1243805 玖、發明說明 【發明所屬之技術領域】 本發明係有關一種介電陶瓷（也稱作「介電材料」或「介 電燒結體」，於此處說明部分，於後文稱作爲「介電陶瓷」）， 特別本發明係關於絕佳之低溫燒結性質及機械強度且於 G Η z區段有絕佳介電特性之介電陶瓷。本發明之介電陶瓷 可寬廣應用作爲電子元件。特別介電陶瓷適合用作爲電子 元件、供於其上安裝電子元件之佈線基板等、成形爲多層 之多層佈線基板；以及進一步用作爲供GHz區段高頻使用 之電子兀件、其封裝體或多層佈線基板（多層佈線基板或 板）。 【先前技術】 介電陶瓷習知採用作爲多種電子元件或供安裝電子元件 於其上之佈線基板。用於此等用途之介電陶瓷要求可於 1 〇〇〇°c之低溫燒結且具有高機械強度。滿足此項需求之介 電陶瓷主要係由玻璃以及無機塡料製成（玻璃：軟化點約 5 00至800°C且含有氧化鉛、鹼土金屬氧化物、鹼金屬氧化 物以及氧化鋅爲主之鋁硼矽酸鹽玻璃粉）以及（無機塡料： 鋁氧、富鋁紅柱石、堇青石、鈦氧、鎂橄欖石、鉻氧及石 英）。 此等介電陶瓷係揭不於JP-A-53-60914、JP-A-60-235744 、JP-A-63-239892、 JP-A-3-33026、 JP-A-7-135379 及 JP-A-9-208258。此等介電陶瓷之介電耗損於百萬赫茲（MHz)爲6 X 1 0_4 至 20 X 1 0·4。 312/發明說明書(補件)/92-04/92102639 1243805 近年來特別要求於使用逐漸增加之GH z區段的介電耗 損減低。因此，要求介電陶瓷，其可與以銀爲主之金屬或 以銅爲主之金屬之低電阻導體同時燒結，機械強度高，燒 結產物之扭曲、彎曲或翹曲（本說明書中偶爾簡稱爲「扭曲」) 減少（扭曲減少將讓尺寸穩定性變佳，而可抑制用於GHz 區段期間之傳輸耗損）。 但難以同時達成低溫絕佳燒結性質及機械強度、以及於 GHz區段之絕佳介電特性的優勢。 【發明內容】 本發明係供解決前述問題，如此本發明之一目的係提供 可同時燒結以銀爲主之金屬及以銅爲主之金屬之低電阻導 體，具有絕佳機械強度且具有絕佳GHz區段之介電特性之 介電陶瓷。 (1)本發明之介電陶瓷含有一種無機塡料及玻璃，其特徵 爲’當無機塡料與玻璃總量爲1 〇〇質量百分比（亦即重量百 分比）時，介電陶瓷含有無機塡料20至60 wt%及玻璃40 至80 wt% ;而當玻璃總量爲1〇〇 wt%時，其含有（分別以氧 化物表示）Si: 20至30重量百分比（wt%)，B: 5至30 wt%， A1: 20 至 30 wt%，Ca: 10 至 20 wt%，Zn: 10 至 20 wt% 以 及含有至少一種驗金屬L i、N a及K總量爲〇 · 2至5 w t %。 此外，本發明之介電陶瓷可讓於3 GHz之介電耗損爲50 X 1〇_4或以下，於3 GHz之相對介電常數爲6至13，此外 於25至400°C之熱膨脹係數爲5至10 ppnW°C，此外抗彎 強度（或抗彎強度）爲185 MPa或以上。 312/發明說明書(補件)/92-04/92102639 1243805 (2 )本發明之介電陶瓷係經由於1 0 0 0 °c或以下燒結一種 供介電陶瓷用之組成物（亦即介電陶瓷組成物），該組成物 胃有無機塡料及玻璃，及其特徵爲，當無機塡料與玻璃總 量爲100 wt%時，介電陶瓷含有無機塡料20至60 wt%及 玻璃40至8〇 wt%;而當玻璃總量爲10〇 wt%時，其含有（分 別以氧化物表示）Si: 20至30 wt%，B: 5至30 wt%，A1: 20 至 30 wt%，Ca: 1 0 至 20 wt%，Ζιι: 1 0 至 20 wt%以及含有 至少一種鹼金屬Li、Na及K總量爲0.2至5 wt%。 (3) 本發明之介電陶瓷含有一種無機塡料及玻璃，及其特 徵爲，當無機塡料與玻璃總量爲100 wt%時，介電陶瓷含 有無機塡料20至60 wt%及玻璃40至8 Owt% ;而當玻璃總 量爲100 wt%時，其含有（分別以氧化物表示）Si: 20至30 Wt°/。，B·· 5 至 30 wt%，A1: 20 至 30 wt%，Ca: 10 至 20 wt%， Zn: 1〇 至 20wt% 且不含 Li、Na、K。 (4) 本發明之介電陶瓷係經由於1 000 °c或以下燒結一種 供介電陶瓷用之組成物而製備，該組成物含有一種無機塡 料及玻璃，及其特徵爲，當無機塡料與玻璃總量爲1 00 wt % 時，介電陶瓷含有無機塡料20至60 wt%及玻璃40至80 wt% ;而當玻璃總量爲1〇〇 wt%時，其含有（分別以氧化物 表示）Si:20 至 30wt%，B:5 至 30wt%，Al:20 至 30wt%， Ca: 1〇 至 20wt%，Ζικ 10 至 20wt% 且不含 Li、Na、K。 本發明之介電陶瓷可獲得3 GHz之介電耗損爲50 χ 1(Γ4 或以下。本發明之介電陶瓷可獲得於3 GHz之相關介電常 數爲6至1 3。 312/發明說明書(補件)/92-04/92102639 1243805 本發明之介電陶瓷可讓於2 5至4 0 0 t：之熱膨脹係數爲5 至 10 p p m / °C 0 本發明之介電陶瓷可獲得抗彎強度爲1 8 5 Μ P a或以上。 無機塡料可含有鋅尖晶石塡料（尖晶石組成的塡料）以及 鈦氧塡料（鈦氧組成物塡料）。 玻璃轉換溫度T g與彎曲溫度μ g間之差異爲3 0至4 5 t。 根據本發明之介電陶瓷，可提供一種介電特性因而可同 時燒結以銀爲主之金屬以及以銅爲主之金屬之低電阻導 體’具有絕佳機械強度以及具有絕佳介電特性。 【實施方式】 將對本發明作細節說明。 即述「無機塡料」依據塡料種類及含量而定，可變更介 電陶瓷之介電特性以及機械特性。至於組成無機塡料之材 料性質例如包括鋅尖晶石、鈦氧、鋁氧、鈦酸鹽（鈦酸鎂、 鈦酸鈣、鈦酸緦、鈦酸鋇）、富鋁紅柱石、鉻氧、石英、堇 青石、鎂橄欖石、瓦礫石（wallastonite)、鈣灰長石、頑灰 石、透輝石、鎂黃長石（akermanite)、鈣黃長石及尖晶石。 其中爲了將高頻區段（特別GHz區段）之相對介電常數（後 文簡稱爲“ ε r”）變大，以鋅尖晶石、鈦氧、鈦酸鹽及鋁氧 爲佳。爲了改良機械強度，以鋅尖晶石、鈦氧、锆氧及鋁 氧爲佳。可含有一種或多於兩種塡料。 爲了分別調整介電陶瓷之特性（介電特性及機械強度）可 組合多於兩種塡料。例如於介電特性中，爲了將於高頻共 振頻率（特別GHz區段）之溫度相依性（後文簡稱爲“ r f”）控 312/發明說明書(補件)/92-04/92102639 1243805 制爲低（將r f絕對値控制爲小）數値，可採用具有負値r f 之無機塡料以及正値r f之無機塡料。其組合例如爲尖晶 石+鈦氧、尖晶石+鈦酸鹽、鋁氧+鈦酸鹽、以及尖晶石+銘 氧+鈦酸鹽。 其中尖晶石塡料與鈦氧塡料之組合顯示充分機械強度， 可於高頻區度（GHz區段）獲得大ε r以及獲得小絕對値 τ f ° 當無機塡料與玻璃之總量爲1〇〇 Wt%時，無機塡料含量 爲20至60 wt%(更佳30至60 wt%及又更佳40至55wt%)。 若無機塡料之含量低於2 0 w t %，則玻璃熔化出而可能與燒 結機架反應，或無法達成充分抗彎強度。另一方面，若無 機塡料含量超過60 wt%，則難以達成低於1 000°C之燒結 溫度，且不可能完成同時與低溫電阻導體一起燒結。 當尖晶石塡料與鈦氧塡料組合使用時，尖晶石塡料與鈦 氧塡料之總量占無機塡料全部總量較佳爲50 wt%或以上 (更佳80 wt%，又更佳90 wt%及甚至允許1 00 wt%)。當總 量低於50 wt%時，無法顯現含有鋅尖晶石塡料與鈦氧塡料 之效果。 至於鈦氧塡料含量mT(以質量（亦即重量）表示）對鋅尖晶 石含量m G (以重量表示）之比，m T / m G比較佳爲0.1至1 . 5， 更佳爲0.4至1 ·0，又更佳爲0.6至0.9。若mT/mG比小於 〇 · 1，則難以獲得將r f絕對値壓抑變小數値的效果。 無機塡料之組態（形狀）並無特殊限制，可使用多種組態 例如粒狀、片狀或織物形狀（特別爲鬚狀）。尋常尺寸較佳 312/發明說明書(補件)/92-04/92102639 1243805 爲1至1 0微米（以粒狀無機塡料爲例，採用平均直徑）。若 尺寸超過1 0微米，則介電陶瓷結構變成過度強勁。若尺寸 小於1微米，則可能難以製造，但對介電陶瓷之特性不會 造成任何影響。 無機塡料存在於介電陶瓷之組態及尺寸係如同介電陶瓷 製造時呈無機塡料粉末添加時之組態及尺寸，包括製造時 以玻璃粉型態添加而呈結晶元體沉澱之無機塡料（鈣灰長 石、尖晶石及鉢尖晶石）。 前述「玻璃」依據種類及含量而定，可改變介電陶瓷之 燒結溫度及介電特性。當無機塡料與玻璃之總量爲1 〇〇 w t %時，玻璃爲4 0至8 0 w t % (較佳4 0至7 0 w t %，又更佳 50至60 wt%)。若玻璃含量低於40 wt%，則難以將燒結溫 度降至低於1 0 0 0 °C，而當超過8 0 wt %時，機械強度降低， 於高頻區段之介電特性也不足。特別ε r非期望地過小。 本發明之一具體實施例，玻璃含有鹼金屬元素，玻璃含 有至少矽元素、硼元素、鋁元素、鈣元素及鋅元素，以及 鋰元素、鈉元素及鉀元素中之至少一種鹼金屬元素（後文簡 稱爲“X”）。對玻璃所含元素製作成之化合物並無特殊限制。 本發明之一具體實施例中，當玻璃含有鹼金屬元素時， 前述以「以氧化物表示」一詞係與玻璃中存在何種S i，B， Al，Ca及Zn以及X化合物獨立無關，Si係以Si02計算， B係以B2〇3計算，A1係以Al2〇3計算，Ca係以CaO計算， Zn係以ZnO計算以及X係以χ2〇計算。 本發明之一具體實施例中，當玻璃不含鹼金屬元素時， 312/發明說明書(補件)/92-04/92102639 1243805 玻璃至少含有矽元素、硼元素、鋁元素、鈣元素及鋅元素。 對玻璃含有此等元素製作成何種化合物並無特殊限制。 本發明之一具體實施例中’當玻璃不含鹼金屬元素時， 前述以「以氧化物表示」一詞係與玻璃中存在何種S i，B， Al,Ca及Z11獨立無關，Si係以Si02計算，B係以B2〇3計 算，A 1係以A 12 〇 3計算’ c a係以C a Ο計算，Ζ η係以Ζ η Ο 計算。 若玻璃總量爲1 0 0 w t%，則以氧化物表示，矽爲2 0至 3 0 wt % (更佳20至27 %，又更佳21至25 wt%)。若矽含量 低於20 wt%，則玻璃之軟化溫度過低，以及與低電阻導體 同時燒結之性質不足’可能造成非期望之扭曲’此外e r 可能非期望地過高。另一方面’當矽含量超過3 0 wt%時， ε r爲中等値，但因燒結溫度變高，故與低電阻導線的同 時燒結變困難。另一方面，可提高玻璃成分燒結之混料速 率，但介電耗損可能非期望地過度升高。 硼含量以氧化物表示爲5至30 wt%。若低於5 wt%，則 燒結溫度過高，與低電阻導體之同時燒結性質不足，經常 造成非期望的扭曲。另一方面，若硼含量超過30 wt%，則 玻璃之軟化溫度過低，與低電阻導體之同時燒結性質不 足，造成扭曲。此外，玻璃於介電陶瓷之化學安定性降低， 因而無法獲得期望之耐化學性質。 藉由含有10至30 wt%之硼，於製造時可將燒結溫度調 整於7 5 0 °C至95 0°C之寬廣範圍。此外，除前述外，經由含 有15至30 wt%之硼，與低電阻導體之同時燒結性質變成 312/發明說明書(補件)/92-04/92102639 1243805 特別不利，因而可有效防止發生扭曲。經由含有20 1 30 wt%之硼，除前述特點外，介電陶瓷之耐化學性變特高’ 例如當製造多層佈線基板之鍍覆處理過程中，可有效I免 介電陶瓷熔化及溶蝕。 此外，以氧化物表示，鋁含量爲20至30 wt % (更佳21 至29 wt%及又更佳22至26 wt%)。若鋁含量低於20 wt% ’ 則無法充分獲得介電陶瓷之機械強度，特別當鋁含量低於 1 0 wt%時，玻璃安定性非期望地受到破壞。另一方面’超 過30 wt %時，燒結溫度變過高而不合所需。 以氧化物表示，鈣含量爲10至20 wt%(更佳12至20 w t %，以及又更佳1 5至1 8 w t %)。錦含量低於1 0 w t %時， 無法充分提高玻璃之熔化性質。另一方面，超過20 wt% 時，熱膨脹係數非期望地變過大。 以氧化物表示，鋅含量爲10至20 wt%(更佳10至18 w t %，及又更佳1 1至1 6 w t %)。鋅含量低於1 0 w t %，於低 溫電阻導體之同時燒結性質不足，非期望地引發扭曲。另 一方面，若含量超過20 wt%，則無法充分獲得介電陶瓷之 耐化學性。 本發明之一具體實施例中，當玻璃含有鹼金屬元素時， 以氧化物表示，X含量爲0.2至5 wt%。若含量低於0.2 wt%，則玻璃轉換溫度可能變過高，燒結性質非期望地受 到破壞。另一方面，含量超過5 wt %時，玻璃轉換溫度可 能降低，因此只有玻璃非期望地被過度燒結。 對鋰、鈉及鉀中之至少任一者，X落入前述範圍即足。 312/發明說明書(補件)/92-04/92102639 1243805 但若使用以銀爲主之金屬作爲多層佈線基板之低電阻導 體’則希望不含鋰。因而可極爲有效抑制銀的遷移。 「本發明之一具體實施例中玻璃不含鹼金屬元素」之事 實表示鋰、鈉及鉀實質未含於玻璃。換言之，此等元素可 能未積極包含，但可能無可避免地包含。此種情況下，希 望不會出現因含有鋰、鈉及鉀造成的影響程度，換言之若 玻璃總量爲100 wt%，則鋰、鈉及鉀之含量較佳低於0.2 wt%(更佳絲毫也未含鋰、鈉及鉀）。當使用以銀爲主之金屬 作爲多層佈線基板之低電阻導體時，若發生銀遷移特別有 疑慮時，例如毗鄰線路間距極小，或絕緣層或絕緣陶瓷層 (於本說明書中偶爾簡稱爲絕緣層）厚度極薄時，則較佳使 用未含鹼金屬之玻璃。 以此等元素之氧化物表示，.可組合個別含量。換言之例 如： 本發明之一具體實施例中，當玻璃含有鹼金屬元素時， 矽含量爲20至27 wt%，硼爲10至30 wt% ’鋁爲21至29 wt%，鈣爲12至20 wt%，鋅爲1〇至18 wt%以及X爲0.2 至5 wt%。此外，也可矽含量爲21至25 wt%，硼爲15至 3 0 w t %，鋁爲2 2至2 6 w t %，鈣爲1 5至1 8 w t %，鋅爲1 1 至16 wt%以及X爲0.2至5 wt%。 本發明之一具體實施例中，當玻璃不含鹼金屬元素時’ 矽含量爲20至27 wt%，硼爲1 〇至30 wt% ’鋁爲2 1至29 wt%，鈣爲12至20 wt%以及鋅爲1〇至1 8 wt%。此外’也 可矽含量爲21至25 wt%，硼爲15至30 wt% ’銘爲22至 312/發明說明書(補件)/92-〇4/92102639 1243805 2 6 w t %，釣爲1 5至1 8 w t %以及鋅爲]1至1 6 w t %。 根據本發明之介電陶瓷，於1至1 5 G H z (特別3至]0 G Η z) 之介電耗損爲50 χ 1〇·4或以下（此外爲40 χ 10·4或以下， 特別爲30 X 10·4或以下以及通常爲20 X 10·4或以上）。通 常隨著使用頻率的變高，介電耗損變大，但於本發明之介 電陶瓷，如前述可將GHz區段之介電耗損控制爲小。此種 介電耗損不僅可藉玻璃組成改變，同時也可藉無機塡料變 更。如此介電耗損藉組成、製造時無機塡料添加量、以及 燒結條件如溫度調整。於本發明，作爲評估高頻介電特性 之値，於3 GHz所得介電特性値爲介電特性之測量及評估 代表値。選用3 GHz之原因在於3 GHz爲無線區段網路 (LAN)常用的區段（如2.4至2.5 GHz)，且容易與既有產物 比較及評估。 此外，也可能於1至15 GHz (通常3至10 GHz)之ε r 爲6至13(此外爲7至13，特別爲9至13)。通常隨著使 用頻率變高，ε r變低。若ε r過小，則須將介電陶瓷製作 成大尺寸才能用於GHz區段，因而造成尺寸微縮化變困 難。因此，慮及於GHz區段的使用，較佳讓ε r變大，因 而多種電子元件之微縮化也可應用於GHz區段。 於1至15 GHz(特別3至10 GHz)之r f(溫度範圍：25 至 80°C )爲-20 至 10 ppm/t：(此外-10 至 10 ppm厂C，特別-10 至5 ppm/°C )。通常隨著使用頻率的變高，共振頻率溫度 係數之絕對値朝向負値方向變大。若絕對値係朝向負値方 向變大，則當用作爲封裝體基板時，難以支援於其中的帶 16 312/發明說明書(補件)/92-(Μ/92102639 1243805 通濾波器，因而電性可靠度降低。因此考慮於GHz區段之 應用，r f之絕對値以小爲佳，因此多種電子元件之操作 穩定也可應用於GHz區段。 此外，由25 °C至400 °C之熱膨脹係數升高爲5至10 ppm/ °C是有可能的。通常近年來使用之印刷線板之熱膨脹係數 爲約13至14 ppm广C，作爲1C之半導體元件之熱膨脹係 數爲約3至4 ppm/°C。若使用介電陶瓷作爲多層佈線基 板，則需要讓熱膨脹係數更爲接近印刷電路板之熱膨脹係 數以及半導體元件之熱膨脹係數，本發明之介電陶瓷可滿 足此項需求。 此外，抗彎強度爲160 MPa或以上（此外180 MPa或以 上，特別190 MPa或以上）。若抗彎強度爲160 MPa或以 上，則當由本發明之介電陶瓷製成之多層佈線基板或電子 元件產物掉落時，可克服因撞擊而破裂之問題。多層佈線 基板或電子元件使用金屬硬焊（例如電磁屏蔽用之密封 環），可克服於此種硬焊過程中因熱應力造成的斷裂。 本發明中可獲得介電陶瓷，此處於1至15 GHz(特別3 至10 GHz)之介電耗損爲50 X 10_4或以下，ε r爲6至13， r f爲-20至10 PPm/°C，於25至400°C之熱膨脹係數爲5 至10 ppm/°C以及抗彎強度爲160 MPa或以上。此外，可 利用介電陶瓷此處於1至15 GHz(特別3至10 GHz)之介電 耗損爲40 X 10_4或以下，e r爲7至13，r f爲-10至lOppm/ °C，於25至400 °C之熱膨脹係數爲5至10 ppm广C以及抗 彎強度爲1 80 MPa或以上。 