200948740 六、發明說明： 【發明所屬之技術領域】 本發明係相關於一種適用爲可與低電阻的銀（Ag )系 導體同時焙燒的低溫焙燒基板用材料之無鉛玻璃陶瓷用組 成物。由本發明製得的低溫焙燒基板，無特別之限制，尤 宜負載例如半導體元素或線圈（L)、電容器（C)、電阻 (R )等電子零件等。 【先前技術】 Ο 先前，使用於電腦及其他日用電器-電子機器之陶瓷基 板材料，一般爲氧化鋁。氧化鋁因焙燒溫度爲1 5 00 °c，故 作爲與基板同時焙燒用配線導體，係使用鎢、鉬等高熔點 金屬材料。惟，此類髙熔點金屬材料有電阻較高之缺點， 故希冀使用銀系金屬材料爲電阻較低之導體。相較於鉬等 高熔點金屬，銀系金屬材料因熔點大幅降低，故無法與氧 化鋁基底的高溫焙燒基板同時焙燒。因此，提議各種低溫 焙燒玻璃陶瓷用組成物，其係可在較低焙燒溫度，特別是 © 可與銀系金屬材料同時焙燒的約850°C~l〇50°C之溫度，焙 燒而得燒結體。 此類可於低溫焙燒的玻璃陶瓷用組成物，係廣泛使用 例如專利文獻1記載的含鉛玻璃和氧化鋁粉末之混合物。 惟，此類玻璃陶瓷用組成物因含有鉛，而成環境污染之原 因。 以硼矽酸玻璃爲基底的玻璃和氧化鋁粉末之混合粉末 而形成之玻璃陶瓷用組成物，亦爲廣知的可與銀系金屬導 200948740 體同時焙燒之組成物。 專利文獻2、3揭示一種在含有10~ 55重量％的氧 (CaO )加氧化鎂（MgO ) 、0〜30重量％的三氧化 (Al2〇3) 、45~75 重量 ％ 的二氧化矽（Si02) 、0〜30 %的三氧化二硼（B2〇3 )而成的玻璃粉末中，混合氧 粉末所得之玻璃陶瓷用組成物。惟，此組成物於焙燒 不易控制其結晶化。其原因係玻璃中不含結晶核材料 更進一步，專利文獻4揭示一種玻璃陶瓷用組成 ® 其中玻璃陶瓷係由玻璃粉末和氧化鋁粉末混合而成， 長石結晶，且依據氧化物換算表記時，係含有2 0〜5 0 %的二氧化矽（Si02)、3〜15重量％的三氧化二硼（B2< 30~60重量％的三氧化二鋁（Al2〇3) 、4·5〜15重量％ 化鈣（CaO)、總量0〜5重量％的氧化鋰（U2〇)、 鈉（Na20)及氧化鉀（K20)、總量0~5重量％的氧 (MgO )、氧化鋇（BaO )和氧化鋅（ΖηΟ )、總量0 量％的二氧化鈦（Ti02 )和二氧化锆（Zr02 )。惟， ® 獻僅揭示使用不含三氧化二鋁（Α12〇3 )構成成分的玻 末之玻璃陶瓷用組成物之實例。製作不含三氧化 (Α12〇3 )構成成分般之玻璃時，易發生分相或局部的 化等不均勻現象，且因液相溫度和結晶化溫度相差甚 取出熔融的玻璃時，提早進行結晶化而無法流出。因 此類玻璃不適於連續生產或大量生產。又，同文獻 玻璃陶瓷用組成物，因不安定且易於結晶化，故焙 劇地進行結晶化，玻璃陶瓷用組成物的焙燒收縮舉 化鈣 二鋁 重量 化鋁 時， 〇 物， 含鈣 重量 〇3)、 的氧 氧化 化鎂 〜5重 此文 璃粉 二鋁 結晶 微， 此， ，載的 ί時急 I亦急 200948740 劇地發生，焙燒後易於發生彎曲，製得的燒結體之尺寸精 度差。 [專利文獻1]特開平1 - 1 7974 1號公報 [專利文獻2]美國專利4748085號公報 [專利文獻3]特開昭6 1 -2743 97號公報 [專利文獻4]特開平5-58720號公報 【發明内容】 發明所欲解決之課題 本發明係鑑於上述問題點而施行，本發明的第1目的 係提供一種無鉛玻璃’其係和無機塡料混合而使用於低溫 焙燒基板之製作，不含有害的鉛且易於生產。 本發明的第2目的係提供一種無鉛玻璃陶瓷用組成 物’其係由此類無鉛玻璃與無機塡料的混合物而成，可於 850〜1000 °C與銀系導體同時焙燒，焙燒時可預防急劇的熱 收縮舉動，且供應尺寸精度高的燒結體。 解決課題之方法 本發明者等爲解決上述課題而致力硏究之結果，發現 一種符合上述訴求之玻璃陶瓷用組成物，而完成本發明。 亦即本發明提供以下。 1.—種無鉛玻璃，其係含有重量百分率爲50〜70重量％ 的二氧化矽（SiO2)、10〜2 0重量％的三氧化二硼（B203)、 0.1〜5重量％的三氧化二鋁（Al2〇3) 、10〜20重量％的氧 化鈣（CaO)、總量 1〜8重量％的1種以上選自氧化鋰 (Li20 )、氧化鈉（Na20 )及氧化鉀（K20 )所成群組之 200948740 鹼金屬氧化物 '及總量0 ·5~6重量％的1種以上選自二氧 化鈦（Ti02)及二氧化鉻（ΖΓ〇2)所成群組之金屬氧化物 而形成。 2. 如上述第1項之無鉛玻璃，其係含有總量爲5.0重量％ 以下之1種以上選自氧化鎂（MgO )、氧化緦（SrO )、氧 化鋇（BaO )及氧化鋅（ZnO )所成群組之金屬氧化物而形 成。 3. 如上述第1或2項之無鉛玻璃，其係無鉛玻璃陶瓷用 ® 玻璃。 4. 一種無鉛玻璃陶瓷用組成物，其係含有40〜60重量％ 的上述第1或2項的無鉛玻璃所成之粉末和60~40重量％ 的粉末形狀的無機塡料而形成之混合物。 5. 如上述第4項之無鉛玻璃陶瓷用組成物，其中此無機 塡料係含有二氧化鈦和氧化鋁之混合物而形成。 6. 如上述第5項之無鉛玻璃陶瓷用組成物，其中此無機 塡料更進一步含有至少1種選自 α -石英、堇青石 (cordierite)、鎂尖晶石（magnesia spinel)、鍩石（zircon)。 7. 如上述第4至6項中任一項之無鉛玻璃陶瓷用組成 物，其中含有1〜10重量％的作爲無機塡料之二氧化鈦。 8. —種燒結體，其係焙燒上述第4至7項中任一項之無 鉛玻璃陶瓷用組成物而形成。 [發明效果] 上述構成之本發明的無鉛玻璃，係作爲無鉛玻璃陶瓷 用組成物，焙燒時可完成高結晶化之適用玻璃，提升玻璃 200948740 狀態之安定化，因此，熔融原料而製作玻璃時，不易發生 分相或局部結晶化等不均勻現象，易於製造。且混合此玻 璃粉末和陶瓷粉末而形成之玻璃陶瓷用組成物，因可焙燒 於85 0~ 1 00 0 °C，可與銀系的配線用導體同時焙燒，且提升 對於結晶化之玻璃安定性，因此，易於控制同時焙燒時之 結晶化。亦即，同時焙燒時可預防玻璃內急劇地進行結晶 化，藉此，因可預防焙燒時的收縮舉動，故焙燒而得的燒 結體不易鸯生彎曲。因此，本發明係提供一種可得高尺寸 精度的燒結體之無鉛玻璃陶瓷用組成物。更進一步，本發 明的無鉛玻璃陶瓷用組成物中，作爲無機塡料且含一定量 之二氧化鈦，係作爲外部核材，因此，焙燒玻璃陶瓷用組 成物時，可製得玻璃部分爲高結晶化度之燒結體，藉此， 可提供具有充分的機械強度之玻璃陶瓷燒結體。且本發明 的無鉛玻璃陶瓷用組成物，因不含鉛而無環境污染之問題。 【實施方式】 [進行發明之最佳型態] 本發明中，「玻璃陶瓷用組成物」係指於規定溫度進 行焙燒，爲製造玻璃陶瓷燒結體之組成物。 本發明說明書中，「銀系導體」係指以銀爲主體之金 屬導體，且其熔點約960〜約1200°C左右。銀系導體之例， 例如銀或銀（Ag) /鈀（Pd)，惟不受限於此。 本發明的無鉛玻璃，於與無機塡料粉末混合時，係以 粉末的形態而使用。此時，無鉛玻璃之顆粒徑宜爲 0·5~5·0μιη’尤宜〇.7〜3·5μηι。又，無機塡料粉末之顆粒徑 200948740 宜爲 0.2〜5.0μπι，尤宜 〇.3~2.5μιη。 在形成本發明的玻璃之過程中，三氧化二鋁（ai2o3 ) 係必要成分，藉由適量地含有而提升對於玻璃熔融時的反 玻璃化或結晶化之玻璃安定性，在玻璃陶瓷用組成物的焙 燒時，可預防組成物發生急劇的收縮舉動。三氧化二鋁 (Α12〇3 )的含量宜爲〇. 1〜5重量％ ，尤宜0.3〜4重量％ ， 更宜爲0.3〜3重量％ 。三氧化二鋁（Α1203 )的含量若低於 0.1重量％ ，則焙燒玻璃陶瓷用組成物時，於玻璃內急劇地 ^ 進行結晶化，而組成物急劇地收縮，因此製得的燒結體發 生彎曲等，且降低尺寸精度，若超過5重量％ ，則焙燒時 過度地抑制結晶化，導致結晶化不充分，而降低燒結體的 機械強度。 二氧化矽（Si02 )係玻璃的網狀成形物。二氧化矽 (Si〇2)之含量宜爲50〜70重量％ ，尤宜6 0〜68重量％ ^ 一氧化矽（Si02 )之含量若低於50重量％ ，則降低玻璃的 化學耐久性，若超過70重量％ ，不易進行玻璃的熔融。 三氧化二硼（B2〇3 )係使用爲溶劑。三氧化二硼（B2〇3 ) 的含量宜爲10〜20重量96 ，尤宜11~18重量％ 。三氧化二 硼（B2〇3)的含量若低於10重量％ ，極不易進行玻璃的熔 融，若超過20重量％ ，則降低玻璃的化學耐久性》 氧化鈣（CaO )係降低玻璃製造時的熔融溫度，同時 亦爲焙燒玻璃陶瓷用組成物時的析出結晶之構成成分。氧 化鈣（CaO)之含量宜爲10~2 0重量％ ，尤宜11~15重量 % 。氧化鈣（CaO)之含量若低於10重量％ ，則提高製造 200948740 玻璃時的熔融溫度，且焙燒玻璃陶瓷組成物時的玻璃結晶 化度不足，而降低燒結體的機械強度，若超過20重量％ ， 則焙燒時亦發生彎曲。 R2〇 ( R爲鋰（Li)、鈉（Na)、鉀（K))係降低玻 璃製造時的熔融溫度，且藉由適量地含有而提升對於玻璃 熔融時的反玻璃化或結晶化之玻璃安定性，係預防焙燒時 的玻璃陶瓷組成物之急劇的收縮舉動之成分。含有氧化鋰 (Li2〇 )、氧化鈉（Na2〇 )及氧化鉀（K20 )中任一種即 可，亦可含有2種或3種全部。其含量宜爲總量1〜8重量 % ，尤宜3〜7重量％ 。其含量若低於1重量％ ，則提高玻 璃製造時的熔融溫度，且焙燒玻璃陶瓷用組成物時，結晶 化係急劇地進行，使燒結體的尺寸精度變差，即使超過8 重量％ ，燒結體的彎曲變大。 二氧化鈦（Ti02)及二氧化锆（Zr02)係提高玻璃製 作時的熔融安定性，同時使用爲焙燒玻璃陶瓷用組成物 時，引發結晶化反應之核材。含有二氧化鈦（Ti02 )及二 氧化鉻（Zr02 )中至少一種即可，亦可同時含有此二種。 宜含量宜爲總量0.5〜6重量％。