^β36〇 Α7 Β7 五、發明説明（1 ) 本發明係指一種可生物降解的玻璃織維組成物。 先有技術提到一些據稱可生物降解的玻璃織維組成物。 根據多項硏究指出，一些直徑小於三微米的超細玻璃纖維可能致 癌，但在同樣大小範圍內的可生物降解玻璃纖維卻不會致癌。因此， 要求玻璃纖維成分具有可生物降解性能是相當重要的。 然而，不僅是生物降解性能，玻璃纖維本身或其成品的機械屬性 與熱屬性，玻璃纖維的阻抗及玻璃纖維成分的可加工性皆具關鍵重要 性。例如，玻璃纖維廣泛應用於各種絕緣目的。在這些應用當中，玻 / 璃纖維就必須具有充分的抗濕性能。 ^ 另，玻璃纖維組成物必須能利用如離心技術，特別是內離心技術 (此項技術見美國專利US-PS4 203 745所舉範例說明）等已知工法 加工成直徑很小的玻璃纖維。 本發明係基於如何提供一種新穎的玻璃纖維組成物，兼具可生物 降解、對濕氣具有良好安定度或阻抗性，又易於加工等特性問題的考 (請先閱讀背面之注意事項再填寫本頁 訂 經濟部中央標隼局Κ〈工消費合作社印製 里 又，本發明係發現前述問題可經由使用一種由大量鹼氧化物與氧 化硼組成，並含有氧化鈦、氧化銷、氧化鋅、氧化鎂、氧化鋇或兩種 或兩種以上此等氧化物混合物獲得解決 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210Χ297公釐） --卜'五、發明説明1 : A7 B7 結果發現該種玻璃纖維組成物符合必要屬性、亦即可生物降解 抗濕與良好加工等屬性的組合。 本發明之主要目的爲一種可生物降解，且具有下列以百分比重量 計組分特性的玻璃纖維組成物： 成分： S i 0 2 5 0至 6 0 A 1 20 3 低於2 C a O+Mg Ο 1 0至 1 6 N a 2 〇 + K a 〇 1 4至 1 9 B 2 〇 3 7至1 6 T i 0 2 0至 4 Z r O 2 0至 5 Z η O 0至 5 Μ η O 0至 4 B a O 0至 5 T i02,Zr02,Zn0,Mn0,Ba0 1至 6 F e 2〇 a, S r O 0至 2 F , L i a O 0至 2 P 2〇 3 0至 4^ β36〇 Α7 Β7 5. Description of the invention (1) The present invention refers to a biodegradable glass weave composition. The prior art mentions some glass-dimensions compositions that are said to be biodegradable. According to several studies, some ultra-fine glass fibers with a diameter of less than three microns may cause cancer, but biodegradable glass fibers in the same size range will not cause cancer. Therefore, it is very important to require the biodegradability of glass fiber components. However, not only the biodegradability, but also the mechanical and thermal properties of the glass fiber itself or its finished product, the resistance of the glass fiber and the processability of the glass fiber components are all critically important. For example, glass fiber is widely used for various insulation purposes. In these applications, glass / glass fibers must have sufficient moisture resistance. ^ In addition, the glass fiber composition must be able to be processed into glass fibers with a very small diameter by known methods such as centrifugal technology, especially internal centrifugal technology (see the example description in US-PS4 203 745 for this technology). The present invention is based on how to provide a novel glass fiber composition, which is biodegradable, has good stability or resistance to moisture, and is easy to process and other characteristics (please read the precautions on the back before filling in this The Ministry of Economic Affairs, Central Standard Falcon Bureau K (printed by the Industrial and Consumer Cooperative Society, the present invention found that the aforementioned problem can be achieved by using a large amount of alkali oxide and boron oxide, and containing titanium oxide, oxide pin, zinc oxide, oxide Magnesium, barium oxide or mixtures of two or more of these oxides have been solved. The paper scale is applicable to the Chinese National Standard (CNS) Λ4 specification (210Χ297mm)-Bu'Five. Description of the invention 1: A7 B7 A glass fiber composition meets the necessary attributes, that is, a combination of biodegradability, moisture resistance, and good processing. The main purpose of the present invention is a glass fiber composition that is biodegradable and has the following component characteristics by weight percent : Composition: S i 0 2 5 0 to 6 0 A 1 20 3 Below 2 C a O + Mg Ο 1 0 to 1 6 N a 2 〇 + K a 〇1 4 to 1 9 B 2 〇3 7 to 1 6 T i 0 2 0 to 4 Z r O 2 0 to 5 Z η O 0 to 5 Μ η O 0 to 4 B a O 0 to 5 T i02, Zr02, Zn0, Mn0, Ba0 1 to 6 F e 2〇 a, S r O 0 to 2 F, L ia O 0 to 2 P 2〇3 0 to 4
