TWI594968B - Glass material with a viscosity temperature at least 150 degrees above the liquefaction temperature - Google Patents
Glass material with a viscosity temperature at least 150 degrees above the liquefaction temperature Download PDFInfo
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- TWI594968B TWI594968B TW104125952A TW104125952A TWI594968B TW I594968 B TWI594968 B TW I594968B TW 104125952 A TW104125952 A TW 104125952A TW 104125952 A TW104125952 A TW 104125952A TW I594968 B TWI594968 B TW I594968B
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- 239000000463 material Substances 0.000 title claims description 174
- 239000011521 glass Substances 0.000 title claims description 139
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 20
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 17
- 239000000395 magnesium oxide Substances 0.000 claims description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 17
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 16
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 7
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000012779 reinforcing material Substances 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910052810 boron oxide Inorganic materials 0.000 claims description 4
- 230000000704 physical effect Effects 0.000 claims description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims 3
- 239000011787 zinc oxide Substances 0.000 claims 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 229910010413 TiO 2 Inorganic materials 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 239000003365 glass fiber Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000004031 devitrification Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- FZFYOUJTOSBFPQ-UHFFFAOYSA-M dipotassium;hydroxide Chemical compound [OH-].[K+].[K+] FZFYOUJTOSBFPQ-UHFFFAOYSA-M 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- UFQXGXDIJMBKTC-UHFFFAOYSA-N oxostrontium Chemical compound [Sr]=O UFQXGXDIJMBKTC-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Description
本發明係一種黏度溫度高於液化溫度至少150度之玻璃材料，尤指控制一強化材料、一助熔材料、一雜質材料及一主體材料之組成比例，令該玻璃材料之介電常數不僅能介於4.5~5.0之間，且尚能使其黏度溫度明顯高於液化溫度之玻璃材料。 The invention relates to a glass material having a viscosity temperature higher than a liquefaction temperature of at least 150 degrees, in particular to controlling a composition ratio of a reinforcing material, a fluxing material, an impurity material and a host material, so that the dielectric constant of the glass material can be introduced not only Between 4.5 and 5.0, and still able to make its viscosity temperature significantly higher than the liquefaction temperature of the glass material.
按，玻璃纖維係屬於一種無機纖維，其截面呈圓形，直徑在數微米至20微米之間，密度則介於2.4~2.7公克/立方厘米，由於具有優良的物理特性，故成為現代產業中不可或缺的重要原料，其中，由電子級玻璃纖維製成的「玻纖紗」，更是印刷電路板中的必要基材之一。 According to the glass fiber, it belongs to an inorganic fiber. Its cross section is circular, the diameter is between several micrometers and 20 micrometers, and the density is between 2.4 and 2.7 grams per cubic centimeter. Due to its excellent physical properties, it has become a modern industry. An important material that is indispensable, among them, "glass fiber yarn" made of electronic grade glass fiber is one of the necessary substrates in printed circuit boards.
玻璃依照其材料的組成、比例又分為多種類型，以往製作電子級玻璃纖維的原料大多為「E型玻璃」(E-Glass)，惟，近年來，隨著各種電子產品逐漸朝輕薄短小、多功能、高速及高頻化方向發展，使印刷電路板必須具備更低的介電常數，但E型玻璃所製成之玻璃纖維，其介電常數約為7.0、介電正切則為12×10-4，其電氣特性難以符合業者需求。 Glass is divided into various types according to the composition and proportion of its materials. In the past, most of the raw materials for making electronic grade glass fibers were "E-glass" (E-Glass). However, in recent years, with the decline of various electronic products, The development of multi-function, high-speed and high-frequency directions makes the printed circuit board have a lower dielectric constant, but the glass fiber made of E-glass has a dielectric constant of about 7.0 and a dielectric tangent of 12×. 10-4, its electrical characteristics are difficult to meet the needs of the industry.