其含量若低於0.5重量％ ， 則焙燒玻璃陶瓷組成物時，玻璃之結晶化度不足，而降低 燒結體之機械強度，若超過6重量％ ，則不易進行玻璃之 熔融。 氧化鋅（ZnO )及鹼土族金屬氧化物中的氧化鎂 (MgO)、氧化鋇（BaO )及氧化緦（Sr〇 )，因係降低玻 璃製作時的熔融溫度之有效成分，亦可含有。惟，一般其 -10- 200948740 總量宜爲整體玻璃成份之5重量％以下。 量％ ，則焙燒玻璃陶瓷組成物時，結晶化 寸精度變差。 亦可適量地含有二氧化硒（Se02 )、二 三氧化二鐵（Fe203 )、二氧化錳（Μη02 )、 氧化鈷（CoO )、二氧化錫（Sn〇2 )、三氧化 五氧化二釩（V205 )、氧化鎳（NiO )、三氧< 及二氧化締（Te02)，其總量宜爲整體玻 ❹ ％以下。 其次，本發明的無鉛玻璃陶瓷用組成 無機塡料，係如以下之說明。 無機塡料之含量，相對於整體玻璃陶 爲40〜60重量％ 。少於40重量％時，無法 強度，若爲60重量％以上，則不易於焙焊 二氧化鈦係作爲本發明的無鉛玻璃陶 機塡料之必要成分，焙燒時，其係作用爲夕 〇 促進從玻璃粉末與無機塡料之界面往玻璃 之反應。因此，將二氧化鈦摻合於無機塡 用組成物的燒結體之玻璃部位，可完成高 升機械強度。考量二氧化鈦若低於玻璃陶 重量％或多於10重量％時，作爲外部核相 與其他無機塡料或玻璃粉末之平衡，二氧 無鉛玻璃陶瓷用組成物的1〜10重量％，尤 氧化鋁係作爲本發明的無鉛玻璃陶瓷 塡料之必要成分，係藉由焙燒而析出於玻 總量若超過5重 失去平衡，且尺 氧化姉（Ce02)、 氧化銅（CuO)、 丨二銻（Sb203 )、 匕二鉻（Cr203 )、 璃成份之2重量 物之構成要素之 瓷用組成物，宜 具有充分的機械 I 〇 瓷用組成物、的無 卜部核材，藉此， 內部而析出結晶 料，於玻璃陶瓷 結晶化度，可提 瓷用組成物的1 之效果變差，及 化鈦之含量宜爲 宜5~ 1 0重量％。 用組成物的無機 璃陶瓷用組成物 11- 200948740 中的結晶之構成成分。氧化鋁之含量宜爲玻璃陶瓷用 物的10〜59重量％ ，尤宜20~45重量％ 。氧化鋁之含 少於10重量％時，焙燒時的析出結晶量不足，而降低 強度，若爲59重量％以上，則不易於焙燒。 雖α -石英及鎂尖晶石（magnesiaspinel)非爲作 機塡料之必要成分，惟係可增大由本發明的無鉛玻璃 用組成物而得的燒結物之熱膨脹係數之成份。依需求 當地調整其種類和用量於玻璃陶瓷用組成物的0〜4 0 〇 %之範圍，藉此，可調整燒結體的熱膨脹係數之增大卷 雖堇青石（cordierite)及锆石（zircon)非爲作 機塡料之必要成分，惟係可降低由本發明的無鉛玻璃 用組成物而得的燒結物之熱膨脹係數之成份。依需求 當地調整其種類和用量於玻璃陶瓷用組成物的〇〜4 0 %之範圍，藉此，可調整燒結體的熱膨脹係數之降低卷 [實例] 以下係參考實例而更詳細地說明本發明，惟本發 φ 受限於這類實例。 調合原料使其形成如第1~3表所示之玻璃組成， 混合並於1 500〜1 650°C熔融此調合原料2小時後，急 卻而形成玻璃。以使用異丙醇作爲有機系媒介之藉由 機的濕式粉碎，將製得的玻璃製作成平均粒徑2 μιη之 粉末。使用雷射散射式粒度分布測定器（日機裝製微_ 來測定製得的玻璃粉末之平均粒徑。以第1〜3表所示 合比率，充分地混合此玻璃粉末、平均粒徑μπι的 化鈦粉末、平均粒徑1.5 μπι的氧化鋁粉末、平均粒徑 組成 量若 機械 ^^2* <fll I- 爲無 陶瓷 而適 重量 :度。 爲無 陶瓷 而適 重量 (度。 明不 進行 速冷 球磨 玻璃 九道） 之摻 二氧 2 μηι -12- 200948740 的α -石英及平均粒徑2μιη的锆石（zircon)，而製得本發 明的無鉛玻璃陶瓷用組成物作爲混合粉末。以微差熱分析 (DTA )來測定製得的混合粉末之玻璃轉移點。使此混合 粉末於lOMPa下進行模具成形，將其維持於第1~3表所示 之焙燒溫度1小時，而製得燒結體。以熱機械測定（TM A ) 來測定製得的燒結體於50至40(TC中之平均熱膨脹係數。 更於上述製得的混合粉末中，添加增塑劑（己二酸二 辛酯）、溶劑（甲苯）及黏著劑（聚乙烯丁縮醛），混合 〇 24小時後製得漿狀物。使用此漿狀物，以刮片法來製作厚 度ΙΟΟμιη之軟質陶瓷片（green sheet)。將此軟質陶瓷片裁 切成75mm角，藉由沖孔以50mm間隔而形成2點的通過 孔（through hole)後，維持軟質陶瓷片於第1~3表所示之 焙燒溫度1小時，而製得燒結體。測定製得的燒結體的通 過孔（throughhole)間之尺寸。尺寸精度之評價方法係以 焙燒收縮後的燒結體的陶瓷孔（wear hole )間之尺寸的偏 差（n=10)而評價，若其偏差低於平均値的0.2¾時，表 φ 示爲〇，爲0.2%以上而低於0.4%時，表示爲△，爲0.4 嗖以上時，表示爲X。 由表清楚可知，實例2所示的本發明的無鉛玻璃陶 瓷用組成物，因可於1〇〇〇 °C以下的溫度焙燒，故可與銀系 導體同時焙燒。又燒結體的結晶化度高，具有實用上充足 的200MPa以上之機械強度（彎曲強度），且尺寸精度亦 優異。相對於此，比較例1的組成物具有200MPa以上的 彎曲強度，然而尺寸精度變差，比較例2〜9的組成物中， 任一者之彎曲強度均爲2 OOMPa以下，其機械強度差。 -13- 200948740 【第1表】 —-Λ-1- 實例1 實例2 實例3 實例4 比較例1 比較例2 比較例3 Si02 68 65 64 62 65 62 59 B2〇3 13 15 13 15 15 15 15 AI2O3 1.3 0.5 3 3 — 3 6 CaO 12 12 13 15 12 12 12 玻璃組 MgO 1 1 1 — — 1 1 成（重 BaO 1 1 1 — 2 1 1 量％ ) ZnO — — — — 1 — — Li20 — — — — — — — Na20 2 2 1 2 — 2 2 K20 2 2 2 2 2 2 3 Ti02 1 1 1 — 2 1 1 Zr02 0.7 0.5 1 1 1 1 — 玻璃勝點CC) 635 625 640 600 630 625 610 玻璃陶 玻璃 52 59 50 56 52 50 55 瓷組成 二氧化鈦 5 1 6 4 — — 5 物（重 氧化鋁 43 40 44 20 48 50 40 量％ ) (2 —石英 — — — 20 — — — 锆石 — — — — — — — 焙燒溫度rc) 920 900 920 880 900 900 900 彎曲強度（MPa) 240 220 230 210 230 170 150 結晶相 多 多 多 多 多 少 少 熱膨脹係數 (xlO-Vt) 55 52 52 68 54 50 53 尺寸精度 〇 〇 〇 〇 X 〇 Δ -14- 200948740 【第2表】 實例5 實例6 實例7 實例8 比較例4 比較例5 比較例6 玻璃 組成 (重 量％ ) Si〇2 69 62 58 52 70 60 64 B203 13 15 12 18 10 21 12 A1203 0.2 3 1 1 2 — 1 CaO 12 15 18 18 13 12 21 MgO — — — — — — — BaO 0.5 — — — 1 1 — ZnO — — — — — — Li20 1 — 1 1 3 — — Na2〇 2 2 2 2 1 2 1 k2o 1.8 2 2 2 — 2 1 Ti〇2 0.5 — 2 2 — 1 — Zr02 — 1 4 4 — 1 — 玻璃輞 够點rc) 670 600 610 580 680 580 590 玻璃 陶瓷 組成 物（重 量％ ) 玻璃 55 57 53 53 60 39 45 二氧化鈦 5 8 2 2 2 1 5 氧化銘 40 35 45 45 38 60 50 α —石英 — — — — — — — 锆石 — — — — — — 一 mm iS (°C) 1000 890 900 890 1000 900 950 彎曲強度（MPa) 210 210 200 200 150 120 110 結晶相 多 多 多 多 少 少 少 熱膨隱數 (xlO_7/°C) 48 52 55 58 58 58 60 尺寸精度 〇 〇 〇 〇 Δ 〇 〇 -15- 200948740 【第3表】 實例9 實例10 實例11 實例12 比較例7 比較例8 比較例9 玻璃 組成 (重 〇% ) Si〇2 69 69 65 60 55 68 65 B203 11 11 13 12 15 11 13 a1203 0.5 0.5 3 2 3.5 0.5 3 CaO 11 11 14 12 18 11 14 MgO — — — 1 2 — — BaO 0.5 0.5 — 1 2 0.5 — ZnO — — — 1 2 — — U2〇 1 1 一 — — 2 — Na20 3 3 2 2 0.5 4 2 K20 3 3 2 3 — 3 2 Ti02 0.5 0.5 — 3 1 — — Zr02 0.5 0.5 1 3 1 — 1 玻璃轉 移點（。C) 590 590 620 650 640 575 620 玻璃 陶瓷 組成 物（重 m% ) 玻璃 50 50 45 55 55 60 32 二氧化鈦 7 7 6 2 2 8 9 氧化鋁 43 20 12 43 43 32 9 <3：—石英 — 37 — — — 50 锆石 — 23 — — — — — 焙燒溫度（。〇 880 880 900 950 930 880 910 彎曲強度（MPa) 210 205 200 210 190 130 120 結晶相 多 多 多 多 多 少 少 熱膨脹係數 (xlO_7/°C) 58 44 79 58 56 60 80 尺寸精度 〇 〇 〇 〇 Δ △ 〇 -16- 200948740 [應用於產業之可能性] 本發明之無鉛玻璃係玻璃陶瓷用組成物中於較低溫度 而可完成高結晶化之適用玻璃，且玻璃狀態較安定化，其 製造時不易發生分相或局部的結晶化等不均勻現象，而易 於製造。