(請先閱讀背面之注意事項再填商本頁) -β 經濟部中央標準局男工消費合作杜印製 本發明之玻璃織維組成物皆可利用離心法加工。而所獲得的繊維 具有良好的抗濕性，此等玻璃纖維的組成物尤爲稱奇之處在於顯示皆 爲可生物降解。織維直徑宜不超過十（1 〇)微米，控制在二點五 (2.5)與五（5)微米之間尤佳。 根據較佳實施例，本發明之玻璃纖維組成物含有以重量計百分之 一至百分之四（1%〜4%)的氧化鈦。 本紙張尺度適用中國园家標準（CNS ) Λ4規格（2〗〇χ 297公f ) 經濟部中央標準局貝工消費合作社印装 Α7 Β7 五、發明説明（） 根據另一較佳實施例’本發明之玻璃纖維組成物含有以重量計爲 百分之一到百分之四（1 %〜4%)的氧化鎂。 根據另一較佳實施例’本發明之玻璃纖維組成物含有以重量計爲 百分之一到百分之四（1 %〜4 %)的氧化鋅。 根據另一較佳實施例’本發明之玻璃纖維組成物含有以重量計爲 百分之零點五到百分之五（0 · 5 %〜5 %)，尤指百分之零點五到 百分之三（0 · 5 %〜3 %)的氧化锆。 又根據另一較佳實施例，本發明之玻璃纖維組成物含有以重量計 爲百分之零點五到百分之四（0 . 5 %〜4 %)的氧化鋇。 特別是本發明組成物宜使用氧化锆、氧化鋅、氧化鈦、氧化鋇與 氧化鎂等氧化物的混合物，尤指其中兩種或兩種以上的混合物。 較佳實施例爲含有以重量計百分之一到百分之四（1 %〜4 %) 的氧化鋇混合氧化鈦或氧化鋅。 在另外的較佳實施例中係以氧化鋅與氧化鈦混合，另可選擇添加 氧化锆；其中各種組分添加量可爲以重量計百分之一到百分之三 (1%〜3%)。 另外在較佳實施例中亦可爲氧化锆與氧化鋅、氧化鈦、氧化鋇與 氧化鎂的混合物；其中各種組分的添加量爲以重量計百分之零點五到 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 83. 3. 10,000 (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部中央樣傘局Μ工消費合作社印聚 A7 B7 五、發明説明（4) 百分之四（0 . 5%〜4%)，尤以重量計添加量爲百分之零點五到 百分之一點五（〇.5%〜1·5%)爲佳。 含有氧化锆以及/或氧化鋇的本發明組成物若同時含有以重量計 百分之零點五到百分之二（〇 · 5 %〜2% )的氟以及/或氧化鋰更 能顯現其優點。 亦可在本發明組成物中添加以重量計至少百分之零點一（〇 · 1 %) ’尤以至少在百分之零點五（0 . 5 %)的氧化鋁爲佳。 五氧化磷可增加生物降解性能。因此本發明組成物宜同時含有以 重量計爲百分之零點一至百分之二（〇.1%〜2%)的五氧化二憐 〇 根據本發明另一較佳實施例，本組成物含有以重量計低於百分之 二的氧化錢。 本發明之玻璃纖維組成物的抗濕性係使用一習稱爲D G G法的標 準方法測定。 此一DGG法實施係先將十（1 〇)克經過細磨具有3 6 0至 4 0 0微米粒度的玻璃放在1 〇 〇毫升的水中加熱維持在沸點五小時 之久。材料經過急速冷卻後將溶液過濾，使過濾物中有部分體積呈乾 蒸汽。以此方式所獲得的乾料可使玻璃含量溶解於水中以計算其重量 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X297公t ) (請先閱讀背面之注意事項再填寫本頁)(Please read the precautions on the back and then fill in this page)-β The printing is produced by the male-consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs. The obtained dimensional fiber has good moisture resistance. The composition of these glass fibers is particularly surprising in that they are all biodegradable. The diameter of the weave dimension should not exceed ten (10) microns, preferably between 2.5 (2.5) and five (5) microns. According to a preferred embodiment, the glass fiber composition of the present invention contains 1 to 4% (1% to 4%) titanium oxide by weight. This paper scale is applicable to the Chinese Gardener Standard (CNS) Λ4 specification (2〗 〇χ 297 public f) Printed by the Central Standards Bureau of the Ministry of Economic Affairs Beigong Consumer Cooperative Α7 Β7 V. Description of invention () According to another preferred embodiment The inventive glass fiber composition contains 1 to 4% (1% to 4%) magnesium oxide by weight. According to another preferred embodiment, the glass fiber composition of the present invention contains 1 to 4% (1% to 4%) zinc oxide by weight. According to another preferred embodiment, the glass fiber composition of the present invention contains 0.5% to 5% by weight (0.5% to 5%), especially 0.5% to Three percent (0.5% ~ 3%) of zirconia. According to yet another preferred embodiment, the glass fiber composition of the present invention contains 0.5% to 4% (0.5% ~ 4%) of barium oxide by weight. In particular, the composition of the present invention preferably uses a mixture of oxides such as zirconium oxide, zinc oxide, titanium oxide, barium oxide, and magnesium oxide, especially