312/發明說明書(補件)/92-04/92102639 1243805 特別若含有鋅尖晶石塡料及鈦氧塡料二者作爲無機塡料 時’可獲得介電陶瓷，此處於3至1 0 GHz之ε r爲9至1 3， τ f爲-1 5至〇 ppmTc以及抗彎強度爲1 80 MPa。此外若含 有鋅尖晶石塡料及鈦氧塡料二者，且無機塡料與玻璃之總 量爲1 00 wt%，讓無機塡料爲30至60 wt%，則可獲得介 電陶瓷’此處於3至10GHz之er爲10至13，rf爲-15 至0 ppm/°C以及抗彎強度爲190 MPa或以上。 右含有鋅尖晶石塡料及鈦氧塡料二者作爲無機塡料，且 無機塡料與玻璃之總量爲1 〇 〇 w t %，讓無機塡料爲3 0至 6 0 w t °/〇，以及m T / m G爲0 · 6或以上，則可獲得介電陶瓷， 此處於3至10 GHz之εΓ爲10至13，rf爲-3至0 ppm/ °C以及抗彎強度爲190 MPa或以上。 本發明之介電耗損、ε r、τ f、熱膨脹係數及抗彎強度 係依據前述實施例測量方法之相同方法決定。 獲得本發明之介電陶瓷之方法並無特殊限制，例如可採 用下列方法。換言之，本發明之一具體實施例中，當玻璃 含有鹼金屬元素時，介電陶瓷組成物之獲得方式係經由混 料無機塡料粉末與玻璃粉末，以及於iOOOt;或以下之溫度 燒結，其中當玻璃粉末總量爲i 〇〇 wt%時，分別以氧化物 表示，Si:20 至 30wt%，B:5 至 30wt%，Al:20 至 30wt%， Ca: 10至20 wt%，Zn: 10至20 wt%，以及至少一種鹼金 屬：Li、Na及K總量爲0.2至5 wt% ;當無機塡料粉末與 玻璃粉末總量爲100 wt%時，無機塡料粉末占20至60 wt% 以及玻璃粉末占4 0至8 0 w t %。 18 312/發明說明書(補件)/92-04/92102639 1243805 換言之，本發明之一具體實施例中，當玻璃不含鹼金屬 元素時’介電陶瓷組成物之獲得方式係經由混料無機塡料 粉末與玻璃粉末，以及於1 ooo°c或以下之溫度燒結，其中 當玻璃粉末總量爲1 0 0 w t %時，分別以氧化物表示，S i : 2 〇 至 30 wt%，B·· 5 至 30 wt%，A1·· 20 至 30 wt%，Ca·· 1〇 至 20wt%，Zn: 10至20wt%，以及驗金屬不含Li、Na或κ; 當無機塡料粉末與玻璃粉末總量爲100 wt %時，無機塡料 粉末占20至60 wt%以及玻璃粉末占40至80 wt %。 至於前述於本製法之無機塡料粉末，分別爲藉燒結製成 之鈦氧、鋁氧及鉻氧粉末。其可單獨或組合使用。 對無機塡料粉末直徑並無特殊限制，以1至1 0微米爲 佳。直徑大於1 0微米時，介電陶瓷結構太過粗糙。直徑小 於1微米時，粉化耗時時間過長且處理操控困難。 無須存在有全量無機塡料粉末作爲介電陶瓷的無機塡 料，只要有部分粉末可熔化成爲玻璃且呈玻璃存在即可。 玻璃粉之獲得方式例如爲經混合而具有前述組成之原料 粉末經加熱及熔化，迅速冷卻成爲玻璃料，以及玻璃料經 粉化。各種元素於玻璃粉末之含量理由同玻璃於介電陶瓷 含量之理由。 對玻璃粉末直徑並無特殊限制。換言之可爲1至1 〇微 米。若直徑超過1 0微米，則當成形爲玻璃板時可能造成非 期望的影響；若直徑小於1微米，則粉化耗時過久且處理 操控困難。 無須存在有全量玻璃粉末作爲介電陶瓷的玻璃，只要有 312/發明說明書(補件)/92-04/92102639 1243805 部分粉末沉澱於介電陶瓷因而呈玻璃存在即可。 玻璃粉之玻璃轉換溫度Tg並無特殊限制，但較佳爲560 至670 °C(更佳爲570至660 °C，又更佳爲570至640 °C)。 於此種範圍，可有利地保有下列性質，同時與低電阻導體 如以銀爲主之金屬（單獨銀、Ag/Pd合金、Ag/Pt合金、Ag/Cu 合金、或Ag/Au合金等）或以銅爲主之金屬（單獨銅但含有 小量其它元素）同時燒結的性質，且可有效克服因燒結引發 的扭曲。 玻璃粉之彎曲溫度Mg[亦即於熱膨脹曲線（DTA曲線）之 軟化溫度，其爲停止膨脹而明顯開始收縮的溫度；偶爾稱 作爲At]並無特殊限制，希望與玻璃轉換溫度Tg之溫度差 異爲30至45 °C (更佳30至40 °C，又更佳30至38 °C)。若 T g與M g間之溫度差異係於此範圍，則可有效抑制因燒結 引起的收縮分散。如此電子元件或佈線基板可以高度尺寸 精度設計。 至於介電陶瓷組成中，無機塡料粉末與玻璃粉末之混合 比，理由同介電陶瓷，希望其混合量獲得無機塡料粉末占 3 0至6 0 w t % (玻璃粉末爲4 〇至7 0 w t %)。較佳希望其混合 量爲無機塡料粉末占40至60 wt % (玻璃粉末占40至60 wt%)，及更佳占45至55 wt%(玻璃粉末占45至5 5 wt%)。 介電陶瓷組成物可由無機塡料粉末與玻璃粉末組成，除 了此等成分外可含有例如黏結劑、溶劑、增塑劑及分散劑。 對介電陶瓷組成物性質並無特殊限制，例如粉末、漿液及 糊劑皆可。此外，介電陶瓷組成物可由此等粉末、漿液及 312/發明說明書(補件)/92-04/92102639 1243805 糊劑透過多種成形形式成形（粉末：粉末加壓、CIP或HIP ; 漿液及糊劑：刀塗法、網版印刷法以及壓縮成形法）。 燒結較佳係於〗 000°C或以下之溫度進行（通常爲75 0°c 或以上，更佳爲800至990 °C，又更佳爲850至990 °C，特 佳爲900至9 8 0°C )。高於1 000 °C時同時與其它低電阻導體 燒結非期望地變困難。 實施例 將參照實施例特別說明本發明。 [1]介電陶瓷使用含鹼金屬元素而不含尖晶石塡料之玻璃 (1)玻璃粉之製備 除了 Si〇2、B2O3、AI2O3、CaO、ZnO、Na2C〇3 及 K2C03 粉末外，MgO、BaO、SrO及ZrO粉末以表1所示比例混 合而製備原料粉末。製備後之原料粉末加熱熔化，投攙ρ λ 水中快速冷卻’且同時於水中造粒而獲得玻璃料。〗离米斗 於球磨機粉化而製造1 0種玻璃粉（1至1 〇號玻璃}，具胃 平均直徑爲3微米。 312/發明說明書(補件)/92-04/92102639 1243805 £ 介電陶瓷 無機塡 料 1 (wt%) 組成(Wt%) Η Ν I 1 1 rn r-H s d 1 1 1 1 Ο ώ 1 o r- o 1 9 PQ 卜 m MgO 1 1 寸 o m T—H d <N r—^ 驗金屬 Na20 Na20 o 1 * Na20 1 * 〇 (N 1 * 1 * Na20 1 * (N rn m (N r-H m 〇 寸· 〇 T-H Τ-Ή r-H 1 * 1 * 1 * 1 * 1 * H 1 * 9 U v〇 VO 1 * 1 * | *0.15 | 卜 1 * ON 00 Al2〇3 艺 G\ v〇 m rp C\ r-H * <N 00 (N (N 00 (N Β2Ο3 00 (N | *45.5 1 卜 r—^ Ό m * VO od (N (N 卜· 00 ΰ5 宕 ο <N οό (N JQ ^T) <N r〇 ΓνΙ fp (N (N 〇\ fp * 玻璃 編號 <N ro vp tp 00 C\ o r-H * < T-H (N cp vp r- 00 〇\ o * ττ fl : v 6e9sls/s-(N6/ffiii)_&^i^®/ne 1243805 (2 )玻璃粉之T g及M g之測量 如上（1)製造之10種玻璃粉之Tg及Mg係藉差異熱測量 裝置（型號「塞莫夫雷特斯（THERMOFLEX TAS) 300 TG8 10D」理學國際公司製造）測量，Tg、Mg及Mg-Tg之 個別値顯示於表2。 表2 玻璃 介電陶瓷之熱特件 編號 Tg(°c ) Mg(°C ) Mg.Tg(°C ) 1 576 6 11 35 2 580 6 13 33 *3 535 650 115 * 4 520 640 120 *5 638 675 37 *6 686 73 1 45 *7 655 695 40 * 8 549 580 3 1 * 9 683 722 39 * 1 0 7 18 765 47 於表2表示「非屬本發明之範圍」。 (3)生片材之製造（介電陶瓷組成物） 1 〇種至前述（2)製造之個別玻璃粉末以及作爲無機塡料 粉末之鋁氧粉末經稱重而具有如表1所示之50 wt%比率， 且於球磨機混合而製造混合粉末。製造的混合粉末加入黏 結劑（丙烯酸系樹脂）、增塑劑{鄰苯二甲酸二丁酯（D B P)} 及溶劑（甲苯），且混合而製備1 〇種料漿。個別料漿藉著刀 塗法成形爲片材，燒結後片材厚度爲1 00微米，因而獲得 23 312/發明說明書(補件)/92-04/92102639 1243805 1 〇種生片材。 (4)供第一測量（供測量介電特性）之陶瓷之製造以及介電 特性之測量 1 〇種於如上（3)製造之生片材被沖壓成爲預定組態，多 塊片材透過熱壓連結共堆疊1 〇片’於900°C燒結1 5分鐘 而製造陶瓷。陶瓷接受拋光處理成爲50毫米x50毫米X 0.63 5毫米片材，製造1〇種供第一測量之陶瓷。經由使用 供第一測量用之陶瓷，透過介電陶瓷之介電共振器-擾動方 法，測定於25 °C於3 GHz之介電耗損及ε r。結果顯示於 表3 〇 表3 實施例 介電陶瓷特性 介電耗損 (X 1 Ο'4) (3GHz) ε r (3GHz) 熱膨脹係數 (25-400〇C ) (ppm/°C ) 1 38 7.4 6.1 2 40 7.2 6.2 *3 13 5.2 5.5 * 4 150 6.5 4.6 *5 30 5.9 7.3 *6 18 5.6 5.5 *7 64 4.9 6.0 * 8 63 6.5 6.4 * 9 19 6.6 4.9 * 1 0 40 7.2 5.4 “ ”於表3表示「非屬本發明之範圍」。 (5)第二測量（供測量熱膨脹係數）用陶瓷之製造以及熱膨 脹係數之測量 24 312/發明說明書(補件)/92-04/92102639 1243805 如上（3 )製造之1 〇種生片材被沖壓成爲預定構形，2 〇塊 片材透過熱壓連結法堆疊，於90〇t：燒結1 5分鐘而製造陶 瓷。陶瓷接受拋光處理成爲3毫米Χ3毫米xl.6毫米管 柱’製造1 0種供第二測量用之陶瓷。使用供第二測量用之 陶瓷’藉差異膨脹熱機器分析裝置（型號“TMA8140D”理學 國際公司製造）測定由25°C升高至400°C之熱膨脹係數。結 果共同顯示於表3。 (6)第三測量（供測量同時燒結性質）用陶瓷之製造以及同 時燒結性質之評比 10種如上（3)製造之生片材使用厚15微米之銀糊劑印刷 於其預定位置。於銀糊層上，藉熱壓連結而層疊其它生片 材’同樣地銀糊也印刷於其它生片材上，重複進行此項工 作’共層疊5片生片材，獲得未經燒結之層疊物，於各層 間於預定圖案使用銀糊印刷。未經燒結之層疊物沖壓成4 厘米直徑’以及於90(TC燒結1 5分鐘。如此製造1 0種配 置有低電阻導體之供第三測量用之陶瓷。 ① 燒結造成扭曲之評比 1 〇種供第三測量用之製造陶瓷鋪於平面上，測定距離平 面最大位置與最小位置（與平面接觸位置）間之差異，若差 異小於50微米（未扭曲至實際程度）或未出現扭曲，則標示 爲“ ”，扭曲超過5 0微米標示爲“ X ”且分別顯示於表4。 ② 因燒結而銀遷移 1 〇種製造妥之供第三測量用之陶瓷於層疊方向切割，切 割面藉ΕΡΜΑ (電子探針微分析儀）分析。結果於陶瓷內部 25 312/發明說明書(補件)/92-04/92102639 1243805 發現銀遷移，遷移距離小於5微米爲“ ◎”，遷移距離爲5 至10微米爲“〇”，遷移距離超過10微米爲“X”，共同顯 示於表4。 表4 實施例 介電陶瓷特性 銀遷移 扭曲 抗彎強度 (MPa) 1 ◎ ◎ 2 10 2 ◎ ◎ 260 * 3 X ◎ - * 4 〇 ◎ <180 *5 X X - *6 〇 X - *7 X ◎ - * 8 ◎ X - * 9 ◎ X - * 1 0 X X - 表4“*”表示「非屬本發明之範圍」。 (7)供第四測量（抗彎強度測量）用陶瓷之製造及抗彎強度 之評比 如上（3)製造之生片材中，對應於實施例1、2及4之生 片材沖壓成爲預定組態，透過熱壓連結法堆疊1 〇片生片 材，且於900 °C燒結1 5分鐘而製造陶瓷。陶瓷接受拋光處 理成爲4毫米X 3毫米X 3 6毫米管柱，製造3種供第四測 量用之陶瓷。經由使用供第四測量用之陶瓷且遵照JIS R 1 6 0 1，測量其抗彎強度（3點彎曲）。結果共同示於表4。 26 312/發明說明書(補件)/92-04/92102639 1243805 (8)實施例1至10之效果 由表1至4結果，實施例3至1 0各自可於9 0 0 °C之低溫 燒結，且顯示某種程度的介電特性。但有部分顯示因玻璃 粉之熱特性不佳造成介電陶瓷扭曲，有些未能提供充分介 電特性，另有些因燒結而造成低電阻導體之遷移，或有些 無法提供充分抗彎強度。此等實施例皆未能帶有個別特性 之充分良好平衡。另一方面，本發明產物實施例1及2可 與低電阻導體於900°C同時燒結，且顯示良好介電特性（介 電耗損：38至40 X 10·4，er: 7.2至7.4，以及抗彎強 度：210至260 MPa)。此外，未發現組成低電阻導體成分 的遷移，也未見基板的扭曲，可知可獲得夠高抗彎強度。 此外，熱膨脹係數爲6.1至6 · 2 p p m / °C，顯示作爲佈線基 板之適當特性。 [2 ]使用含有鹼金屬元素以及含有鋅尖晶石塡料之玻璃之 介電陶瓷 (1)供第五測量（測量介電特性）用之陶瓷之製造以及介電 特性之測量 使用如上[1 ]，（ 1)製造之1、2、4、6及9號玻璃作爲玻 璃粉’以及使用鋅尖晶石粉末、鈦氧粉末及碳酸鈣粉末作 爲無機塡料，該等物質係以表5所示比率組合且混合，如 上[1] ’（3)所示製造生片材。隨後類似如上[1]，（4)進行燒 結以及進行拋光處理’共製造1 1種供第五測量用之陶瓷。 製造得之介電陶瓷中，除了實施例1 1於燒結時冒氣泡以及 實施例1 9至2 1引發扭曲外，其餘7種介電陶瓷，以類似 27 312/發明說明書(補件)/92-04/92102639 1243805 前述[1]，（4)之方式測定於3 GHz之相對介電常數ε r以及 於2 5至8 0 °C之共振頻率溫度係數τ f。結果共同顯示於表1243805 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a dielectric ceramic (also referred to as a "dielectric material" or a "dielectric sintered body"), which is described here, and is hereinafter referred to as "the dielectric "Electroceramics"), in particular, the present invention relates to a dielectric ceramic having excellent low-temperature sintering properties and mechanical strength and having excellent dielectric characteristics in the G Η z section. The dielectric ceramic of the present invention can be widely used as an electronic component. Special dielectric ceramics are suitable for use as electronic components, wiring substrates on which electronic components are mounted, etc., multilayer wiring substrates formed into multiple layers; and further used as electronic components, packages or Multilayer wiring substrate (multilayer wiring substrate or board). [Prior art] Dielectric ceramics are conventionally used as wiring boards for various electronic components or for mounting electronic components thereon. Dielectric ceramics used for these applications are required to be sinterable at a low temperature of 1000 ° C and have high mechanical strength. Dielectric ceramics to meet this demand are mainly made of glass and inorganic materials (glass: softening point is about 500 to 800 ° C and contains lead oxide, alkaline earth metal oxides, alkali metal oxides and zinc oxide. Aluminoborosilicate glass powder) and (inorganic materials: aluminite, mullite, cordierite, titania, forsterite, chromite and quartz). These dielectric ceramics are not disclosed in JP-A-53-60914, JP-A-60-235744, JP-A-63-239892, JP-A-3-33026, JP-A-7-135379, and JP -A-9-208258. The dielectric loss of these dielectric ceramics ranges from 6 X 1 0_4 to 20 X 1 0 · 4 in millions of hertz (MHz). 