為符合電子產業的需求，目前業界已開發出新類型的玻璃：D型玻璃(D-Glass)，D型玻璃的主要成份為SiO2、B2O3、CaO、MgO、LiO2、Na2O及K2O，其介電常數能達到4.3、介電正切(dielectric tangent)則有10×10-4，但D型玻璃卻有著熔融性較差的缺點，容易在加工時產生條紋與泡沫，導致玻璃纖維斷裂；此外，D型玻璃的耐水性及其與樹脂之附著性亦較差，故很容易自印刷電路板上剝離，而有許多可改良之處。 In order to meet the needs of the electronics industry, a new type of glass has been developed in the industry: D-glass (D-Glass). The main components of D-glass are SiO 2 , B 2 O 3 , CaO, MgO, LiO 2 , Na 2 . O and K 2 O have a dielectric constant of 4.3 and a dielectric tangent of 10×10-4, but D-type glass has the disadvantage of poor meltability, and it is easy to produce streaks and foam during processing. The glass fiber is broken; in addition, the water resistance of the D-type glass and its adhesion to the resin are also poor, so that it is easy to peel off from the printed circuit board, and there are many improvements.
前述D型玻璃之所以無法穩定地製作成玻璃纖維，其主要原因在於其「液化溫度」與「黏度溫度」的溫度差過於接近之故，一般言，業者欲以一玻璃材料製作玻璃纖維時，係先將玻璃材料置入一加熱熔爐， 加熱至預期的「黏度溫度」後，再利用一抽絲盒(Bushing)，將玻璃材料分離成玻璃纖維。前述「黏度溫度」係指玻璃材料經熔融後，其黏度達103poise(泊)時的溫度，又稱Log3溫度，由於一般D型玻璃的黏度溫度僅超出其液化溫度(即，開始熔化之溫度)大約30℃，因此，在業者將該玻璃材料加熱至該黏度溫度，以進行拉絲作業時，由於該玻璃材料之黏度溫度僅高於該液化溫度約30℃，故，加熱熔爐很容易誤判該玻璃材料已完全達到該黏度溫度，惟，該玻璃材料中部份材料事實上尚處於該液化溫度，而未達到適合進行拉絲作業之程度，此時，進行拉絲作業，即會因該玻璃材料中部份材料尚未達到該黏度溫度，而造成該玻璃纖維發生失透、結晶或纖維斷裂的問題。 The reason why the above-mentioned D-type glass cannot be stably produced into a glass fiber is that the temperature difference between the "liquefaction temperature" and the "viscosity temperature" is too close. In general, when the manufacturer wants to make a glass fiber from a glass material, First, the glass material is placed in a heating furnace. After heating to the desired "viscosity temperature", the glass material is separated into glass fibers by a bushing. The aforementioned "viscosity temperature" refers to the temperature at which the glass material has a viscosity of 103 poise after being melted, which is also called Log3 temperature. Since the viscosity temperature of the general D-type glass only exceeds its liquefaction temperature (ie, the temperature at which melting begins) About 30 ° C, therefore, when the manufacturer heats the glass material to the viscosity temperature for the drawing operation, since the viscosity temperature of the glass material is only about 30 ° C higher than the liquefaction temperature, the heating furnace is easy to misjudge the glass. The material has completely reached the viscosity temperature. However, some of the material in the glass material is actually at the liquefaction temperature, but it is not suitable for the drawing operation. At this time, the drawing operation is performed because the middle portion of the glass material is The material has not reached the viscosity temperature, causing the glass fiber to undergo devitrification, crystallization or fiber breakage.
目前，雖有許多業者設計出不同的D型玻璃之成份比例，以提高生產玻璃纖維時的良率(如：依專利合作條約(Patent Cooperation Treaty,PCT)申請之第WO02/094728號專利及美國第20030054936號專利)，但依據該等成份比例所製成之D型玻璃，並無法明顯增加黏度溫度與液化溫度之溫度差，因此，如何調整D型玻璃內各成份的比例，以提昇黏度溫度與液化溫度之溫度差，進而改善製作玻璃纖維時的良率，即成為本發明在此亟欲解決的重要問題。 At present, there are many manufacturers who have designed different ratios of D-type glass to improve the yield of glass fiber (eg, Patent No. WO02/094728, filed under the Patent Cooperation Treaty (PCT) and the United States. Patent No. 20040054936), but the D-type glass made according to the proportion of the components does not significantly increase the temperature difference between the viscosity temperature and the liquefaction temperature. Therefore, how to adjust the proportion of each component in the D-type glass to increase the viscosity temperature The difference in temperature from the liquefaction temperature and the improvement in the yield when the glass fiber is produced are an important problem to be solved by the present invention.
