric loss are measured;
所述拉丝温度是指玻璃液粘度为1000泊时的温度，本发明采用高温粘度仪测试玻璃液在不同温度下的粘度，从而确定拉丝温度；The drawing temperature refers to the temperature at which the viscosity of the glass liquid is 1000 poise. The present invention adopts a high-temperature viscometer to test the viscosity of the glass liquid at different temperatures, thereby determining the drawing temperature;
所述失透上限温度是指玻璃液长期保温而不发生析晶或分相而使玻璃失透的温度上限，本发明采用梯度炉法测试失透上限温度。The devitrification upper limit temperature refers to the upper limit temperature at which glass liquid is kept warm for a long time without devitrification or phase separation, and the present invention uses a gradient furnace method to test the devitrification upper limit temperature.
所述耐水性通过测定研磨至360微米～400微米的玻璃粉在80℃的水中放置24小时的重量损失来表征。The water resistance is characterized by measuring the weight loss of glass powder ground to 360-400 microns in water at 80° C. for 24 hours.
表1本发明实施例及比较例提供的玻璃纤维的配方及性能Formulation and performance of the glass fibers provided by the embodiments of the present invention and comparative examples in table 1
由表1可知，本发明提供的玻璃纤维具有良好的工艺性、操作性、耐水性、较低的介电性能和较低的介电损耗：本发明实施例提供的玻璃纤维的拉丝温度都低于1280℃，大大低于比较例2提供的D玻璃纤维的拉丝温度；本发明实施例提供的玻璃纤维的拉丝温度与失透上限温度之差均大于100℃，部分甚至高于200℃，非常有利于拉丝作业；本发明实施例提供的玻璃纤维的介电性能和比较例2提供的D玻璃纤维相近，优于比较例1提供的E玻璃纤维；本发明实施例提供的玻璃纤维的耐水性优于比较例1提供的E玻璃纤维和比较例2提供的D玻璃纤维。因此，本发明提供的玻璃纤维可以适用于传统E玻璃纤维和D玻璃纤维所应用的印刷电路板领域。As can be seen from Table 1, the glass fibers provided by the present invention have good manufacturability, operability, water resistance, lower dielectric properties and lower dielectric loss: the drawing temperatures of the glass fibers provided by the embodiments of the present invention are all low At 1280°C, it is much lower than the drawing temperature of the D glass fiber provided in Comparative Example 2; the difference between the drawing temperature and the devitrification upper limit temperature of the glass fiber provided in the embodiment of the present invention is greater than 100°C, and some are even higher than 200°C, which is very It is beneficial to the drawing operation; the dielectric properties of the glass fibers provided by the embodiments of the present invention are similar to the D glass fibers provided by Comparative Example 2, and are better than the E glass fibers provided by Comparative Example 1; the water resistance of the glass fibers provided by the embodiments of the present invention It is superior to the E glass fiber provided in Comparative Example 1 and the D glass fiber provided in Comparative Example 2. Therefore, the glass fiber provided by the present invention can be applicable to the printed circuit board field where the traditional E glass fiber and D glass fiber are applied.
应当理解的是，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，而所有这些改进和变换都应属于本发明所附权利要求的保护范围。It should be understood that those skilled in the art can make improvements or changes based on the above description, and all these improvements and changes should fall within the protection scope of the appended claims of the present invention.
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| CN103482876B (en) * | 2013-09-18 | 2016-01-20 | 重庆理工大学 | A kind of glass fibre for printed circuit board (PCB) and preparation method thereof |
| CN104973791A (en) * | 2015-04-28 | 2015-10-14 | 安徽丹凤集团桐城玻璃纤维有限公司 | Alkali-free glass fiber yarn production process |
| CN104973792A (en) * | 2015-04-28 | 2015-10-14 | 安徽丹凤集团桐城玻璃纤维有限公司 | Heat-resistant glass fiber cloth |
| US10479721B2 (en) | 2015-05-13 | 2019-11-19 | Ppg Industries Ohio, Inc. | Use of MgO, ZnO, and rare earth oxides for making improved low dielectric fibers with improved low thermal expansion coefficient for high boron aluminosilicate compositions |
| CN107337350B (en) * | 2017-07-20 | 2020-01-21 | 太仓市格雷得五金有限公司 | High-strength glass fiber and preparation method thereof |
| JP7438711B2 (en) * | 2019-02-05 | 2024-02-27 | 住友化学株式会社 | resin composition |
| TWI694976B (en) * | 2019-12-31 | 2020-06-01 | 富喬工業股份有限公司 | Low dielectric constant glass composition with low bubble number and glass fiber |
| CN111943515A (en) * | 2020-08-25 | 2020-11-17 | 四川华原玻璃纤维有限责任公司 | Low-dielectric-constant glass fiber and preparation method thereof |
| CN113135666B (en) * | 2020-11-18 | 2021-11-19 | 南京玻璃纤维研究设计院有限公司 | Low-dielectric glass fiber, preparation method, glass fiber product, composite material and application |
| CN115806391B (en) * | 2022-12-15 | 2024-03-29 | 清远忠信世纪电子材料有限公司 | Glass fiber with low expansion coefficient and preparation method thereof |
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