312 / Invention Specification (Supplement) / 92-04 / 92102639 1243805 In recent years, it has been particularly required to reduce the dielectric loss of the GH z section which is gradually increasing. Therefore, a dielectric ceramic is required, which can be sintered at the same time as a low-resistance conductor of silver-based metal or copper-based metal, with high mechanical strength, and distortion, bending or warping of sintered products (occasionally referred to as " ("Twisting") reduction (reduction of distortion will improve dimensional stability while suppressing transmission loss during use in the GHz band). However, it is difficult to achieve the advantages of excellent low-temperature sintering properties and mechanical strength, as well as excellent dielectric properties in the GHz region. [Summary of the Invention] The present invention is intended to solve the foregoing problems. Therefore, an object of the present invention is to provide a low-resistance conductor capable of simultaneously sintering a silver-based metal and a copper-based metal, which has excellent mechanical strength and excellent Dielectric ceramics with dielectric properties in the GHz range. (1) The dielectric ceramic of the present invention contains an inorganic filler and glass, which is characterized in that 'when the total amount of the inorganic filler and the glass is 100% by mass (ie, weight percentage), the dielectric ceramic contains the inorganic filler 20 To 60 wt% and glass 40 to 80 wt%; and when the total amount of glass is 100 wt%, it contains (represented by oxides respectively) Si: 20 to 30 weight percent (wt%), B: 5 to 30 wt%, A1: 20 to 30 wt%, Ca: 10 to 20 wt%, Zn: 10 to 20 wt%, and a total amount of at least one test metal Li, Na, and K is 0.2 to 5 wt% . In addition, the dielectric ceramic of the present invention allows the dielectric loss at 3 GHz to be 50 X 10-4 or lower, the relative dielectric constant at 3 GHz is 6 to 13, and the coefficient of thermal expansion at 25 to 400 ° C It is 5 to 10 ppnW ° C, and furthermore the flexural strength (or flexural strength) is 185 MPa or more. 312 / Invention Specification (Supplement) / 92-04 / 92102639 1243805 (2) The dielectric ceramic of the present invention is obtained by sintering a composition for a dielectric ceramic (that is, dielectric) at 100 ° C or below Ceramic composition), the composition has an inorganic filler and glass, and is characterized in that when the total amount of the inorganic filler and the glass is 100 wt%, the dielectric ceramic contains 20 to 60 wt% of the inorganic filler and the glass 40 to 80% by weight; and when the total glass content is 100% by weight, it contains (represented by oxides) Si: 20 to 30 wt%, B: 5 to 30 wt%, A1: 20 to 30 wt%, Ca: 10 to 20 wt%, Zm: 10 to 20 wt% and a total amount of 0.2 to 5 wt% containing at least one alkali metal Li, Na, and K. (3) The dielectric ceramic of the present invention contains an inorganic filler and glass, and is characterized in that when the total amount of inorganic filler and glass is 100 wt%, the dielectric ceramic contains 20 to 60 wt% of inorganic filler and glass 40 To 8 Owt%; and when the total amount of glass is 100 wt%, it contains (represented by oxides respectively) Si: 20 to 30 Wt ° /. , B ·· 5 to 30 wt%, A1: 20 to 30 wt%, Ca: 10 to 20 wt%, Zn: 10 to 20 wt% and no Li, Na, K. (4) The dielectric ceramic of the present invention is prepared by sintering a composition for dielectric ceramic at 1 000 ° C or below. The composition contains an inorganic filler and glass, and its characteristics are as follows: When the total amount of glass is 100 wt%, the dielectric ceramic contains 20 to 60 wt% of inorganic filler and 40 to 80 wt% of glass; and when the total amount of glass is 100 wt%, it contains (respectively oxidized) (Material): Si: 20 to 30% by weight, B: 5 to 30% by weight, Al: 20 to 30% by weight, Ca: 10 to 20% by weight, Zilka 10 to 20% by weight and no Li, Na, or K. The dielectric ceramic of the present invention can obtain a dielectric loss of 3 x 1 GHz at 50 x 1 (Γ4 or less. The dielectric ceramic of the present invention can obtain a relative dielectric constant of 6 to 13 at 3 GHz. 312 / Invention Specification ( (Supplement) / 92-04 / 92102639 1243805 The dielectric ceramic of the present invention can make the thermal expansion coefficient of 25 to 4 0 0 t: 5 to 10 ppm / ° C 0 The dielectric ceramic of the present invention can obtain the bending strength It is 1 8 5 MPa or more. The inorganic material may contain zinc spinel material (a material consisting of spinel) and titanium oxide material (a material consisting of titanium oxide). The glass transition temperature T g and The difference between the bending temperature μ g is 30 to 4 5 t. The dielectric ceramic according to the present invention can provide a low-resistance conductor with a dielectric characteristic and can simultaneously sinter a silver-based metal and a copper-based metal. 'It has excellent mechanical strength and excellent dielectric properties. [Embodiment] The present invention will be described in detail. The "inorganic filler" depends on the type and content of the filler, and the dielectric properties of the dielectric ceramic can be changed. And mechanical properties. As for the properties of materials that make up inorganic materials, such as zinc Spar, titanium oxide, aluminum oxide, titanate (magnesium titanate, calcium titanate, hafnium titanate, barium titanate), mullite, chrome oxide, quartz, cordierite, forsterite, rubble ( wallastonite), calcareous feldspar, refractory, diopside, akermanite, calcareous feldspar, and spinel. Among them, in order to change the relative dielectric constant of the high-frequency region (especially the GHz region) (hereinafter (Referred to as "ε r") becomes larger, preferably zinc spinel, titanium oxide, titanate, and aluminum oxide. In order to improve mechanical strength, zinc spinel, titanium oxide, zirconium oxide, and aluminum oxide are preferred. It can contain one or more two kinds of materials. In order to adjust the characteristics (dielectric properties and mechanical strength) of the dielectric ceramic, more than two kinds of materials can be combined. For example, in the dielectric characteristics, in order to adjust the high-frequency resonance frequency (Special GHz section) temperature dependence (hereinafter abbreviated as "rf") control 312 / Invention Specification (Supplement) / 92-04 / 92102639 1243805 is made low (controls the absolute rf to be small), Inorganic materials with negative 値 rf and inorganic materials with positive 値 rf can be used. The combination is, for example, sharp Stone + titanium oxide, spinel + titanate, aluminum oxide + titanate, and spinel + Ming oxygen + titanate. The combination of spinel aggregate and titanium oxide aggregate shows sufficient mechanical strength, Large ε r and small absolute 値 τ f ° can be obtained in the high-frequency region (GHz range). When the total amount of inorganic filler and glass is 100 Wt%, the content of inorganic filler is 20 to 60 wt% (More preferably 30 to 60 wt% and even more preferably 40 to 55 wt%). If the content of the inorganic aggregate is less than 20 wt%, the glass may melt out and may react with the sintering frame or fail to achieve sufficient bending strength . On the other hand, if the content of the inorganic aggregate exceeds 60 wt%, it is difficult to achieve