本發明之無鉛玻璃陶瓷用組成物因不含有害的鉛 化合物，且可焙燒於約85(TC〜1000 °C之較低溫度，又可預 防焙燒時的急劇之焙燒收縮舉動，給予製得的燒結體具有 實用上充足之機械強度，故適用爲與銀系導體同時焙燒用 的其他各種用途之低溫焙燒基板用玻璃陶瓷用組成物。 【圈式簡單說明】BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lead-free glass-ceramic composition suitable for a material for a low-temperature baking substrate which can be simultaneously fired with a low-resistance silver (Ag)-based conductor. The low-temperature calcined substrate produced by the present invention is not particularly limited, and is preferably loaded with an electronic component such as a semiconductor element or a coil (L), a capacitor (C), a resistor (R), or the like. [Prior Art] 先前 Previously, ceramic substrate materials used in computers and other household appliances-electronic machines were generally alumina. Since the alumina has a calcination temperature of 1,500 ° C, a high-melting-point metal material such as tungsten or molybdenum is used as a wiring conductor for simultaneous baking with a substrate. However, such a bismuth melting point metal material has a disadvantage of high electrical resistance, so it is desirable to use a silver-based metal material as a conductor having a lower electrical resistance. Compared with a high melting point metal such as molybdenum, the silver metal material cannot be baked at the same time as the high temperature baking substrate of the alumina substrate because the melting point is greatly lowered. Therefore, various compositions for low-temperature calcination glass ceramics are proposed which can be calcined at a lower calcination temperature, in particular, at a temperature of about 850 ° C to 10 ° C which can be simultaneously calcined with a silver-based metal material. body. Such a composition for a glass ceramic which can be calcined at a low temperature is widely used, for example, a mixture of lead-containing glass and alumina powder described in Patent Document 1. However, such glass-ceramic compositions contain lead and cause environmental pollution. A composition for a glass ceramic formed by mixing a powder of glass and alumina powder based on borosilicate glass is also known as a composition which can be simultaneously fired with a silver-based metal conductor 200948740. Patent Documents 2 and 3 disclose an amount of 10 to 55 wt% of oxygen (CaO) plus magnesium oxide (MgO), 0 to 30% by weight of trioxide (Al2?3), and 45 to 75 wt% of ceria ( In the glass powder obtained by mixing SiO 2 and 0 to 30% of boron trioxide (B 2 〇 3 ), a composition for a glass ceramic obtained by mixing an oxygen powder. However, it is not easy to control the crystallization of this composition upon firing. The reason for this is that the glass does not contain crystal core material. Patent Document 4 discloses a composition for glass ceramics. The glass ceramic is a mixture of glass powder and alumina powder, feldspar crystals, and according to the oxide conversion table. Containing 20 to 50% of cerium oxide (SiO 2 ), 3 to 15% by weight of boron trioxide (B 2 < 30 to 60% by weight of aluminum oxide (Al 2 〇 3), 4·5 to 15 weight Calcium (CaO), total amount of 0 to 5% by weight of lithium oxide (U2 〇), sodium (Na20) and potassium oxide (K20), total amount of 0 to 5% by weight of oxygen (MgO), cerium oxide (BaO And zinc oxide (ΖηΟ), a total amount of 0% by weight of titanium dioxide (Ti02) and zirconium dioxide (Zr02). However, ® only reveals the use of glass containing no constituents of aluminum oxide (Α12〇3) An example of a composition for a glass ceramic. When a glass containing no constituents of trioxide (Α12〇3) is produced, unevenness such as phase separation or localization is likely to occur, and the difference between the liquidus temperature and the crystallization temperature is taken out. When molten glass is used, it is crystallized early and cannot flow out. Therefore, the glass type is not suitable for the connection. Production or mass production. Moreover, the composition of the glass ceramics in the same literature is crystallized by baking due to instability and crystallization, and when the composition of the glass ceramic is calcined and shrunk, the calcium alumino-weighted aluminum is used. Material, calcium-containing weight 〇 3), oxy-magnesia hydride ~ 5 heavy granules of varnish, aluminum, crystal, micro, this, ί 急 urgent I also urgent 200948740 drama occurred, easy to bend after roasting, made The sintered body has poor dimensional accuracy. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above problems, and a first object of the present invention is to provide a lead-free glass which is mixed with an inorganic pigment and used for the production of a low-temperature baking substrate. Contains harmful lead and is easy to produce. A second object of the present invention is to provide a composition for lead-free glass ceramics which is obtained by mixing a mixture of such lead-free glass and an inorganic material, and can be simultaneously baked at a temperature of 850 to 1000 ° C with a silver-based conductor, and can be prevented during baking. A sharp heat shrinking action and supply of a sintered body with high dimensional accuracy. MEANS FOR SOLVING THE PROBLEMS As a result of intensive research to solve the above problems, the inventors of the present invention have found a composition for a glass ceramic that meets the above-mentioned requirements and completed the present invention. That is, the present invention provides the following. 1. A lead-free glass comprising 50 to 70% by weight of cerium oxide (SiO2), 10 to 20,000% by weight of boron trioxide (B203), 0.1 to 5% by weight of trioxide Aluminum (Al 2 〇 3), 10 to 20% by weight of calcium oxide (CaO), and a total amount of 1 to 8 wt% of one or more selected from the group consisting of lithium oxide (Li20), sodium oxide (Na20), and potassium oxide (K20) A group of 200948740 alkali metal oxides and a total amount of 0.5 to 6% by weight of one or more metal oxides selected from the group consisting of titanium oxide (Ti02) and chromium dioxide (ΖΓ〇2) are formed. 2. The lead-free glass according to the above item 1, wherein the total amount of the lead-free glass is 5.0% by weight or less selected from the group consisting of magnesium oxide (MgO), strontium oxide (SrO), barium oxide (BaO), and zinc oxide (ZnO). Formed by a group of metal oxides. 3. Lead-free glass according to item 1 or 2 above, which is a lead-free glass ceramic ® glass. A composition for lead-free glass ceramics comprising a mixture of 40 to 60% by weight of the powder of the lead-free glass of the above item 1 or 2 and 60 to 40% by weight of a powdery inorganic material. 5. The composition for lead-free glass ceramics according to item 4 above, wherein the inorganic tantalum is formed by a mixture of titanium oxide and aluminum oxide. 6. The lead-free glass ceramic composition according to item 5 above, wherein the inorganic material further contains at least one selected from the group consisting of α-quartz, cordierite, magnesia spinel, and vermiculite ( Zircon). 7. The composition for lead-free glass ceramics according to any of the above items 4 to 6, which contains 1 to 10% by weight of titanium dioxide as an inorganic tantalum. A sintered body formed by baking the composition for lead-free glass ceramics according to any one of items 4 to 7 above. [Effect of the Invention] The lead-free glass of the present invention is a composition for lead-free glass ceramics, and can be used for high-crystallization crystallization in the case of firing, and the stability of the glass is improved in the state of 200948740. Therefore, when the raw material is melted and glass is produced, It is not easy to cause unevenness such as phase separation or partial crystallization, and it is easy to manufacture. The glass-ceramic composition formed by mixing the glass powder and the ceramic powder can be baked at a temperature of 85 to 100 ° C, and can be simultaneously fired with a silver-based wiring conductor, and the glass stability for crystallization can be improved. Therefore, it is easy to control the crystallization at the time of baking. In other words, it is possible to prevent rapid crystallization in the glass during the