a mixture of two or more thereof. A preferred embodiment is a mixed titanium oxide or zinc oxide containing one to four percent by weight (1% to 4%) of barium oxide. In another preferred embodiment, zinc oxide and titanium oxide are mixed, and zirconia can be optionally added; wherein the amount of various components can be 1% to 3% by weight (1% ~ 3% ). In addition, in the preferred embodiment, it can also be a mixture of zirconia and zinc oxide, titanium oxide, barium oxide and magnesium oxide; the amount of each component added is 0.5% by weight to the paper size applicable to China National Standard (CNS) Α4 specification (210Χ297mm) 83. 3. 10,000 (please read the precautions on the back before filling in this page) Order the Central Sample Umbrella Bureau of the Ministry of Economic Affairs Mgong Consumer Cooperative Printed A7 B7 V. Description of invention ( 4) Four percent (0.5% ~ 4%), especially the added amount by weight is 0.5% to 1.5% (0.5% ~ 1.5%). The composition of the present invention containing zirconium oxide and / or barium oxide can also show it if it contains 0.5% to 2% (0.5% to 2%) of fluorine and / or lithium oxide by weight advantage. It is also possible to add at least 0.1% (0.1%) by weight to the composition of the present invention, particularly preferably alumina at least 0.5% (0.5%). Phosphorus pentoxide can increase biodegradability. Therefore, the composition of the present invention preferably contains 0.1% to 2% (0.1% to 2%) of pentoxide by weight. According to another preferred embodiment of the present invention, the composition The substance contains less than 2% by weight of oxidized money. The moisture resistance of the glass fiber composition of the present invention is measured using a standard method commonly known as the DG method. This DGG method is implemented by first placing ten (10) grams of finely ground glass with a particle size of 360 to 400 microns in 100 ml of water and heating to maintain the boiling point for five hours. After the material is rapidly cooled, the solution is filtered, so that part of the volume of the filtrate is dry steam. The dry material obtained in this way can dissolve the glass content in water to calculate its weight. The paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210X297g) (Please read the precautions on the back before filling this page)
、1T Α7 Β7 五、發明説明（5) -此重量以受測玻璃每克的毫克含量表示。 一如同法所說明的，藉著將一（1 )克的玻璃粉導入含有以下所 示組分’酸鹸値爲7.4的生理溶液試驗本發明之玻璃纖維組成物的 可生物降解性： N a C 1 6 · 7 8 N Η 4 C 1 0 , 5 3 5 N a HC 0 a 2 2 6 8 N a H 2 P 0 4 H 2 O 0 · 1 6 6 (Na 3檸檬酸鹽）2H2〇 0 · 0 5 9 氨基醋酸 0 4 5 0 Η 2 S Ο 4 0 0 4 9 C a C 1 2 0 < 0 2 2 (請先閱讀背面之注意寧頊再填艿本頁) 經濟部中央標準局晃工消费合作社印製 動態試驗選自於Scholze與Conradt說明的條件。流速爲每天三 百毫升（3 0 0 m1 )。此項試驗進行時間爲十四（1 4)天。試驗 結果以十四天（14)後在溶液中的二氧化矽百分比表示。 在此配合下列範例當可更詳細說明本發明： 範例 將含有表一與表二列示的組成物的玻璃熔解。 所有的玻璃組成物皆可利用離心技術獲得圓滿的加工。 表一下方的倒數第二行列出使用D G G法所測得的値，倒數第一 行表示根據前述測定方法所得到的可生物降解値° 訂 本纸張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） 表1 範例1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 SiOi 54 53 53.5 54 53 54 53 53.5 53.5 53.5 55.5 52 53 52.5 54.7 AUQ, 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 1.9 1 0.5 0.5 CaO ,8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.0 8.5 8.5 8.5 MgO 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.6 3.5 3.5 3.5 Na20 17 17 17 17' 17 17 17 17 17 - 17 15.8 14.5 17 17 14.0 K20 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 α.2 0.5 0.5 0.5 1.0 ΒΛ 13 13 13 13 13 13 13 12 12 12 12 14.5 13 12. 