a sintering temperature of less than 1 000 ° C, and it is impossible to complete the sintering together with the low-temperature resistance conductor at the same time. When a spinel aggregate and a titanate aggregate are used in combination, the total amount of the spinel aggregate and the titanate aggregate is preferably 50 wt% or more (more preferably 80 wt%, Even better is 90 wt% and even allows 100 wt%). When the total amount is less than 50 wt%, the effect of containing zinc spinel aggregate and titanium oxide aggregate cannot be exhibited. As for the ratio of the titanic oxide content mT (expressed by mass (that is, weight)) to the zinc spinel content m G (expressed by weight), m T / m G is more preferably 0.1 to 1.5, and more preferably 0.4 to 1.0, and more preferably 0.6 to 0.9. If the mT / mG ratio is less than 0.1, it is difficult to obtain the effect of suppressing r f absolute 値 suppression to a decimal 値. There are no special restrictions on the configuration (shape) of inorganic materials, and various configurations such as granular, sheet, or fabric shapes (especially whiskers) can be used. Ordinary size is better 312 / Invention Specification (Supplement) / 92-04 / 92102639 1243805 is 1 to 10 microns (take granular inorganic aggregate as an example, average diameter is used). If the size exceeds 10 micrometers, the dielectric ceramic structure becomes excessively strong. If the size is less than 1 micron, it may be difficult to manufacture, but it will not affect the characteristics of the dielectric ceramic. The configuration and size of the inorganic aggregates present in the dielectric ceramics are the same as those of the inorganic aggregates when they are added during the manufacture of the dielectric ceramics, including the inorganics that are precipitated as crystals when they are added in the form of glass powder during manufacture. Concrete (calcium feldspar, spinel and bowl spinel). The aforementioned "glass" depends on the type and content, and can change the sintering temperature and dielectric characteristics of the dielectric ceramic. When the total amount of the inorganic aggregate and the glass is 100 wt%, the glass is 40 to 80 wt% (preferably 40 to 70 wt%, and more preferably 50 to 60 wt%). If the glass content is less than 40 wt%, it is difficult to reduce the sintering temperature to less than 1000 ° C, and when it exceeds 80 wt%, the mechanical strength is reduced, and the dielectric characteristics in the high frequency range are also insufficient. In particular, ε r is undesirably too small. In a specific embodiment of the present invention, the glass contains an alkali metal element, and the glass contains at least one of the elements of silicon, boron, aluminum, calcium, and zinc, and at least one of the elements of lithium, sodium, and potassium (later (Referred to as "X"). There are no special restrictions on the compounds made of the elements contained in glass. In a specific embodiment of the present invention, when the glass contains an alkali metal element, the aforementioned "represented by an oxide" is independent of what Si, B, Al, Ca, Zn, and X compounds are present in the glass. Si is calculated as SiO2, B is calculated as B2O3, A1 is calculated as Al2O3, Ca is calculated as CaO, Zn is calculated as ZnO and X is calculated as χ2. In a specific embodiment of the present invention, when the glass does not contain an alkali metal element, 312 / Invention (Supplement) / 92-04 / 92102639 1243805 The glass contains at least silicon, boron, aluminum, calcium and zinc . There is no particular limitation on what kind of compound the glass contains these elements. In a specific embodiment of the present invention, when the glass does not contain an alkali metal element, the aforementioned term "expressed as an oxide" is independent of what Si, B, Al, Ca and Z11 are present in the glass, and the Si system Calculated by Si02, B is calculated by B2 03, A 1 is calculated by A 12 0 ', ca is calculated by Ca 0, and Z η is calculated by Z η 0. If the total amount of glass is 100 wt%, expressed in terms of oxides, silicon is 20 to 30 wt% (more preferably 20 to 27%, still more preferably 21 to 25 wt%). If the silicon content is less than 20 wt%, the softening temperature of the glass is too low, and the properties of sintering at the same time as the low-resistance conductor are insufficient, may cause undesired distortion, and further, Er may be undesirably too high. On the other hand, when the silicon content exceeds 30 wt%, ε r is medium 値, but since the sintering temperature becomes higher, sintering at the same time as a low-resistance wire becomes difficult. On the other hand, the sintering rate of the glass component can be increased, but the dielectric loss may be increased undesirably. The boron content is 5 to 30 wt% in terms of oxides. If it is less than 5 wt%, the sintering temperature is too high, and the sintering properties are insufficient at the same time as the low-resistance conductor, often causing undesired distortion. On the other hand, if the boron content exceeds 30 wt%, the softening temperature of the glass is too low, and the sintering properties at the same time as the low-resistance conductor are insufficient, causing distortion. In addition, the chemical stability of glass to dielectric ceramics is reduced, so that desired chemical resistance cannot be obtained. By containing 10 to 30 wt% of boron, the sintering temperature can be adjusted to a wide range from 750 ° C to 950 ° C during manufacture. In addition, in addition to the foregoing, the simultaneous sintering properties of low-resistance conductors containing 15 to 30 wt% of boron become particularly disadvantageous 312 / Invention Specification (Supplement) / 92-04 / 92102639 1243805, which can effectively prevent distortion. By containing 20 1 30 wt% of boron, in addition to the aforementioned characteristics, the chemical resistance of the dielectric ceramic becomes extremely high. For example, during the plating process of manufacturing a multilayer wiring substrate, it can effectively prevent the dielectric ceramic from melting and dissolving. In addition, the aluminum content is 20 to 30 wt% (more preferably 21 to 29 wt% and still more preferably 22 to 26 wt%) in terms of oxides. If the aluminum content is less than 20 wt%, the mechanical strength of the dielectric ceramic cannot be sufficiently obtained, and particularly when the aluminum content is less than 10 wt%, the glass stability is undesirably destroyed. On the other hand, when it exceeds 30 wt%, the sintering temperature becomes too high, which is undesirable. Expressed as an oxide, the calcium content is 10 to 20 wt% (more preferably 12 to 20 wt%, and still more preferably 15 to 18 wt%). When the bromine content is less than 10 wt%, the melting properties of the glass cannot be sufficiently improved. On the other hand, when it exceeds 20 wt%, the thermal expansion coefficient becomes undesirably excessively large. In terms of oxides, the zinc content is 10 to 20 wt% (more preferably 10 to 18 wt%, and still more preferably 11 to 16 wt%). The zinc content is less than 10 wt%, and the sintering properties are insufficient at the same time as the low-temperature resistance conductor, which undesirably causes distortion. On the other hand, if the content exceeds 20 wt%, the chemical resistance of the dielectric ceramic cannot be sufficiently obtained. In a specific embodiment of the present invention, when the glass contains an alkali metal element, expressed as an oxide, the X content is 0.2 to 5 wt%. If the content is less than 0.2 wt%, the glass transition temperature may become too high, and the sintering properties may be undesirably deteriorated. On the other hand, when the content exceeds 5 wt%, the glass transition temperature may decrease, so that only the glass is undesirably excessively sintered. For at least any one of lithium, sodium, and potassium, it is sufficient that X falls within the aforementioned range. 