有鑑於習知D型玻璃之黏度溫度與液化溫度間的溫度差過近，致使用於製作玻璃纖維時良率過低的問題，發明人憑藉著多年來的實務經驗，並經過不斷地反覆測試、分析與研究後，終於設計出本發明之一種黏度溫度高於液化溫度至少150度之玻璃材料，期能解決前述拉絲作業上的良率問題。 In view of the fact that the temperature difference between the viscosity temperature of the D-type glass and the liquefaction temperature is too close, and the yield is too low for the production of the glass fiber, the inventor relies on years of practical experience and has been repeatedly tested. After analysis and research, the glass material of the present invention having a viscosity temperature higher than the liquefaction temperature of at least 150 degrees is finally designed, and the yield problem in the above drawing operation can be solved.
本發明之一目的，係提供一種黏度溫度高於液化溫度至少150度之玻璃材料，該玻璃材料係用以製作玻璃纖維，其成份包括一強化材料、一助熔材料、一雜質材料及一主體材料；該強化材料包括氧化鋁，該氧化鋁之重量百分比為該玻璃材料之10~12.5%，係用以提高該玻璃材料的結構強度；該助熔材料包括氧化鈣、氧化鎂、氧化硼、氧化鈦、氧化鈉及氧化鉀，其中該氧化鈣之重量百分比為該玻璃材料之5~10%、該氧化鎂 之重量百分比為該玻璃材料之2~5%、該氧化硼之重量百分比為該玻璃材料之15~25%、氧化鈦之重量百分比為該玻璃材料之2~5%、該氧化鈉之重量百分比為該玻璃材料之0.001~0.2%、該氧化鉀之重量百分比為該玻璃材料之0.001~0.2%，該助熔材料能降低玻璃熔化時的黏性；該雜質材料包括氧化鐵，但不包括任何的氟，該氧化鐵之重量百分比為該玻璃材料之0.05~0.15%，該雜質材料能影響該玻璃材料之介電常數與液化溫度；該主體材料包括氧化矽，其重量百分比為該玻璃材料扣除前述材料後的剩餘比例，據此，藉由該等材料之比例，該玻璃材料之介電常數即能被控制於4.5~5.0之間，且具有液化溫度小於1100℃、黏度溫度高於該液化溫度150℃之物理特性。如此，當一加熱熔爐對該玻璃材料進行加熱，且偵測到該玻璃材料達到或接近該黏度溫度時，因該玻璃材料之黏度溫度遠高於該液化溫度，即能確保該玻璃材料中任何部份絕非處於該液化溫度，而是均已達到適合進行拉絲作業之溫度，此時，利用一抽絲盒，將該玻璃材料分離成玻璃纖維，即能確保所製成之該玻璃纖維不致發生失透、結晶或纖維斷裂的問題。 An object of the present invention is to provide a glass material having a viscosity temperature higher than a liquefaction temperature of at least 150 degrees, the glass material being used for making glass fibers, the composition comprising a reinforcing material, a fluxing material, an impurity material and a host material. The reinforcing material comprises alumina, and the weight percentage of the alumina is 10~12.5% of the glass material, which is used to increase the structural strength of the glass material; the fluxing material comprises calcium oxide, magnesium oxide, boron oxide, oxidation Titanium, sodium oxide and potassium oxide, wherein the weight percentage of the calcium oxide is 5 to 10% of the glass material, the magnesium oxide The weight percentage is 2 to 5% of the glass material, the weight percentage of the boron oxide is 15 to 25% of the glass material, and the weight percentage of titanium oxide is 2 to 5% of the glass material, and the weight percentage of the sodium oxide. 0.001~0.2% of the glass material, the weight percentage of the potassium oxide is 0.001~0.2% of the glass material, the fluxing material can reduce the viscosity of the glass when melting; the impurity material includes iron oxide, but does not include any Fluorine, the weight percentage of the iron oxide is 0.05~0.15% of the glass material, the impurity material can affect the dielectric constant and the liquefaction temperature of the glass material; the host material comprises cerium oxide, and the weight percentage thereof is deducted from the glass material. The remaining ratio after the foregoing materials, according to the ratio of the materials, the dielectric constant of the glass material can be controlled between 4.5 and 5.0, and the liquefaction temperature is less than 1100 ° C, and the viscosity temperature is higher than the liquefaction. Physical properties at a temperature of 150 °C. Thus, when a heating furnace heats the glass material and detects that the glass material reaches or approaches the viscosity temperature, since the viscosity temperature of the glass material is much higher than the liquefaction temperature, any of the glass materials can be ensured. The part is not at the liquefaction temperature, but has reached a temperature suitable for the drawing operation. At this time, the glass material is separated into glass fibers by using a spinning box, thereby ensuring that the glass fiber is not made. The problem of devitrification, crystallization or fiber breakage occurs.