12 TiOj 2 2 2 2 1.0 2 2 1.0 MnO 2 2 2 ZnO 2 2 1 1.5 ZrO, 2 2 2 2 BaO 2 3.5 4.0 ΡΛ 1.0 1 1 1 F*Cj〇3 0.3 SrtX 0.3 F 0.6 〇J u2o 0.4 0.3 DGG 45 45 40 40 40 35 35 30 30 30 30 25 50 35 20 可生物 降解質500 550 500 550 600 550 600 450 450 500 550 500 550 450 450 表2 範例 16 17 18 19 Si02 54 53.9 52.7 55.0 ΑΙΑ 0.5 0.4 0.5 0.5 CaO 8.5 8.5 8.0 8.0 MgO 1.8 1.5 1.8 1.5 Na20 18.0 18.0 17.3 16.0 K20 0.7 0.7 0.7 0.5 B203 13.5 13.0 14.0 12.5 m 2.0 2.0 NfiiO ZnO 3.0 Zr02 2.0 2.0 \ BaO 3.0 P：〇5 FeiOa Sr02 F Li20 0.4： 0.4 雜質 1.0 1.0 0.6 0.6, 1T Α7 Β7 5. Description of the invention (5)-This weight is expressed in milligrams per gram of the glass under test. As described in the method, the biodegradability of the glass fiber composition of the present invention was tested by introducing one (1) gram of glass powder into a physiological solution containing the component 'acid value 7.4 shown below: N a C 1 6 · 7 8 N Η 4 C 1 0, 5 3 5 N a HC 0 a 2 2 6 8 N a H 2 P 0 4 H 2 O 0 · 1 6 6 (Na 3 citrate) 2H2〇0 0 5 9 glycine 0 4 5 0 Η 2 S Ο 4 0 0 4 9 C a C 1 2 0 < 0 2 2 (please read the note on the back first and then fill in this page) Central Bureau of Standards, Ministry of Economic Affairs The dynamic test printed by the Huanggong Consumer Cooperative was selected from the conditions described by Scholze and Conradt. The flow rate is 300 ml per day (300 m1). The duration of this test is fourteen (14) days. The test results are expressed as the percentage of silica in the solution after 14 days (14). The present invention can be explained in more detail with the following examples: Example The glass containing the compositions listed in Table 1 and Table 2 is melted. All glass components can be processed successfully using centrifugal technology. The penultimate row below Table 1 lists the values measured using the DGG method, and the penultimate row represents the biodegradable value obtained according to the aforementioned measurement method. The paper size of the order is applicable to the Chinese National Standard (CNS) Λ4 specification ( 210X297 mm) Table 1 Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 SiOi 54 53 53.5 54 53 54 53 53.5 53.5 53.5 55.5 52 53 52.5 54.7 AUQ, 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 1.9 1 0.5 0.5 CaO, 8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.0 8.5 8.5 8.5 MgO 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.6 3.5 3.5 3.5 Na20 17 17 17 17 '17 17 17 17 17- 17 15.8 14.5 17 17 14.0 K20 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 α.2 0.5 0.5 0.5 1.0 ΒΛ 13 13 13 13 13 13 13 12 12 12 12 14.5 13 12. 12 TiOj 2 2 2 2 1.0 2 2 1.0 MnO 2 2 2 ZnO 2 2 1 1.5 ZrO, 2 2 2 2 BaO 2 3.5 4.0 ΡΛ 1.0 1 1 1 F * Cj〇3 0.3 SrtX 0.3 F 0.6 〇J u2o 0.4 0.3 DGG 45 45 40 40 40 35 35 30 3 0 30 30 25 50 35 20 Biodegradable 500 550 500 550 600 550 600 450 450 500 550 500 550 450 450 Table 2 Example 16 17 18 19 Si02 54 53.9 52.7 55.0 ΑΙΑ 0.5 0.4 0.5 0.5 CaO 8.5 8.5 8.0 8.0 MgO 1.8 1.5 1.8 1.5 Na20 18.0 18.0 17.3 16.0 K20 0.7 0.7 0.7 0.5 B203 13.5 13.0 14.0 12.5 m 2.0 2.0 NfiiO ZnO 3.0 Zr02 2.0 2.0 \ BaO 3.0 P: 〇5 FeiOa Sr02 F Li20 0.4: 0.4 Impurity 1.0 1.0 0.6 0.6