312 / Invention Specification (Supplement) / 92-04 / 92102639 1243805 However, if a low-resistance conductor of a multilayer wiring substrate using a metal mainly composed of silver is used, it is desirable that it does not contain lithium. Therefore, the migration of silver can be extremely effectively suppressed. The fact that "the glass does not contain an alkali metal element in one embodiment of the present invention" means that lithium, sodium, and potassium are not substantially contained in the glass. In other words, these elements may not be actively included, but may inevitably be included. In this case, it is hoped that the degree of influence caused by the inclusion of lithium, sodium and potassium will not occur. In other words, if the total glass content is 100 wt%, the content of lithium, sodium and potassium is preferably less than 0.2 wt% (more preferably in the slightest It does not contain lithium, sodium and potassium). When a silver-based metal is used as a low-resistance conductor of a multilayer wiring substrate, when silver migration is particularly suspect, such as a very small distance between adjacent lines, or an insulating layer or an insulating ceramic layer (occasionally referred to as an insulating layer in this specification) ) When the thickness is very thin, it is better to use glass without alkali metal. The oxides of these elements indicate that individual contents can be combined. In other words, for example: In a specific embodiment of the present invention, when the glass contains an alkali metal element, the silicon content is 20 to 27 wt%, the boron is 10 to 30 wt%, the aluminum is 21 to 29 wt%, and the calcium is 12 to 20 wt%, zinc is 10 to 18 wt% and X is 0.2 to 5 wt%. In addition, the silicon content is 21 to 25 wt%, boron is 15 to 30 wt%, aluminum is 22 to 26 wt%, calcium is 15 to 18 wt%, and zinc is 1 1 to 16 wt%. And X is 0.2 to 5 wt%. In a specific embodiment of the present invention, when the glass does not contain an alkali metal element, the silicon content is 20 to 27 wt%, the boron is 10 to 30 wt%, the aluminum is 2 1 to 29 wt%, and the calcium is 12 to 20 The wt% and zinc are 10 to 18 wt%. In addition, the silicon content can be 21 to 25 wt%, and boron can be 15 to 30 wt%. The inscription is 22 to 312 / Invention Specification (Supplement) / 92-〇4 / 92102639 1243805 2 6 wt%, and fishing is 1 5 To 18 wt% and zinc to 1 to 16 wt%. According to the dielectric ceramic of the present invention, the dielectric loss at 1 to 15 GH z (particularly 3 to) 0 G Η z is 50 χ 10.4 · or less (otherwise 40 χ 10 · 4 or less, particularly 30 X 10 · 4 or less and usually 20 X 10 · 4 or more). Generally, the dielectric loss becomes larger as the frequency of use becomes higher, but in the dielectric ceramic of the present invention, the dielectric loss in the GHz region can be controlled as small as described above. This dielectric loss can be changed not only by the glass composition, but also by the inorganic filler. In this way, the dielectric loss depends on the composition, the amount of inorganic filler added during manufacture, and the sintering conditions such as temperature adjustment. In the present invention, the dielectric characteristics obtained at 3 GHz are used as a measure for evaluating high-frequency dielectric characteristics, and the dielectric characteristics are representative of measurement and evaluation of the dielectric characteristics. The reason for choosing 3 GHz is that 3 GHz is a common segment of wireless segment network (LAN) (such as 2.4 to 2.5 GHz), and it is easy to compare and evaluate with existing products. In addition, it is also possible that the ε r is from 1 to 15 GHz (typically from 3 to 10 GHz) from 6 to 13 (otherwise from 7 to 13, especially from 9 to 13). Generally, as the frequency of use becomes higher, ε r becomes lower. If ε r is too small, it is necessary to make the dielectric ceramic into a large size before using it in the GHz region, thereby making size reduction difficult. Therefore, considering the use of the GHz band, it is preferable to make ε r larger, and thus miniaturization of various electronic components can also be applied to the GHz band. The rf (temperature range: 25 to 80 ° C) at 1 to 15 GHz (especially 3 to 10 GHz) is -20 to 10 ppm / t: (other than -10 to 10 ppm plant C, especially -10 to 5 ppm / ° C). Generally, as the operating frequency becomes higher, the absolute value of the temperature coefficient of the resonance frequency becomes larger toward the negative direction. If the absolute system becomes larger in the negative direction, when used as a package substrate, it is difficult to support the band-pass filter 16 312 / Invention Specification (Supplement) / 92- (Μ / 92102639 1243805). The reliability is reduced. Therefore, considering the application in the GHz region, the absolute value of rf is preferably small, so the stable operation of various electronic components can also be applied to the GHz region. In addition, the thermal expansion coefficient from 25 ° C to 400 ° C It is possible to raise it to 5 to 10 ppm / ° C. The thermal expansion coefficient of printed wiring boards commonly used in recent years is about 13 to 14 ppm wide C, and the thermal expansion coefficient of 1C semiconductor components is about 3 to 4 ppm / ° C. If a dielectric ceramic is used as the multilayer wiring substrate, the thermal expansion coefficient needs to be closer to the thermal expansion coefficient of the printed circuit board and the thermal expansion coefficient of the semiconductor element. The dielectric ceramic of the present invention can meet this demand. In addition, it is resistant to bending The strength is 160 MPa or more (in addition to 180 MPa or more, especially 190 MPa or more). If the flexural strength is 160 MPa or more, when the multilayer wiring substrate or the electronic element is made of the dielectric ceramic of the present invention When the product is dropped, it can overcome the problem of cracking due to impact. Multi-layer wiring substrates or electronic components use metal brazing (such as sealing rings for electromagnetic shielding) to overcome the fracture caused by thermal stress during such brazing. Dielectric ceramics can be obtained in the present invention, where the dielectric loss at 1 to 15 GHz (especially 3 to 10 GHz) is 50 X 10_4 or less, ε r is 6 to 13, rf is -20 to 10 PPm / ° C The thermal expansion coefficient at 25 to 400 ° C is 5 to 10 ppm / ° C and the flexural strength is 160 MPa or more. In addition, dielectric ceramics can be used here at 1 to 15 GHz (especially 3 to 10 GHz). Power loss is 40 X 10_4 or less, er is 7 to 13, rf is -10 to 10 ppm / ° C, thermal expansion coefficient is 25 to 400 ° C at 5 to 10 ppm wide C, and flexural strength is 1 80 MPa or Above. 