TW201228978A - Unleaded low-melting glass composition - Google Patents
Unleaded low-melting glass composition Download PDFInfo
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- TW201228978A TW201228978A TW100142419A TW100142419A TW201228978A TW 201228978 A TW201228978 A TW 201228978A TW 100142419 A TW100142419 A TW 100142419A TW 100142419 A TW100142419 A TW 100142419A TW 201228978 A TW201228978 A TW 201228978A
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- glass
- glass composition
- low
- melting glass
- lead
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- 239000011521 glass Substances 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 238000002844 melting Methods 0.000 title claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 6
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 6
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 4
- 239000012776 electronic material Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims 1
- 239000010980 sapphire Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 238000007789 sealing Methods 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 239000000292 calcium oxide Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007496 glass forming Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- -1 aluminum-calcium boron Chemical compound 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005303 weighing Methods 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
-
- 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
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
-
- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
-
- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
Landscapes
- 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
Description
201228978 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種用作電漿顯示面板、液晶顯示面板、 電致發光面板、螢光顯示面板、電子呈色顯示面板、發光 二極體顯示面板、氣體放電式顯示面板等所代表之電子材 料基板用之絕緣性覆膜材料及熔封材料的無鉛低熔點玻璃 組合物。 【先前技術】 自先别使用玻璃，作為電子零件之接著或熔封之材料， 或作為用以對電子零件上所形成之電極或電阻器進行保護 或絕緣的被覆材料。特別是隨著近年來電子零件之發展， 開發出電漿顯示面板、液晶顯示面板、電致發光面板、螢 光顯示面板、電子呈色顯示面板、發光二極體顯示面板、 氣體放電式顯示面板等較多種類之顯示面板。 用於該等之玻璃視其用途要求化學穩定性、機械性強 度、流動性、電氣絕緣性等各種特性，特別是於用作熔封 材料之情形時，可列舉低溫下之流動性作為重要之因素。 於流動性不充分之情形時’冑自密封部分洩漏之虞，且未 獲得顯示面板所要求之特性。因此無論何種㈣亦廣泛 使用含有大量降低玻璃熔點之效果極大之Pb〇的低熔點玻 璃（例如’參照專利文獻1)。 然而Pb〇對人體或環境造成之弊端較Λ，且近年來有避 免採用其之趨勢，從而對以PDP(piasma Display 卜電 漿顯不裔）為首之電子材料中之無鉛化進行研究（例如，參 1602I2.doc 201228978 照專利文獻2、專利文獻3 )。 先前技術文獻 專利文獻 專利文獻1 .日本專利特開200U2621號公報 專利文獻2 ·日本專利特開2〇〇〇_2丨95 3 6號公報 專利文獻3 .日本專利特開平9·2272丨4號公報 【發明内容】 發明所欲解決之問題 鉛成分雖然於使玻璃為低熔點方面為重要之成分，但對 人體或環境造成之弊端較大，且近年來有避免採用其之趨 勢，從而於以PDP為首之電子材料中，要求無錯玻璃。 於替代PbO系之無鉛組成中，不穩定之玻璃較多’且於 而溫下進行處王里之情形時，於锻燒中途進行結晶化，而未 充分發揮其功能。 即，上述日本專利特開2〇〇1_52621號公報雖發現作為低 熔點玻璃之效果，但有含有鉛之基本性問題。 進而，上述日本專利特開2〇〇〇_219536號公報及上述日 本專利特開平9-2272 14號公報所揭示者雖不含有鉛，但為 不穩定之玻璃’且於高溫τ進行處理之情料，於炮燒中 途結晶化，而未充分發揮其功能。 解決問題之技術手段 本發明係-種無船低熔點玻璃組合物，其特徵在於.^ 質量。/。計含有：η之Si〇2、5〜 5〜20之 Zn〇、（Μ〜kR〇(Mg〇+Ca〇+ Sr〇+Ba〇)、〇 卜7 之201228978 VI. Description of the Invention: [Technical Field] The present invention relates to a plasma display panel, a liquid crystal display panel, an electroluminescence panel, a fluorescent display panel, an electronic color display panel, and a light emitting diode display. An insulating coating material for an electronic material substrate represented by a panel, a gas discharge display panel, or the like, and a lead-free low-melting glass composition of a sealing material. [Prior Art] Glass is used as a material for subsequent or sealing of electronic parts, or as a covering material for protecting or insulating electrodes or resistors formed on electronic parts. In particular, with the development of electronic components in recent years, plasma display panels, liquid crystal display panels, electroluminescent panels, fluorescent display panels, electronic color display panels, light-emitting diode display panels, gas discharge display panels have been developed. Wait for more types of display panels. The glass used for such a glass requires various properties such as chemical stability, mechanical strength, fluidity, electrical insulation, etc., particularly when used as a sealing material, and it is important to mention fluidity at low temperatures. factor. In