為便 貴審查委員能對本發明之技術特徵及其目的有更進一步的認識與理解，茲以發明人實際研究出之若干實施例，進行說明如後： In order that the reviewer can have a further understanding and understanding of the technical features and the objects of the present invention, some embodiments actually studied by the inventors are described as follows:
本發明係一種黏度溫度高於液化溫度至少150度之玻璃材料，係用於製作玻璃纖維，依據不同的材料特性，該玻璃材料之成份可包括一強化材料、一助熔材料、一雜質材料及一主體材料，其中，該強化材料包括氧化鋁(Al2O3)，該氧化鋁之重量百分比為該玻璃材料之10~12.5%，係用以提高該玻璃材料的結構強度，氧化鋁(Al2O3)是影響該玻璃材料之黏度溫度與液化溫度過高的主要關鍵，一旦比例過多，即無法有效控制黏度溫度與液化溫度間的溫度差。 The invention relates to a glass material having a viscosity temperature higher than a liquefaction temperature of at least 150 degrees, which is used for making glass fibers. The composition of the glass material may comprise a reinforcing material, a fluxing material, an impurity material and a material according to different material properties. The main material, wherein the reinforcing material comprises alumina (Al 2 O 3 ), the weight percentage of the alumina is 10 to 12.5% of the glass material, which is used to increase the structural strength of the glass material, and the aluminum oxide (Al 2 ) O 3 ) is the main key affecting the viscosity temperature and liquefaction temperature of the glass material. Once the ratio is too large, the temperature difference between the viscosity temperature and the liquefaction temperature cannot be effectively controlled.
該助熔材料係用以降低玻璃熔化時的黏性，包括氧化鈣 (CaO)、氧化鎂(MgO)、氧化硼(B2O3)、氧化鈦(TiO2)、氧化鈉(Na2O)及氧化鉀(K2O)，各成份之特性與比例含量如下：(1)氧化鈣(CaO)，其重量百分比為該玻璃材料之5~10%，能影響該玻璃材料內之網絡、破壞該玻璃材料之結晶純度，以降低該玻璃材料之黏度溫度與液化溫度，此外，氧化鈣(CaO)尚能抑制氧化硼(B2O3)轉換成硼酸鹽(H3BO3)，以提高該玻璃材料之耐水性；(2)氧化鎂(MgO)，其重量百分比為該玻璃材料之2~5%，能使該玻璃材料更易熔化，但比例過多時會影響其耐水性；(3)氧化硼(B2O3)，其重量百分比為該玻璃材料之15~25%，根據發明人的研究與測試結果，當氧化硼(B2O3)比例低於15%時，將會導致該玻璃材料熔融後的黏度偏高、黏度溫度與液化溫度亦有過高現象；而在其比例高於25%時，不僅會提高原料成本，且會使熔融後的玻璃材料不穩定、易揮發，進而影響到工藝流程以及抽絲的品質與良率；(4)氧化鈦(TiO2)，其重量百分比為該玻璃材料之2~5%，能大幅降低該玻璃材料的介電常數與介電正切；及(5)氧化鈉(Na2O)與氧化鉀(K2O)，其重量百分比皆為該玻璃材料之0.001~0.2%，但比例過多時會使該玻璃材料之介電正切上升。 The fluxing material system for reducing viscosity during glass melting, including calcium oxide (CaO), magnesium oxide (MgO), boron oxide (B2O 3), titanium oxide (TiO 2), sodium oxide (Na 2 O) and Potassium oxide (K2O), the characteristics and proportions of the components are as follows: (1) calcium oxide (CaO), the weight percentage of which is 5-10% of the glass material, can affect the network within the glass material, destroy the glass material Crystal purity to reduce the viscosity temperature and liquefaction temperature of the glass material. In addition, calcium oxide (CaO) can inhibit the conversion of boron oxide (B 2 O 3 ) to borate (H 3 BO 3 ) to enhance the glass material. Water resistance; (2) Magnesium oxide (MgO), the weight percentage of which is 2 to 5% of the glass material, can make the glass