simultaneous firing, whereby the sintered body obtained by baking can be prevented from being bent and bent because the shrinkage behavior during baking can be prevented. Accordingly, the present invention provides a composition for a lead-free glass ceramic which can obtain a sintered body of high dimensional accuracy. Further, in the composition for lead-free glass ceramics of the present invention, as an inorganic material, a certain amount of titanium dioxide is contained as an external core material. Therefore, when the composition for glass ceramics is fired, the glass portion can be made highly crystallized. A sintered body of a degree, whereby a glass ceramic sintered body having sufficient mechanical strength can be provided. Further, the composition for lead-free glass ceramics of the present invention has no problem of environmental pollution because it does not contain lead. [Embodiment] [Best Mode for Carrying Out the Invention] In the present invention, the "composition for glass ceramics" means a composition for producing a glass ceramic sintered body by baking at a predetermined temperature. In the specification of the present invention, "silver-based conductor" means a metal conductor mainly composed of silver, and has a melting point of about 960 to about 1200 °C. Examples of silver-based conductors, such as silver or silver (Ag) / palladium (Pd), are not limited thereto. The lead-free glass of the present invention is used in the form of a powder when it is mixed with an inorganic tantalum powder. At this time, the particle diameter of the lead-free glass is preferably 0·5~5·0μιη', particularly 〇.7~3·5μηι. Further, the particle diameter of the inorganic tantalum powder is preferably 0.2 to 5.0 μm, and particularly preferably 0.3 to 2.5 μm. In the process of forming the glass of the present invention, aluminum oxide (ai2o3) is an essential component, and the glass stability for devitrification or crystallization during glass melting is enhanced by an appropriate amount, and the composition for glass ceramics is improved. During the calcination, it is possible to prevent the composition from undergoing a sharp contraction behavior. The content of the aluminum oxide (Α12〇3) is preferably from 1 to 5% by weight, particularly preferably from 0.3 to 4% by weight, more preferably from 0.3 to 3% by weight. When the content of the aluminum oxide (Α1203) is less than 0.1% by weight, when the composition for a glass ceramic is fired, crystallization is rapidly performed in the glass, and the composition is sharply shrunk, so that the obtained sintered body is bent. When the amount is more than 5% by weight, the crystallization is excessively suppressed during baking, and crystallization is insufficient, and the mechanical strength of the sintered body is lowered. A network of cerium oxide (SiO 2 )-based glass. The content of cerium oxide (Si〇2) is preferably 50 to 70% by weight, particularly preferably 60 to 68% by weight. If the content of cerium oxide (SiO 2 ) is less than 50% by weight, the chemical durability of the glass is lowered. If it exceeds 70% by weight, it is difficult to melt the glass. Boron trioxide (B2〇3) is used as a solvent. The content of boron trioxide (B2〇3) is preferably 10 to 20 by weight 96, particularly preferably 11 to 18% by weight. When the content of boron trioxide (B2〇3) is less than 10% by weight, it is extremely difficult to melt the glass, and if it exceeds 20% by weight, the chemical durability of the glass is lowered. Calcium oxide (CaO) reduces the production of glass. The melting temperature is also a constituent of the precipitated crystals when the composition for glass ceramics is fired. The content of calcium oxide (CaO) is preferably from 10 to 20% by weight, particularly preferably from 11 to 15% by weight. When the content of calcium oxide (CaO) is less than 10% by weight, the melting temperature at the time of producing 200948740 glass is increased, and the degree of glass crystallization when the glass ceramic composition is fired is insufficient, and the mechanical strength of the sintered body is lowered, and if it exceeds 20% by weight %, then bending also occurs during firing. R2〇 (R is lithium (Li), sodium (Na), or potassium (K)) is a glass which lowers the melting temperature at the time of glass production, and increases the amount of devitrification or crystallization when the glass is melted by an appropriate amount. Stability is a component that prevents rapid shrinkage of the glass-ceramic composition during firing. Any one of lithium oxide (Li2〇), sodium oxide (Na2〇) and potassium oxide (K20) may be contained, and two or three types may be contained. The content is preferably from 1 to 8 % by weight, particularly preferably from 3 to 7 % by weight. When the content is less than 1% by weight, the melting temperature at the time of glass production is increased, and when the composition for glass ceramics is fired, the crystallization is rapidly performed, and the dimensional accuracy of the sintered body is deteriorated, and even if it exceeds 8% by weight, sintering is performed. The curvature of the body becomes larger. Titanium dioxide (Ti02) and zirconium dioxide (ZrO2) are used to improve the melt stability during the production of glass, and a core material which initiates a crystallization reaction when a composition for baking a glass ceramic is used. It may contain at least one of titanium oxide (Ti02) and chromium dioxide (ZrO 2 ), and may contain both of them. Preferably, the content is from 0.5 to 6% by weight based on the total amount. When the content is less than 0.5% by weight, when the glass ceramic composition is fired, the degree of crystallization of the glass is insufficient to lower the mechanical strength of the sintered body, and if it exceeds 6% by weight, the glass is not easily melted. Magnesium oxide (MgO), barium oxide (BaO), and strontium oxide (Sr〇) in zinc oxide (ZnO) and an alkaline earth metal oxide may be contained as an effective component for lowering the melting temperature at the time of glass production. However, in general, the total amount of -10-200948740 should be less than 5% by weight of the total glass component. When the amount is %, the crystallizing precision is deteriorated when the glass ceramic composition is fired. It may also contain selenium dioxide (Se02), diiron trioxide (Fe203), manganese dioxide (Μη02), cobalt oxide (CoO), tin dioxide (Sn〇2), vanadium pentoxide (5). V205), nickel oxide (NiO), trioxane <RTIgt; and teoxide(Te02), the total amount thereof is preferably less than or equal to the entire glass. Next, the composition of the lead-free glass ceramic of the present invention is as follows. The content of the inorganic tantalum is 40 to 60% by weight relative to the whole glass. When the amount is less than 40% by weight, the strength is not high, and if it is 60% by weight or more, the titanium dioxide is not easily soldered as an essential component of the lead-free glassware of the present invention, and when it is baked, it acts to promote the glass. The reaction between the powder and the inorganic tantalum to the glass. Therefore, by adding titanium dioxide to the glass portion of the sintered body of the inorganic cerium composition, high mechanical strength can be achieved. When the amount of titanium dioxide is less than or equal to 10% by weight of the glass ceramics, the balance of the external core phase with other inorganic materials or glass powders is 1 to 10% by weight of the composition of the lead-free glass ceramics, especially alumina. It is an essential component of the lead-free glass-ceramic crucible of the present invention, and is decomposed by calcination to a total amount of more than 5 weights, and is cerium oxide (Ce02), copper oxide (CuO), and bismuth (Sb203). The porcelain composition of the constituent elements of the bismuth chrome (Cr203) and the two components of the glass component preferably has a sufficient mechanical I enamel composition and a non-nuclear core material, whereby the crystal material is precipitated internally. In the degree of crystallinity of the glass ceramics, the effect of the composition for extracting porcelain is deteriorated, and the content of titanium is preferably from 5 to 10% by