the case of insufficient fluidity, the leakage from the sealed portion is not obtained, and the characteristics required for the display panel are not obtained. Therefore, a low-melting glass containing a large amount of Pb 降低 having a large effect of lowering the melting point of the glass is widely used (see, for example, Patent Document 1). However, Pb〇 has a disadvantage to the human body or the environment, and in recent years there has been a tendency to avoid it, thereby studying lead-free in electronic materials such as PDP (piasma Display) (for example, Reference 1602I2.doc 201228978 Patent Document 2, Patent Document 3). PRIOR ART DOCUMENT PATENT DOCUMENT Patent Document 1 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 2, No. 2, No. 2, No. 2, No. 2, No. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The lead component is an important component in making glass a low melting point, but it has a drawback to the human body or the environment, and in recent years, there has been a tendency to avoid it. In the electronic materials led by PDP, error-free glass is required. In the lead-free composition of the PbO-based system, when the glass is unstable, and the temperature is lowered, the crystallization is performed in the middle of the calcination, and the function is not sufficiently exerted. In other words, although the effect of the low-melting glass is found, the basic problem of containing lead is found in the above-mentioned Japanese Patent Publication No. JP-A No. Hei. Further, as disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei 9-2272, and the above-mentioned Japanese Patent Publication No. Hei 9-2272, the disclosure of which is incorporated herein by reference. It is crystallized in the middle of the artillery, but its function is not fully exerted. Technical Solution to Problem The present invention is a non-vessel low-melting glass composition characterized by a mass. /. Zn〇, (Μ~kR〇(Mg〇+Ca〇+Sr〇+Ba〇), 〇卜7, including: 〇Si〇2, 5~5~20
CuO、60〜75 之 Bi203。 160212.doc 201228978 又’如請求項1之無鉛低熔點玻璃組合物，其中3〇〜 3〇〇C中之熱膨脹係數為（70〜100)χ10-7/Χ：，軟化點為 400°C以上500°C以下。 進而 種電子材料用基板，其特徵在於：其使用上述 無錯低熔點玻璃組合物。 進而，一種顯示器用面板，其特徵在於：其使用上述無 錯低溶點玻璃組合物。 發明之效果 可藉由本發明而獲得於電漿顯示面板、液晶顯示面板、 電致發光面板、螢光顯示面板、電子呈色顯示面板、發光 二極體顯示面板、氣體放電式顯示面板等所代表之電子材 料中，於南溫時不易結晶且穩定之無鉛低熔點玻璃組合 物。進而，因貫際上不含有鉛成分，故不會對人體或環境 造成危害。 【實施方式】 本發明係一種無鉛低熔點玻璃組合物，其特徵在於：以 質量。/。計含有：卜6之Si〇2、5〜12之]82〇3、〇〜5之Al2〇3、 5〜20 之 ZnO、0.1 〜3 之 R〇(Mg〇+CaO+SrO+BaO)、0.1 〜7 之CuO, Bi203 of 60~75. 160212.doc 201228978 Further, the lead-free low-melting glass composition of claim 1, wherein the thermal expansion coefficient in the range of (3 to 3 〇〇C) is (70 to 100) χ 10-7/Χ: the softening point is above 400 ° C. Below 500 °C. Further, a substrate for an electronic material characterized in that the above-mentioned error-free low-melting glass composition is used. Further, a panel for display is characterized in that the above-mentioned error-free low-melting point glass composition is used. The effects of the invention can be obtained by the present invention, which are represented by a plasma display panel, a liquid crystal display panel, an electroluminescence panel, a fluorescent display panel, an electronic color display panel, a light emitting diode display panel, a gas discharge display panel, and the like. Among the electronic materials, the lead-free low-melting glass composition which is difficult to crystallize and stabilize at the south temperature. Furthermore, since it does not contain lead components in a continuous manner, it does not cause harm to the human body or the environment. [Embodiment] The present invention is a lead-free low-melting glass composition characterized by mass. /. It includes: 〇6〇, 5~12 of 82〇3, 〇~5 of Al2〇3, 5~20 of ZnO, 0.1~3 of R〇(Mg〇+CaO+SrO+BaO), 0.1 to 7
CuO、60〜75之 Bi203。 又，如技術方案1之無銘低溶點玻璃組合物，其中 30〜300°C中之熱膨脹係數為（70〜1〇〇)xl〇-7广c，軟化點為 400°C以上500°C以下。CuO, Bi203 of 60~75. Further, according to the first embodiment of the present invention, the low-melting point glass composition has a thermal expansion coefficient of (70 to 1 Torr) at 30 to 300 ° C, and a softening point of 400 ° C or more and 500 ° C. the following.