312 / Invention Specification (Supplement) / 92-04 / 92102639 1243805 Especially if it contains both zinc spinel and titanium oxide materials as inorganic materials, dielectric ceramics can be obtained, here 3 to 10 The ε r of the GHz is 9 to 1 3, the τ f is -15 to 0 ppm Tc, and the flexural strength is 1 80 MPa. In addition, if zinc spinel aggregate and titania are contained Both, and the total amount of inorganic material and glass is 100 wt%, and the inorganic material is 30 to 60 wt%, then the dielectric ceramic can be obtained. Here, the er at 3 to 10 GHz is 10 to 13, and the rf is -15 to 0 ppm / ° C and flexural strength of 190 MPa or more. The right contains both a zinc spinel aggregate and a titanate aggregate as an inorganic aggregate, and the total amount of the inorganic aggregate and glass is 100%. Dielectric ceramics can be obtained with a weight percentage of 30 to 60 wt ° / 〇 and m T / m G of 0 or 6 or more. This εΓ at 3 to 10 GHz is 10 to 13 , Rf is -3 to 0 ppm / ° C and flexural strength is 190 MPa or more. The dielectric loss, ε r, τ f, thermal expansion coefficient, and flexural strength of the present invention are determined in the same manner as the measurement method of the foregoing embodiment. The method for obtaining the dielectric ceramic of the present invention is not particularly limited, and for example, the following methods can be used. In other words, in a specific embodiment of the present invention, when the glass contains an alkali metal element, the dielectric ceramic composition is obtained by mixing an inorganic aggregate powder and a glass powder, and sintering at a temperature of 10,000 t or below, wherein When the total amount of glass powder is 100% by weight, expressed in terms of oxides, Si: 20 to 30% by weight, B: 5 to 30% by weight, Al: 20 to 30% by weight, Ca: 10 to 20% by weight, and Zn: 10 to 20 wt%, and at least one alkali metal: the total amount of Li, Na, and K is 0.2 to 5 wt%; when the total amount of the inorganic aggregate powder and the glass powder is 100 wt%, the inorganic aggregate powder accounts for 20 to 60 wt% and glass powder account for 40 to 80 wt%. 18 312 / Invention Specification (Supplement) / 92-04 / 92102639 1243805 In other words, in a specific embodiment of the present invention, when the glass does not contain an alkali metal element, the method of obtaining the dielectric ceramic composition is via a mixed inorganic 塡Powder and glass powder, and sintered at a temperature of 1 ooo ° C or below, wherein when the total amount of glass powder is 100 wt%, it is expressed in terms of oxide, S i: 20 to 30 wt%, B · · 5 to 30 wt%, A1 ·· 20 to 30 wt%, Ca ·· 10 to 20wt%, Zn: 10 to 20wt%, and the test metal does not contain Li, Na or κ; When inorganic powder and glass When the total powder amount is 100 wt%, the inorganic aggregate powder accounts for 20 to 60 wt% and the glass powder accounts for 40 to 80 wt%. As for the aforementioned inorganic agglomerate powders in this production method, they are titanium oxide, aluminum oxide and chromium oxide powders made by sintering, respectively. They can be used individually or in combination. There is no particular restriction on the diameter of the inorganic aggregate powder, and it is preferably 1 to 10 microns. When the diameter is greater than 10 microns, the dielectric ceramic structure is too rough. When the diameter is less than 1 micron, pulverization takes too long and handling is difficult. It is not necessary to have the entire amount of the inorganic filler powder as the inorganic filler of the dielectric ceramic, as long as a part of the powder can be melted into glass and exist as glass. The glass frit is obtained, for example, by mixing the raw material powder having the aforementioned composition by heating and melting, rapidly cooling it into a glass frit, and pulverizing the glass frit. The reason for the content of various elements in glass powder is the same as the reason for the content of glass in dielectric ceramics. There is no particular restriction on the diameter of the glass powder. In other words, it can be 1 to 10 micrometers. If the diameter exceeds 10 micrometers, it may cause undesired effects when forming into a glass plate; if the diameter is less than 1 micrometer, pulverization takes too long and handling is difficult. There is no need to have glass with a full amount of glass powder as the dielectric ceramic, as long as a part of the powder 312 / Invention Specification (Supplement) / 92-04 / 92102639 1243805 precipitates in the dielectric ceramic and thus exists as glass. The glass transition temperature Tg of the glass powder is not particularly limited, but it is preferably 560 to 670 ° C (more preferably 570 to 660 ° C, and even more preferably 570 to 640 ° C). In this range, it is advantageous to maintain the following properties, and at the same time with low resistance conductors such as silver-based metals (silver alone, Ag / Pd alloy, Ag / Pt alloy, Ag / Cu alloy, or Ag / Au alloy, etc.) Or the copper-based metal (single copper but containing a small amount of other elements) is sintered at the same time, and can effectively overcome the distortion caused by sintering. The bending temperature of glass frit Mg [that is, the softening temperature in the thermal expansion curve (DTA curve), which is the temperature at which the expansion stops and obviously begins to shrink; occasionally referred to as At] is not particularly limited, and the temperature difference from the glass transition temperature Tg is expected 30 to 45 ° C (more preferably 30 to 40 ° C, more preferably 30 to 38 ° C). If the temperature difference between T g and M g falls within this range, shrinkage and dispersion due to sintering can be effectively suppressed. In this way, electronic components or wiring boards can be designed with high dimensional accuracy. As for the composition ratio of the inorganic ceramic powder and the glass powder in the composition of the dielectric ceramics, the reason is the same as that of the dielectric ceramics. It is desired that the mixing amount of the inorganic ceramic powder accounts for 30 to 60 wt% (the glass powder is 40 to 70). wt%). It is preferable that the mixing amount thereof is 40 to 60 wt% of inorganic aggregate powder (40 to 60 wt% of glass powder), and more preferably 45 to 55 wt% (45 to 55 wt% of glass powder). The dielectric ceramic composition may be composed of an inorganic aggregate powder and a glass powder. In addition to these components, it may contain, for example, a binder, a solvent, a plasticizer, and a dispersant. There are no particular restrictions on the properties of the dielectric ceramic composition, such as powders, slurries, and pastes. In addition, the dielectric ceramic composition can be formed by such powders, slurries, and 312 / Invention Specification (Supplement) / 92-04 / 92102639 1243805 through various molding forms (powder: powder pressing, CIP or HIP; slurry and paste Agent: knife coating method, screen printing method and compression molding method). Sintering is preferably carried out at a temperature of 000 ° C or below (usually 75 0 ° C or above, more preferably 800 to 990 ° C, still more preferably 850 to 990 ° C, and particularly preferably 900 to 9 8 0 ° C). Above 1 000 ° C it is undesirably difficult to sinter simultaneously with other low resistance conductors. Examples The present invention will be specifically explained with reference to examples. [1] Dielectric ceramics use alkali-containing glass without spinel aggregate (1) Preparation of glass powder In addition to Si02, B2O3, AI2O3, CaO, ZnO, Na2C03 and K2C03 powder, MgO , BaO, SrO and ZrO powders were mixed at the ratios shown in Table 1 to prepare raw material powders. The raw material powder after the preparation is heated and melted, poured into ρρ λ and rapidly cooled in water, and granulated in water to obtain a glass frit. 〗 Li rice bucket is pulverized in a ball mill to produce 10 kinds of glass powder (glasses 1 to 10), with an average stomach diameter of 3 microns. 