material more easily melted, but when the ratio is too large, the water resistance is affected; (3) boron oxide ( B 2 O 3 ), the weight percentage is 15~25% of the glass material. According to the research and test results of the inventors, when the proportion of boron oxide (B 2 O 3 ) is less than 15%, the glass material will be caused. The viscosity after melting is too high, the viscosity temperature and the liquefaction temperature are too high; when the ratio is higher than 25%, not only the raw materials are increased. Present, and make the glass material after melt unstable, volatile, and thus affect the quality and yield of the spinning process and; (4) titanium oxide (Ti02 2), for weight percentage of glass materials 2 - 5%, can significantly reduce the dielectric constant and dielectric tangent of the glass material; and (5) sodium oxide (Na 2 O) and potassium oxide (K 2 O), the weight percentage of which is 0.001 ~ 0.2 of the glass material %, but too much proportion will cause the dielectric tangential rise of the glass material.
該雜質材料包括氧化鐵(Fe2O3)，該氧化鐵之重量百分比必須大於該玻璃材料之0.03%，始能對該玻璃材料之特性產生具體變化，而本發明之一較佳實施例則係控制於0.05~0.15%，氧化鐵(Fe2O3)能影響該玻璃材料之純度，進而改變介電常數與液化溫度，且能與玻璃中的氧化硼(B2O3)與氧化矽(SiO2，如後文所述)形成非橋接氧，而增加該玻璃材料之介電常數。該主體材料包括氧化矽(SiO2)，為玻璃材料的主要成份，該氧化矽之重量百分比為該玻璃材料扣除前述材料後的剩餘比例，至少佔該玻璃材料之52%，若小於50%，介電常數將會過高，而若高於60%，則會有熔融後黏度過大的問題。藉由該等材料之比例，該玻璃材料之介電常數即能被控制於4.5~5.0之間、且具有液化溫度小於1100℃、黏度溫度高於該液化溫度150℃之物理特性。 The impurity material comprises iron oxide (Fe 2 O 3 ), the weight percentage of the iron oxide must be greater than 0.03% of the glass material, and a specific change can be made to the characteristics of the glass material, and a preferred embodiment of the present invention Controlled at 0.05~0.15%, iron oxide (Fe 2 O 3 ) can affect the purity of the glass material, and then change the dielectric constant and liquefaction temperature, and can be combined with boron oxide (B2O3) and yttrium oxide (SiO2, in glass). The non-bridged oxygen is formed as described later to increase the dielectric constant of the glass material. The host material comprises cerium oxide (SiO2), which is a main component of the glass material, and the weight percentage of the cerium oxide is the remaining proportion of the glass material after subtracting the foregoing materials, at least 52% of the glass material, and if less than 50%, The electric constant will be too high, and if it is higher than 60%, there will be a problem that the viscosity after melting is too large. By the ratio of the materials, the dielectric constant of the glass material can be controlled between 4.5 and 5.0, and has a physical property of a liquefaction temperature of less than 1100 ° C and a viscosity temperature of 150 ° C above the liquefaction temperature.