weight. The constituents of the crystals in the inorganic ceramics composition of the composition 11-200948740. The content of the alumina is preferably from 10 to 59% by weight, particularly preferably from 20 to 45% by weight, based on the amount of the glass ceramics. When the content of the alumina is less than 10% by weight, the amount of precipitated crystals at the time of firing is insufficient, and the strength is lowered. If it is 59% by weight or more, baking is not easy. Although α-quartz and magnesium spinel are not essential components for the coating, the composition of the thermal expansion coefficient of the sintered body obtained from the lead-free glass composition of the present invention can be increased. Adjust the type and amount of the glass ceramic composition in the range of 0 to 40% by weight according to the demand, thereby adjusting the thermal expansion coefficient of the sintered body, although the cordierite and zircon (zircon) It is not a necessary component of the machine material, but is a component which can reduce the thermal expansion coefficient of the sintered product obtained from the lead-free glass composition of the present invention. The type and amount of the composition for the glass ceramics are adjusted locally according to the demand, and the reduction coefficient of the thermal expansion coefficient of the sintered body can be adjusted. [Examples] Hereinafter, the present invention will be described in more detail with reference to examples. However, the present φ is limited to such instances. The raw materials were blended to form a glass composition as shown in Tables 1 to 3, and the mixed raw materials were melted at 1,500 to 1,650 ° C for 2 hours, and then rapidly formed to form glass. The obtained glass was formed into a powder having an average particle diameter of 2 μη by wet pulverization using an isopropanol as an organic medium. The average particle diameter of the obtained glass powder was measured using a laser scattering type particle size distribution measuring apparatus (daily machined micro_). The glass powder was uniformly mixed at a mixing ratio shown in Tables 1 to 3, and the average particle diameter μπι was used. A titanium powder, an alumina powder having an average particle diameter of 1.5 μm, and an average particle diameter composition amount if the mechanical ^^2* <fll I- is a ceramic-free weight: a degree: a ceramic-free weight (degree. The α-quartz doped with dioxins 2 μηι -12-200948740 and zircon having an average particle diameter of 2 μm are not subjected to rapid cooling ball milling, and the composition for lead-free glass ceramics of the present invention is prepared as a mixed powder. The glass transition point of the obtained mixed powder was measured by differential thermal analysis (DTA), and the mixed powder was subjected to mold molding at 10 MPa, and maintained at the baking temperature shown in Tables 1 to 3 for 1 hour. A sintered body was obtained. The obtained sintered body was measured by thermomechanical measurement (TM A ) at an average thermal expansion coefficient of 50 to 40 (TC). Further, a plasticizer (adipate) was added to the mixed powder prepared above. Dioctyl ester), solvent (toluene) and viscosity The agent (polyvinyl butyral) was mixed for 24 hours to obtain a slurry. Using this slurry, a soft green sheet having a thickness of ΙΟΟμηη was produced by a doctor blade method. After cutting into a 75 mm angle, a through hole of 2 points was formed by punching at intervals of 50 mm, and then the soft ceramic piece was maintained at the baking temperature shown in Tables 1 to 3 for 1 hour to obtain a sintered body. The dimension between the through holes of the obtained sintered body. The method for evaluating the dimensional accuracy is evaluated by the deviation (n=10) between the sizes of the ceramic holes of the sintered body after the baking shrinkage, if When the deviation is less than 0.23⁄4 of the average enthalpy, the table φ is 〇, and when it is 0.2% or more and less than 0.4%, it is represented by Δ, and when it is 0.4 嗖 or more, it is represented by X. As is clear from the