312 / Invention Specification (Supplement) / 92-04 / 92102639 1243805 £ Dielectric Ceramic Inorganic Material 1 (wt%) Composition (Wt%) Η Ν I 1 1 rn rH sd 1 1 1 1 〇 Free 1 o r- o 1 9 PQ mm MgO 1 1 inch om T—H d < N r— ^ Test metal Na20 Na20 o 1 * Na20 1 * 〇 (N 1 * 1 * Na20 1 * (N rn m (N rH m 〇 inch · 〇TH Τ-Ή rH 1 * 1 * 1 * 1 * 1 * H 1 * 9 U v〇VO 1 * 1 * | * 0.15 | Bu 1 * ON 00 Al2〇3 Art G \ v〇m rp C \ rH * < N 00 (N (N 00 (N Β2Ο3 00 (N * 45.5 1 Bu r— ^ Ό m * VO od (N (N Bu 00 00 5 5 ο < N οό (N JQ ^ T) < N r〇ΓνΙ fp (N (N 〇 \ fp * glass number < N ro vp tp 00 C \ o rH * < TH (N cp vp r- 00 〇 \ o * ττ fl: v 6e9sls / s- (N6 / ffiii) _ & ^ i ^ ® / ne 1243805 (2 ) The measurement of T g and M g of glass powder is as above. (1) The Tg and Mg of 10 kinds of glass powder manufactured are based on the differential thermal measurement device (model "THERMOFLEX TAS 300 TG8 10D". Measured by Xue Xue International Co., Ltd., the individual 値 of Tg, Mg and Mg-Tg are shown in Table 2. Table 2 Thermal Feature Number of Glass Dielectric Ceramics Tg (° c) Mg (° C) Mg.Tg (° C) 1 576 6 11 35 2 580 6 13 33 * 3 535 650 115 * 4 520 640 120 * 5 638 675 37 * 6 686 73 1 45 * 7 655 695 40 * 8 549 580 3 1 * 9 683 722 39 * 1 0 7 18 765 47 is shown in Table 2 as “not within the scope of the present invention.” (3) Manufacturing of green sheets (dielectric ceramic composition) 10 to individual glass powders manufactured as described in (2) above and as inorganic fillers The powdery aluminum oxide powder was weighed to have a ratio of 50 wt% as shown in Table 1, and was mixed in a ball mill to produce a mixed powder. The produced mixed powder was added with a binder (acrylic resin), a plasticizer {dibutyl phthalate (DBP)}, and a solvent (toluene), and mixed to prepare 10 kinds of slurries. The individual slurry was formed into a sheet by a knife coating method, and the thickness of the sintered sheet was 100 micrometers, thereby obtaining 23 312 / Invention Specification (Supplement) / 92-04 / 92102639 1243805 10 kinds of green sheets. (4) Manufacturing of ceramics for the first measurement (for measuring the dielectric characteristics) and measurement of dielectric characteristics 10 kinds of green sheets manufactured as above (3) are punched into a predetermined configuration, and a plurality of sheets are allowed to pass through the heat A total of 10 pieces of pressure-bonded co-stacks were sintered at 900 ° C for 15 minutes to produce ceramics. The ceramics were polished to become 50 mm x 50 mm X 0.63 5 mm sheets, and 10 kinds of ceramics were manufactured for the first measurement. The dielectric loss and ε r at 25 ° C and 3 GHz were measured by using the ceramic for the first measurement through the dielectric resonator-disturbance method of the dielectric ceramic. The results are shown in Table 3 〇 Table 3 Characteristics of the dielectric ceramics Example Dielectric loss (X 1 Ο'4) (3GHz) ε r (3GHz) Coefficient of thermal expansion (25-400 ° C) (ppm / ° C) 1 38 7.4 6.1 2 40 7.2 6.2 * 3 13 5.2 5.5 * 4 150 6.5 4.6 * 5 30 5.9 7.3 * 6 18 5.6 5.5 * 7 64 4.9 6.0 * 8 63 6.5 6.4 * 9 19 6.6 4.9 * 1 0 40 7.2 5.4 "" in the table 3 means "outside the scope of the present invention". (5) The second measurement (for measuring the coefficient of thermal expansion) for the manufacture of ceramics and the measurement of the coefficient of thermal expansion 24 312 / Instruction for Inventory (Supplement) / 92-04 / 92102639 1243805 The 10 types of green sheets made in (3) above are Pressing into a predetermined configuration, 20 sheets were stacked by a thermocompression bonding method, and sintered at 90 kt for 15 minutes to produce a ceramic. The ceramics were polished to form 3 mm x 3 mm x 1.6 mm pipe columns' to make 10 types of ceramics for the second measurement. The coefficient of thermal expansion from 25 ° C to 400 ° C was measured using a ceramic for a second measurement by a differential expansion thermal machine analysis device (model "TMA8140D" manufactured by Rigaku International Corporation). The results are collectively shown in Table 3. (6) The third measurement (for measuring the simultaneous sintering properties) for the manufacture of ceramics and the evaluation of the simultaneous sintering properties. Ten kinds of green sheets manufactured as above (3) were printed at a predetermined position using a silver paste with a thickness of 15 microns. Laminate other green sheets on the silver paste layer by thermocompression bonding. 'Similarly, the silver paste is also printed on other green sheets. Repeat this operation.' A total of 5 green sheets were laminated to obtain an unsintered laminate. , Use a silver paste to print in a predetermined pattern between the layers. The unsintered laminate was punched to a diameter of 4 cm 'and sintered at 90 ° C for 15 minutes. In this way, 10 kinds of ceramics with low resistance conductors for the third measurement were manufactured. ① Evaluation of 10 kinds of distortion caused by sintering For the third measurement, the manufacturing ceramics are laid on a plane, and the difference between the maximum position and the minimum position (contact position with the plane) from the plane is determined. Is “”, twisted more than 50 microns is marked as “X” and shown in Table 4. ② Silver migration due to sintering 10 kinds of ceramics manufactured for the third measurement were cut in the stacking direction, and the cut surface was cut by EPMA ( Electron probe microanalyzer). The results were found in the ceramic interior 25 312 / Invention Specification (Supplement) / 92-04 / 92102639 1243805 Silver migration was found. The migration distance is less than 5 microns as "◎", and the migration distance is 5 to 10 microns. It is "0", and the migration distance is "X" when it exceeds 10 micrometers, and is shown in Table 4. Table 4 Example Dielectric Ceramic Characteristics Silver Migration Torsion Flexural Strength (MPa) 1 ◎ ◎ 2 10 2 ◎ ◎ 260 * 3 X ◎-* 4 〇 ◎ < 180 * 5 XX-* 6 〇X-* 7 X ◎-* 8 ◎ X-* 9 ◎ X-* 1 0 XX-Table 4 "*" means "not a property The scope of the present invention ". (7) For the fourth measurement (bending strength measurement) for the manufacture of ceramics and the evaluation of the bending strength, as described in (3) above, the green sheets correspond to those of Examples 1, 2, and 4. The green sheet is punched into a predetermined configuration, and 10 green sheets are stacked by thermocompression bonding and sintered at 900 ° C for 15 minutes to produce ceramics. The ceramics are polished to become 4 mm X 3 mm X 3 6 mm tubes The column was manufactured with three types of ceramics for the fourth measurement. The flexural strength (three-point bending) was measured by using the ceramics for the fourth measurement in accordance with JIS R 1601. The results are shown in Table 4. 