如此，在業者利用一加熱熔爐，將該玻璃材料加熱至該黏度 溫度，並利用一抽絲盒，將熔化後之該玻璃材料分離成玻璃纖維時，由於該玻璃材料之黏度溫度高於該液化溫度至少150℃，遠高於習知玻璃材料的30℃溫度差，故，在該加熱熔爐偵測到該玻璃材料達到或接近該黏度溫度時，即能確保該玻璃材料中任何部份絕非處於該液化溫度，而是均已達到適合進行拉絲作業之溫度，以有效避免因該玻璃材料中部份材料尚在該液化溫度，進而在後續利用一抽絲盒對該玻璃材料進行拉絲作業，以將該玻璃材料分離成玻璃纖維時，能確保所製成之該玻璃纖維完全不會發生失透、結晶或纖維斷裂的問題。 Thus, the manufacturer uses a heating furnace to heat the glass material to the viscosity. Temperature, and using a wire drawing box to separate the molten glass material into glass fiber, since the viscosity temperature of the glass material is higher than the liquefaction temperature by at least 150 ° C, which is much higher than the temperature difference of 30 ° C of the conventional glass material. Therefore, when the heating furnace detects that the glass material reaches or approaches the viscosity temperature, it can ensure that any part of the glass material is not at the liquefaction temperature, but has reached a temperature suitable for drawing operation. In order to effectively prevent some of the glass material from being at the liquefaction temperature, and subsequently drawing the glass material by using a spinning box to separate the glass material into glass fibers, the preparation can be ensured. The glass fiber does not suffer from devitrification, crystallization or fiber breakage at all.
此外，習知的D型玻璃材料中，大多會加入氟(F2)，以控制玻璃的黏度、介電常數與介電正切，但由於氟(F2)亦會明顯提高該玻璃材料的液化溫度，致使習知玻璃材料之液化溫度與黏度溫度過於接近，而本發明所使用的玻璃材料，完全無須摻入氟(F2)，故始能在限定其他材料的比例後，順利使該液化溫度與黏度溫度間的溫度差高於150℃，且同時兼顧該玻璃材料的介電常數、介電正切等特性。 In addition, in the conventional D-type glass materials, fluorine (F 2 ) is often added to control the viscosity, dielectric constant and dielectric tangent of the glass, but fluorine (F 2 ) also significantly improves the liquefaction of the glass material. The temperature causes the liquefaction temperature of the conventional glass material to be too close to the viscosity temperature, and the glass material used in the present invention does not need to be doped with fluorine (F 2 ) at all, so that the liquefaction can be smoothly performed after limiting the ratio of other materials. The temperature difference between the temperature and the viscosity temperature is higher than 150 ° C, and at the same time, the dielectric constant and dielectric tangent of the glass material are taken into consideration.
另，業者尚可加入氧化鋅(ZnO)與氧化鍶(SrO)等材料，以調整該玻璃材料之物理與電氣特性，該氧化鋅(ZnO)之重量百分比為該玻璃材料之0.001~0.2%、氧化鍶(SrO)之重量百分比為該玻璃材料之0.001~0.2%。根據發明人的實際測試，在前述成份比例的條件下，且該氧化矽(SiO2)之重量百分比為該玻璃材料之52~56%時，該玻璃材料之黏度溫度能低於1300℃、液化溫度則低於1100℃。請參閱下列表格所示，係本發明之玻璃材料之一較佳實施例之成份比例：
根據上述成份比例，發明人測試該玻璃材料之物理與電氣特性如下，其中，該玻璃材料之黏度溫度、液化溫度、介電常數、介電正切係根據美國測試及材料學會(American Society for Testing and Material，下稱ASTM)所定義之標準方法進行，該等方法均可自ASTM之標準年報(Annual Book of ASTM Standards)中得知：黏度溫度係利用ASTM之C965方法加以測量；液化溫度係利用ASTM之C829方法加以測量；介電常數、介電正切則係利用ASTM之D150與D2149二方法，先藉標準石英(standard quartz，其介電常數為4.2)校正後加以測量而得：
由上表可清楚看出，本發明之玻璃材料，不僅具有明顯的溫度差，可確保拉絲作業上之良率，且其抗濕性(即，上表中之防水性)以鹼溶解表示為小於「0.055毫克Na2O/克玻璃」，故能大幅改善玻璃纖維易自印刷電路板上剝離的缺點。 As is apparent from the above table, the glass material of the present invention not only has a significant temperature difference, but also ensures the yield on the drawing operation, and its moisture resistance (i.e., water repellency in the above table) is expressed by alkali dissolution. Less than "0.055 mg Na 2 O / gram glass", it can greatly improve the disadvantage that the glass fiber is easily peeled off from the printed circuit board.