Si〇2為玻璃形成成分，且可藉由與作為其他玻璃形成成 分之B2〇3共存而形成穩定之玻璃，並且於1〜（質量％， 160212.doc 201228978 於以下亦相同）之範圍内含有Si〇2。若超過6%，則玻璃之 軟化點上升，從而成形性、作業性變困難。更佳為2〜4% 之範圍。 B2〇3為玻璃形成成分，且使玻璃熔融變容易，抑制玻璃 之熱膨脹係數之過度上升，且於燒製時贼予玻璃適當之流 動性，並使玻璃之介電常數下降。較佳為於玻璃中於 5〜12%之範圍内含有ha。於未達5%時，玻璃之流動性變 得不充分，而損害燒結性β另一方面，若超過丨2%，則玻 璃之軟化點上升，從而成形性、作業性變困難。更佳為 6〜10%之範圍。 ΖηΟ係使玻璃之軟化點下降，並將熱膨脹係數調整為適 當範圍者’且於玻璃中，於5〜20%之範圍内含有Ζη〇。於 未達5¾時’無法發揮上述作用，若超過2〇%，則玻璃變得 不穩定，且容易產生失透。更佳為8〜15%之範圍。 RO(MgO+CaO+SrO+Ba〇)係使玻璃之軟化點下降，適當 賦予流動性’並將熱膨脹係數調整為適當範圍者，且於 〇.1~3%之範圍内含有R〇(MgO+CaO+Sr〇+BaO)。若超過 3°/〇 ’則熱膨脹係數變得過高。更佳為〇·〗〜2%之範圍。Si〇2 is a glass forming component, and can be formed by coexistence with B2〇3 which is a component of other glass forming, and is contained in a range of 1 to (% by mass, 160212.doc 201228978 is the same below) Si〇2. When it exceeds 6%, the softening point of the glass rises, and the moldability and workability become difficult. More preferably, it is in the range of 2 to 4%. B2〇3 is a glass forming component, and it is easy to melt the glass, and the excessive increase in the thermal expansion coefficient of the glass is suppressed, and the thief gives appropriate fluency to the glass during firing, and the dielectric constant of the glass is lowered. It is preferred to contain ha in the range of 5 to 12% in the glass. When the amount is less than 5%, the fluidity of the glass is insufficient, and the sinterability is impaired. On the other hand, when the content exceeds 丨2%, the softening point of the glass increases, and the moldability and workability become difficult. More preferably in the range of 6 to 10%. The ΖηΟ system lowers the softening point of the glass and adjusts the coefficient of thermal expansion to an appropriate range' and contains Ζη〇 in the range of 5 to 20% in the glass. When the temperature is less than 5⁄4, the above effect cannot be exhibited. If it exceeds 2%, the glass becomes unstable and devitrification is likely to occur. More preferably in the range of 8 to 15%. RO(MgO+CaO+SrO+Ba〇) lowers the softening point of the glass, appropriately imparts fluidity and adjusts the coefficient of thermal expansion to an appropriate range, and contains R〇(MgO) in the range of ~.1 to 3%. +CaO+Sr〇+BaO). If it exceeds 3 ° / 〇 ', the coefficient of thermal expansion becomes too high. More preferably 〇·〗 ~ 2% of the range.
CuO係抑制玻璃之熔融時或烺燒時之失透者，且於 0.1〜7%之範圍内含有CuO。若超過7%，則使玻璃之穩定性 下降。更佳為2~5%之範圍。CuO suppresses devitrification of the glass when it is melted or calcined, and contains CuO in the range of 0.1 to 7%. If it exceeds 7%, the stability of the glass is lowered. More preferably in the range of 2 to 5%.