table, the example 2 shows The lead-free glass ceramic composition of the present invention can be calcined at a temperature of 1 ° C or lower, so that it can be simultaneously fired with a silver-based conductor, and the sintered body has a high degree of crystallization, and has a practically sufficient 200 MPa or more. Mechanical strength (bending strength), and dimensional accuracy On the other hand, the composition of Comparative Example 1 has a bending strength of 200 MPa or more, but the dimensional accuracy is deteriorated, and the bending strength of any of the compositions of Comparative Examples 2 to 9 is 200 MPa or less, and the mechanical strength thereof is obtained. -13- 200948740 [Table 1] —-Λ-1- Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Si02 68 65 64 62 65 62 59 B2〇3 13 15 13 15 15 15 15 AI2O3 1.3 0.5 3 3 — 3 6 CaO 12 12 13 15 12 12 12 Glass group MgO 1 1 1 — — 1 1 (weight BaO 1 1 1 — 2 1 1 %) ZnO — — — — 1 — — Li20 — — — — — — — Na20 2 2 1 2 — 2 2 K20 2 2 2 2 2 2 3 Ti02 1 1 1 — 2 1 1 Zr02 0.7 0.5 1 1 1 1 — Glass wins CC) 635 625 640 600 630 625 610 Glass terracotta glass 52 59 50 56 52 50 55 Porcelain composition Titanium dioxide 5 1 6 4 — 5 (heavy alumina 43 40 44 20 48 50 40% by volume) (2 — Quartz — — — 20 — — — Zircon — — — — — — — Calcination temperature rc) 920 900 920 880 900 900 900 Flexural strength (MPa) 240 220 230 210 23 0 170 150 Crystalline phase more or less thermal expansion coefficient (xlO-Vt) 55 52 52 68 54 50 53 Dimensional accuracy 〇〇〇〇X 〇Δ -14- 200948740 [Table 2] Example 5 Example 6 Example 7 Example 8 Comparison Example 4 Comparative Example 5 Comparative Example 6 Glass composition (% by weight) Si〇2 69 62 58 52 70 60 64 B203 13 15 12 18 10 21 12 A1203 0.2 3 1 1 2 — 1 CaO 12 15 18 18 13 12 21 MgO — — — — — — — BaO 0.5 — — — 1 1 — ZnO — — — — — — Li20 1 — 1 1 3 — — Na2〇2 2 2 2 1 2 1 k2o 1.8 2 2 2 — 2 1 Ti〇2 0.5 — 2 2 — 1 — Zr02 — 1 4 4 — 1 — Glass 辋 rc) 670 600 610 580 680 580 590 Glass-ceramic composition (% by weight) Glass 55 57 53 53 60 39 45 Titanium dioxide 5 8 2 2 2 1 5 Oxidation 40 35 45 45 38 60 50 α — Quartz — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — 200 150 120 110 Crystalline phase more or less thermal expansion (xlO_7/°C) 48 5 2 55 58 58 58 60 Dimensional accuracy 〇〇〇〇Δ 〇〇-15- 200948740 [Table 3] Example 9 Example 10 Example 11 Example 12 Comparative Example 7 Comparative Example 8 Comparative Example 9 Glass composition (% by weight) Si〇 2 69 69 65 60 55 68 65 B203 11 11 13 12 15 11 13 a1203 0.5 0.5 3 2 3.5 0.5 3 CaO 11 11 14 12 18 11 14 MgO — — — 1 2 — — BaO 0.5 0.5 — 1 2 0.5 — ZnO — — — 1 2 — — U2〇1 1 ——— 2 — Na20 3 3 2 2 0.5 4 2 K20 3 3 2 3 — 3 2 Ti02 0.5 0.5 — 3 1 — — Zr02 0.5 0.5 1 3 1 — 1 Glass transition point (. C) 590 590 620 650 640 575 620 Glass-ceramic composition (weight m%) Glass 50 50 45 55 55 60 32 Titanium dioxide 7 7 6 2 2 8 9 Alumina 43 20 12 43 43 32 9 <3: - Quartz - 37 — — — 50 Zircon — 23 — — — — — Calcination temperature (.〇880 880 900 950 930 880 910 Flexural strength (MPa) 210 205 200 210 190 130 120 Crystalline phase more or less thermal expansion coefficient (xlO_7/° C) 58 44 79 58 56 60 80 Dimensional accuracy 〇〇〇〇Δ △ 〇-16- 200948740 [Possibility for application in the industry] The composition for lead-free glass-based glass ceramics of the present invention can be completed at a lower temperature. The crystallized glass is used, and the glass state is relatively stable, and it is less likely to cause unevenness such as phase separation or partial crystallization during production, and is easy to manufacture. The lead-free glass ceramic composition of the present invention does not contain harmful lead compounds. And can be calcined at a lower temperature of about 85 (TC~1000 °C), and can prevent a sharp baking contraction behavior during baking, and the obtained sintered body has practically sufficient mechanical strength, so it is suitable for A glass-ceramic composition for a low-temperature baking substrate for various other uses for simultaneous calcination with a silver-based conductor.
Awrt. 無。 【主要元件符號說明】 4τττ 無0 ❹Awrt. None. [Main component symbol description] 4τττ No 0 ❹