又，為進一步比較本發明之玻璃材料的特性，茲以美商AGY公司申請之台灣第I363744號專利為「對照材料1」、日商日東紡績公司申請之美國第20030054936號專利為「對照材料2」、第WO02/094728號專利為「對照材料3」、一般E型玻璃為「對照材料4」，比較該等對照材料及本發明之玻璃材料如下(下表中的R*代表鹼土金屬或鹼金屬，且表格中之數字為重量百分比)：
由上表可清楚看出，本發明與其他對照材料在「氧化鋁(Al2O3)」的比例上有著關鍵的差異，本發明使用的比例明顯低於該等對照材料；而比對其他成份，前述對照材料1~3中，與本發明較為相似的為日東紡績所研發之玻璃材料「對照材料2」，惟，本發明在成份比例上仍與對照材料2有多處不同，致使能讓玻璃材料之黏度溫度與液化溫度間的溫度差更大，茲詳細說明如後。 As is clear from the above table, the present invention has a key difference in the ratio of "alumina (Al2O3)" to other control materials, and the ratio used in the present invention is significantly lower than that of the comparative materials; Among the comparative materials 1 to 3, similar to the present invention, the glass material "Control Material 2" developed by Nitto Kokusai Co., Ltd., however, the present invention is still different in composition ratio from the control material 2, so that the glass material can be made. The temperature difference between the viscosity temperature and the liquefaction temperature is larger, as described in detail later.
首先，在「助熔材料」方面，主要成份包括氧化硼(B2O3)、氧化鈣(CaO)與氧化鎂(MgO)三者，而根據發明人的實際測試，氧化硼(B2O3)之比例在大於20%時，製作玻璃纖維時較容易產生有明顯的斷裂現象，故氧化硼(B2O3)之最佳比例不應高於20%，對照材料2與本發明相同，皆有控制氧化硼(B2O3)之比例，然而，對於另外兩種助熔材料「氧化鈣(CaO)與氧化鎂(MgO)」，本發明與對照材料則有極大的區別，對照材料2係使用較多的氧化鎂(MgO)，本發明則係以氧化鈣(CaO)為主，氧化鈣(CaO)能夠影響玻璃材料的結晶純度，意即，可讓液化溫度與黏度溫度皆明顯下降，但反過來說，也易導致該玻璃材料之結構強度過低。 First, in terms of "fusible materials", the main components include boron oxide (B 2 O 3 ), calcium oxide (CaO) and magnesium oxide (MgO), and according to the actual test of the inventors, boron oxide (B 2 O) 3 ) When the ratio is more than 20%, the glass fiber is more likely to have obvious fracture phenomenon, so the optimum ratio of boron oxide (B 2 O 3 ) should not be higher than 20%, and the control material 2 is the same as the present invention. The ratio of boron oxide (B 2 O 3 ) is controlled. However, for the other two fluxing materials, "calcium oxide (CaO) and magnesium oxide (MgO)", the present invention is greatly different from the control material. Material 2 uses more magnesium oxide (MgO), and the present invention mainly uses calcium oxide (CaO). Calcium oxide (CaO) can affect the crystal purity of the glass material, that is, the liquefaction temperature and the viscosity temperature are both Significantly decreased, but conversely, it is also easy to cause the structural strength of the glass material to be too low.
承上，根據發明人的測試結果，在控制氧化矽(SiO2)、氧化鋁(Al2O3)與氧化硼(B2O3)的比例後，此時，若氧化鈣(CaO)之比例大於10%，則會導致玻璃材料的結構強度過低，但若將氧化鈣(CaO)之比例控制在5~10%之間，則能在符合玻璃纖維規範的前提下，讓玻璃材料具有更低的黏度溫度與液化溫度。而「氧化鈣(CaO)與氧化鎂(MgO)之比例差異」，即為本發明能達成更佳性能的第一個關鍵差異。 According to the test results of the inventors, after controlling the ratio of cerium oxide (SiO2), alumina (Al2O3) and boron oxide (B 2 O 3 ), at this time, if the ratio of calcium oxide (CaO) is more than 10% , the structural strength of the glass material is too low, but if the ratio of calcium oxide (CaO) is controlled to between 5 and 10%, the glass material can have a lower viscosity under the premise of conforming to the glass fiber specification. Temperature and liquefaction temperature. The "difference in the ratio of calcium oxide (CaO) to magnesium oxide (MgO)" is the first key difference for achieving better performance in the present invention.