BhO3係使玻璃之軟化點下降，賦予流動性，並將熱膨 脹係數調整為適當範圍者’且較期望於6〇〜75%之範圍内 含有Bi2〇3。於未達60%時’無法發揮上述作用’若超過 I602l2.doc 201228978 75/〇則熱膨脹係數變得過高。更佳為65〜75°/。之範圍。 于、匕x外，亦可於不損及上述性質之圍内適當加入通 常以氧化物表示之Α1Λ、ln203、Ti02、Sn02、7>〇2等。 . 可藉由實際上不含有Pb0而完全消除對人體或環境造成 t ^響1^處’所謂實際上不含有PbO意指PbO作為雜質 玻璃原料中之程度之量。例如只要為低熔點玻璃中之 〇·3質量％以下之範圍，則上述危害即對人體、環境之影 響，對絕緣特性等造成之影響幾乎沒有，從而實際上變得 不受PbO之影響。 又，如技術方案1之無鉛低熔點玻璃組合物，其中3〇〜 300 C中之熱膨脹係數為（7〇〜1〇〇)xl〇-7rc ，軟化點為 400°C 以上 500。(：以下。’ 本發明之無鉛低熔點玻璃組合物可較佳用於電子材料用 基板、顯示器用面板。 較多情況下將本發明之無鉛低熔點玻璃組合物進行粉末 化而使用。該經粉末化之玻璃通常視需要與導電性粉末、 财火物填充料、耐熱顏料等混合，繼而與有機油混練 成膏。 作為玻璃基板，較乡使用透明之玻璃基板，特別是納鈣 氧化矽系玻璃，或與其類似之玻璃（高軟化點玻璃），或鹼 性成分較少（或幾乎沒有）之鋁鈣硼矽酸系玻璃。 實施例 以卡TFFSlTim···—------------------------------------------------------------ 首先，以玻璃粉末成為實施例所揭示之特定組成之方弋 I60212.doc 201228978 稱量並混合各種無機原料’從而製作原料母料。將該原料 母料杈入鉑坩堝中，並於電加熱爐内於1〇〇〇〜l3〇〇(>c下， 進行1〜2小時之加熱熔融，從而獲得表i之實施例卜5、表2 之比較例1〜4所示組成之玻璃。玻璃之一部分流入模具 中，並製成塊狀而供於熱物性（熱膨脹係數、軟化點）測定 用。剩餘之玻璃係利用急冷雙輥成形機而製成薄片狀，並 利用粉碎裝置整粒為平均粒徑丨〜4 μ〇ι、最大粒徑未達1〇 μιη之粉末狀。 再者，軟化點係使用熱分析裝置TG_DTA(Rigaku(股）製 造）而進行測定。又，熱膨脹係數係使用熱膨脹計，根據 以5°C /min升溫時之30〜3〇(rc下的延伸量而求出。 對於所獲得之玻璃粉末’使用手壓機而壓製成形為1〇 mm X 10 mm多之圓筒狀，並於5〇〇 下進行30分鐘炮燒。 結晶性之評價係關於壓製成形體之煅燒後之外觀，將不 結晶化而保持透明性者作為A，將進行結晶化而喪失透明 性者作為B。 (結果） 將低熔點玻璃組成及各種試驗結果示於表中。 I602l2.doc 201228978 [表i]The BhO3 system lowers the softening point of the glass, imparts fluidity, and adjusts the coefficient of thermal expansion to an appropriate range, and contains Bi2〇3 in a range of 6 〇 to 75%. If it is less than 60%, the above effect cannot be achieved. If it exceeds I602l2.doc 201228978 75/〇, the coefficient of thermal expansion becomes too high. More preferably 65~75°/. The scope. In addition to 匕x, Α1Λ, ln203, Ti02, Sn02, 7> 〇2, etc., which are usually represented by oxides, may be appropriately added in the range which does not impair the above properties. It can completely eliminate the human body or the environment by actually not containing Pb0. The so-called actually does not contain PbO means PbO as the amount of impurities in the glass raw material. For example, as long as it is in the range of 3·3 mass% or less in the low-melting glass, the above-mentioned hazard affects the human body and the environment, and has little effect on the insulating properties and the like, and thus is virtually unaffected by PbO. Further, the lead-free low-melting glass composition of the first aspect, wherein the thermal expansion coefficient in the range of 3 Torr to 300 C is (7 〇 〜 1 〇〇) x l 〇 -7 rc , and the softening point is 400 ° C or more and 500 Å. (The following. The lead-free low-melting glass composition of the present invention can be preferably used for a substrate for an electronic material or a panel for a display. In many cases, the lead-free low-melting glass composition of the present invention is powdered and used. The powdered glass is usually mixed with a conductive powder, a fossil filler, a heat-resistant pigment, etc., and then mixed with an organic oil to form a paste. As a glass substrate, a transparent glass substrate, particularly a nano-calcium oxide system, is used as a glass substrate. Glass, or a glass similar thereto (high softening point glass), or an aluminum-calcium boron borosilicate glass having less (or almost no) alkaline components. Embodiments are card TFFSlTim···-------- -------------------------------------------------- --- First, the glass powder is used as a specific composition disclosed in the examples. I60212.doc 201228978 Weighing and mixing various inorganic raw materials' to prepare a raw material masterbatch. The raw material masterbatch is poured into a platinum crucible, and In an electric heating furnace, heat-melting is performed for 1 to 2 hours under 1 〇〇〇 to 13 〇〇 (>c, thereby obtaining the ratio of the examples of Table i and Table 2 The glass of the composition shown in Examples 1 to 4. One part of the glass flows into the mold and is formed into a block shape for measurement of thermal properties (thermal expansion coefficient, softening point). The remaining glass is formed into a thin film by a quenching twin roll forming machine. And the granules are granulated into a powder having an average particle diameter of 44 μ〇ι and a maximum particle diameter of less than 1 μm. Further, the softening point is a thermal analysis device TG_DTA (manufactured by Rigaku Co., Ltd.). Further, the coefficient of thermal expansion was determined by using a thermal dilatometer according to 30 to 3 Torr at a temperature of 5 ° C /min (the amount of elongation at rc. The obtained glass powder was pressed and formed using a hand press) It is a cylindrical shape of 1 〇mm X 10 mm, and is fired at 5 〇〇 for 30 minutes. The evaluation of crystallinity is about the appearance of the pressed molded body after calcination, and it is not crystallized to maintain transparency. A. Those who lose crystallization by crystallization are referred to as B. (Results) The composition of the low-melting glass and various test results are shown in the table. I602l2.doc 201228978 [Table i]
實施例 1 2 3 4 5 Si02 3.3 5.0 2.3 3.5 3.5 02〇3 8.5 6.1 11.0 10.2 11.2 ZnO 13.6 8.0 19.0 12.7 7.5 MgO 0.5 玻璃組成[wt%] CaO 1.8 1.3 SrO 1.6 BaO 1.0 2.5 1.0 CuO 4.6 6.0 0.5 2.1 1.5 B12O3 69.0 72.3 65.2 68.2 74.0 Al2〇3 0.5 0.2 0.8 熱膨脹係數 xlO'7/°C 87 97 82 83 92 軟化點 °C 460 420 485 480 445 結晶性 A A A A AExample 1 2 3 4 5 Si02 3.3 5.0 2.3 3.5 3.5 02〇3 8.5 6.1 11.0 10.2 11.2 ZnO 13.6 8.0 19.0 12.7 7.5 MgO 0.5 Glass composition [wt%] CaO 1.8 1.3 SrO 1.6 BaO 1.0 2.5 1.0 CuO 4.6 6.0 0.5 2.1 1.5 B12O3 69.0 72.3 65.2 68.2 74.0 Al2〇3 0.5 0.2 0.8 Thermal expansion coefficient xlO'7/°C 87 97 82 83 92 Softening point °C 460 420 485 480 445 Crystalline AAAAA
[表2] 比較例 1 2 3 Si02 0.7 1.2 B2〇3 1.0 14.4 4.0 ZnO 10.0 17.8 8.9 MgO 玻璃組成[wt%] CaO SrO BaO 1.2 5.2 CuO 7.8 8.9 Bi2〇3 80.0 58.4 77.0 AI2O3 3.5 熱膨脹係數 xl0'7/〇C _ 83 87 軟化點 °C - 510 420 結晶性 B B 備考 結晶化 軟化點較高 結晶化傾向 如表1中之實施例1〜5所示，於本發明之組成範圍内，結 160212.doc 201228978 晶化程度較低，流動性較高 顯示面板用之熔封材料。 即較佳作為電子材料基板或 另一方面，偏離本發明之組成範圍之表2中的比較例1〜4 般燒時之結晶化顯著，或不顯示較佳之物性值，從而無法 適用作炼封材料。 I602l2.doc 10-[Table 2] Comparative Example 1 2 3 Si02 0.7 1.2 B2〇3 1.0 14.4 4.0 ZnO 10.0 17.8 8.9 MgO Glass composition [wt%] CaO SrO BaO 1.2 5.2 CuO 7.8 8.9 Bi2〇3 80.0 58.4 77.0 AI2O3 3.5 Thermal expansion coefficient xl0'7 /〇C _ 83 87 Softening point °C - 510 420 Crystallinity BB Preparation crystallization softening point Higher crystallization tendency as shown in Examples 1 to 5 in Table 1, within the composition range of the present invention, the knot 160212. Doc 201228978 The degree of crystallization is lower, and the fluidity is higher. That is, it is preferably used as an electronic material substrate or, on the other hand, in Comparative Examples 1 to 4 which deviate from the composition range of the present invention, the crystallization is remarkable at the time of firing, or does not exhibit a preferable physical property value, so that it is not suitable for use as a refining seal. material. I602l2.doc 10-
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