另，本發明與對照材料2的第二個差異，乃本發明具有相對較高比例的氧化鈦(TiO2)，氧化鈦(TiO2)能夠降低該玻璃材料的黏度與介電常數，讓本發明之玻璃材料的電氣特性能更符合業界對於玻璃纖維的需求；本發明與對照材料2的第三點差異，乃本發明利用了氧化鐵(Fe2O3) 作為雜質材料，在氧化鐵(Fe2O3)與玻璃中的氧化硼(B2O3)與氧化矽(SiO2)形成非橋接氧後，除了增加該玻璃材料之介電常數外，尚能進一步拉低該玻璃材料的液化溫度，據此，即能讓該玻璃材料的黏度溫度能明顯高於該液化溫度。 In addition, the second difference between the present invention and the control material 2 is that the present invention has a relatively high proportion of titanium oxide (TiO 2 ), and the titanium oxide (TiO 2 ) can reduce the viscosity and dielectric constant of the glass material. The electrical characteristics of the inventive glass material are more in line with the industry's demand for glass fibers; the third difference between the present invention and the control material 2 is that the present invention utilizes iron oxide (Fe 2 O 3 ) as an impurity material in iron oxide ( After Fe 2 O 3 ) forms non-bridged oxygen with boron oxide (B 2 O 3 ) and yttrium oxide (SiO 2 ) in the glass, in addition to increasing the dielectric constant of the glass material, the glass material can be further pulled down. The liquefaction temperature, according to which the viscosity temperature of the glass material can be significantly higher than the liquefaction temperature.
此外，本發明與前述對照材料1~3相比，由於無須使用氟(F2)，故能確保生產過程中的環保，讓業者無須擔心生產中使用的氟(F2)會破壞大氣層的臭氧，使本發明技術更易於實施。 In addition, the present invention can ensure environmental protection in the production process because it does not require the use of fluorine (F 2 ) as compared with the above-mentioned comparative materials 1 to 3, so that the manufacturer does not have to worry that fluorine (F 2 ) used in production may damage the ozone of the atmosphere. The technique of the present invention is made easier to implement.
綜上所述，本發明之玻璃材料之所以能實現「黏度溫度高於液化溫度至少150度」之原因，係在於使用了相對較少的氧化鋁(Al2O3)、且調高氧化鈣(CaO)之比例，同時，添加了氧化鈦(TiO2)與氧化鐵(Fe2O3)，但卻不含任何的氟(F2)，據此，始能在確保玻璃材料之原料成本、結構強度及製程環保的前提下，有效增加黏度溫度與液化溫度間的溫度差。 In summary, the reason why the glass material of the present invention can achieve a "viscosity temperature of at least 150 degrees above the liquefaction temperature" is to use relatively less alumina (Al 2 O 3 ) and to increase the calcium oxide. The ratio of (CaO), at the same time, adds titanium oxide (TiO 2 ) and iron oxide (Fe 2 O 3 ), but does not contain any fluorine (F 2 ), thereby ensuring the raw material cost of the glass material. Under the premise of structural strength and environmental protection of the process, the temperature difference between the viscosity temperature and the liquefaction temperature is effectively increased.
以上所述，僅為本發明之若干較佳實施例，惟，本發明之技術特徵並不以此為限，凡相關技術領域之人士，在參酌本發明之技術內容後所能輕易思及之等效變化，均應不脫離本發明之保護範疇。 The above description is only a few preferred embodiments of the present invention, but the technical features of the present invention are not limited thereto, and those skilled in the relevant art can easily think of it after considering the technical content of the present invention. Equivalent changes should not depart from the scope of protection of the present invention.
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| TW201542492A (en) | 2015-11-16 |
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