26 312 / Invention Specification (Supplement) / 92-04 / 92102639 1243805 (8) Effects of Examples 1 to 10 The results are shown in Tables 1 to 4. Examples 3 to 10 can be sintered at a low temperature of 9 0 ° C. It also shows a certain degree of dielectric properties. However, some of them show that the dielectric ceramics are distorted due to the poor thermal properties of glass frit, and some do not provide sufficient dielectric properties. The migration of low-resistance conductors due to sintering, or some of them cannot provide sufficient flexural strength. None of these examples has a sufficiently good balance of individual characteristics. On the other hand, the product examples 1 and 2 of the present invention can be compared with low The resistance conductor is sintered at 900 ° C at the same time and shows good dielectric properties (dielectric loss: 38 to 40 X 10 · 4, er: 7.2 to 7.4, and flexural strength: 210 to 260 MPa). In addition, no migration of the components constituting the low-resistance conductor was observed, and no warpage of the substrate was observed. It was found that a sufficiently high bending strength can be obtained. In addition, the coefficient of thermal expansion is 6.1 to 6.2 p p m / ° C, which shows suitable characteristics as a wiring board. [2] Dielectric ceramics using glass containing alkali metal elements and glass containing zinc spinel (1) Manufacture of ceramics for fifth measurement (measurement of dielectric properties) and measurement of dielectric properties are as above [1] ], (1) No. 1, 2, 4, 6 and 9 glass manufactured as glass powder 'and zinc spinel powder, titanium oxide powder and calcium carbonate powder as inorganic fillers, these materials are shown in Table 5 The ratios are combined and mixed, and green sheets are produced as shown in [1] '(3) above. Subsequently, similar to the above [1], (4) sintering and polishing are performed 'to produce a total of 11 ceramics for the fifth measurement. Among the manufactured dielectric ceramics, except for Example 11 where bubbles were generated during sintering and Examples 1 to 2 to 1 caused distortion, the remaining 7 types of dielectric ceramics were similar to 27 312 / Invention Specification (Supplement) / 92 -04/92102639 1243805 The method of [1], (4) above is used to measure the relative permittivity ε r at 3 GHz and the temperature coefficient τ f of the resonance frequency at 25 to 80 ° C. The results are shown together in the table
28 312/發明說明書(補件)/92-〇4/92102639 124380528 312 / Invention Specification (Supplement) / 92-〇4 / 92102639 1243805
介電陶瓷特性 CQ (MPa) 燒結時冒泡 180 190 (N 〇\ r*H 190 220 I cn Ό r—H r-H 1 扭曲 ◎ ◎ ◎ ◎ ◎ ◎ ◎ X (ppm/°C) as r-H 1 t—H rn to ▼-H 1 卜 rn 1 ㈦ (3GHz) 卜 cK 10.6 10.6 10.3 cK (N r-H r-H 10.7 » 介電陶瓷 無機塡料 (wt%) r-H * 5 種類·比例(重量） mT/mG 0.86 0.91 1 0·71 1 0.76 0.74 1 °·42 1 1 0.74 0.72 1其它| 1 CaTi03 20 鈦氧 卜 o 卜 〇\ V-H 寸 r-H 1 00 鋅尖晶石 00 r-H (N m Ό (N (N 玻璃 (wt%) I wn 00 * as ON ΙΟ v〇 m m yr) cn 玻璃 編號 ψ i r—1 t—^ r*eH <N v〇 On < * (N r-H cn r—^ 寸 r-H ^T) v〇 卜 00 * *20 r-H CN ϋώ 1-< 63 鲁鲁 6e9sls/K}-s/ff4ii)»^_a^/ne 1243805 (2)供第六測量（測量同時燒結性質）用之陶瓷之製造以及 同時燒結性質之評比 類似前述[1 ]，（6)測定扭曲，根據相同評比參考，“◎” 或 X 藏不於表5。 (3 )供第七測量（測量抗彎強度）用之陶瓷之製造以及抗彎 強度之評比 除了使用前述[2]，（1)之生片材（此處可製造於如上[2]， (1)及（2)不會冒氣泡或扭曲之陶瓷）外，7種供第七測量用 之陶瓷係以前述[1 ]，（ 7)之相同方式製造。然後遵照相同 方式測量抗彎強度，結果共同顯示於表5。 (4 )實施例1 1至2 1之效果 由表5結果可知，實施例12至18各自可於如900 °C之 低溫燒結。另一方面，於實施例1 1中，因玻璃與無機塡料 之比値非屬本發明之範圍，故於燒結期間出現氣泡，實施 例1 1之產物無法用作爲介電陶瓷。實施例1 9至2 1出現扭 曲。 只含玻璃之情況下，ε r通常約爲6。相反地，無機塡料 爲鋅尖晶石塡料及鈦氧塡料製成之介電陶瓷（實施例1 2至 16及18)之高達9.5至10.7。此外，rf有一在-15至1 PpmTC之小絕對値。另一方面，於無機塡料爲鋅尖晶石塡 料及鈦酸鈣塡料之介電陶瓷（實施例1 7)之例中，ε r高達 11.2，同時rf也具有7 ppin7°C之小絕對値。 於無機塡料爲鋅尖晶石塡料以及鈦酸鈣塡料之介電陶瓷 案例，可提供1 65 MPa之抗彎強度。特別，於無機塡料爲 30 312/發明說明書(補件)/92-04/92102639 1243805 鋅尖晶石塡料及鈦氧塡料之介電陶瓷案例，可提供1 8 0至 2 2 0 Μ P a之絕佳抗彎強度。 以陶瓷總量爲1 〇〇 %爲例’鋅尖晶石塡料及鈦氧塡料 之含量共計至47 wt% ;此外於鋅尖晶石塡料（m G)及鈦 氧塡料（mT)之mT/mG爲0.71至0.76之例中，可見陶瓷可 維持ε r高達1 0.3至1 0 · 6，而r f被壓抑至極小値，_ 3至 1 p p m厂(3，同時仍維持抗彎強度高達1 9 0至1 9 2 Μ P a。 [3 ]介電陶瓷使用不含鹼金屬元素以及不含鋅尖晶石塡料 之玻璃 (1)玻璃粉之製備 除了 Si〇2、B2〇3、A1203' CaO 以及 ZnO 粉末外，MgO、 BaO、SrO及Zr02粉末以表6所示比例混合而製備原料粉 末。製備後之原料粉末加熱熔化，投擲入水中快速冷卻， 且同時於水中造粒而獲得玻璃料。玻璃料於球磨機粉化而 製造1 1種玻璃粉（1至Π號玻璃），具有平均直徑爲3微米。 312/發明說明書(補件)/92-04/92102639 1243805 介電陶瓷 祕芑 Μ ^ <a\ w (wt%) 誠(wt%) Η Ν 1 1 1 1 s d 1 1 1 1 r ,mm< 〇 1 d r- d \ PQ 卜 m 1 1 寸 o m ，… o (N r—H 鹼金屬 1 1 1 1 * 1 Na20 1 1 * O 1 * 1 * Na20 1 * T—H r〇 〇 寸 〇 (Ν cn (Ν 1 * 1 * 1 * 1 * 1 * r—^ 1 * U 卜 00 卜 1 * 1 * | *0.15 | 卜 r-H v〇 1 * ON 00 Al2〇3 CN Ό (Ν (Ν Os v〇 cn rn 〇\ * (N 00 CN CN oo (N Β2〇3 \〇 (Ν 口 1 *45.5 1 r- r-H Ό m * v〇 00 寸 CN (N CN 00 宕 (Ν CN ^Τ) (Ν 00 (Ν jn (N rn (N rn (N <N Os rn * 玻璃 編號 (Ν m up v〇 r- 00 Os o T—H * r—H r-H * < r-H (Ν m ip v〇 ST 00 On o * r-H ▼-H *Dielectric ceramic characteristics CQ (MPa) Sintering 180 190 (N 〇 \ r * H 190 220 I cn Ό r—H rH 1 Twisted ◎ ◎ ◎ ◎ ◎ ◎ X (ppm / ° C) as rH 1 t —H rn to ▼ -H 1 rn rn 1 ㈦ (3GHz) c cK 10.6 10.6 10.3 cK (N rH rH 10.7 »Dielectric ceramic inorganic material (wt%) rH * 5 Type · Ratio (weight) mT / mG 0.86 0.91 1 0 · 71 1 0.76 0.74 1 ° · 42 1 1 0.74 0.72 1 Others | 1 CaTi03 20 Titanium oxide o 〇 〇 0 VH inch rH 1 00 zinc spinel 00 rH (N m Ό (N (N glass ( wt%) I wn 00 * as ON ΙΟ v〇mm yr) cn glass number ψ ir—1 t— ^ r * eH < N v〇On < * (N rH cn r— ^ inch rH ^ T) v 〇00 00 * * 20 rH CN 1- < 63 Lulu 6e9sls / K} -s / ff4ii) »^ _ a ^ / ne 1243805 (2) Manufacture of ceramics for sixth measurement (measurement of simultaneous sintering properties) And the evaluation of simultaneous sintering properties is similar to the aforementioned [1], (6) to measure distortion, according to the same evaluation reference, "◎" or X is not shown in Table 5. (3) Ceramics for the seventh measurement (measurement of bending strength) System And the flexural strength is evaluated in addition to using the above-mentioned [2], (1) green sheet (here can be manufactured as above [2], (1) and (2) ceramics that will not bubble or twist), 7 A ceramic for seventh measurement was manufactured in the same manner as in the above [1], (7). Then the bending strength was measured in the same manner, and the results are shown in Table 5. (4) Examples 1 to 2 of 1 From the results in Table 5, it can be known that each of Examples 12 to 18 can be sintered at a low temperature such as 900 ° C. On the other hand, in Example 11, the ratio of glass to inorganic materials is outside the scope of the present invention. Therefore, bubbles occur during sintering, and the product of Example 11 cannot be used as a dielectric ceramic. Examples 19 to 21 are distorted. In the case of only containing glass, ε r is usually about 6. On the contrary, inorganic filler The dielectric ceramics (Examples 12 to 16 and 18) made of zinc spinel and titanium oxide materials are as high as 9.5 to 10.7. In addition, rf has a small absolute mean of -15 to 1 PpmTC. On the other hand, in the case of a dielectric ceramic (Example 17) in which the inorganic material is zinc spinel material and calcium titanate material, ε r is as high as 11.2, and rf also has a small absolute value of 7 ppin7 ° C. value. In the case of dielectric ceramics in which the inorganic material is zinc spinel material and calcium titanate material, it can provide a bending strength of 1 65 MPa. In particular, in the case of inorganic ceramics with dielectric materials of 30 312 / Invention Specification (Supplement) / 92-04 / 92102639 1243805 Zinc spinel materials and titanium oxide materials, we can provide 180 to 2 2 Μ P a Excellent bending strength. Take 100% of ceramics as an example. The content of zinc spinel aggregate and titanium oxide aggregate is 47 wt%. In addition, zinc spinel aggregate and titanium oxide aggregate (mT) In the case where mT / mG is 0.71 to 0.76, it can be seen that ceramics can maintain ε r as high as 10.3 to 1 0 · 6, while rf is suppressed to a very small value, _ 3 to 1 ppm factory (3, while still maintaining bending strength Up to 190 to 192 MPa. [3] Dielectric ceramics use glass containing no alkali metal elements and no zinc spinel materials. (1) Preparation of glass powder except Si02 and B203. In addition to A1203 'CaO and ZnO powders, MgO, BaO, SrO and Zr02 powders were mixed in the proportions shown in Table 6 to prepare raw material powders. The prepared raw material powders were heated and melted, thrown into water for rapid cooling, and simultaneously granulated in water. A glass frit was obtained. The glass frit was pulverized in a ball mill to produce 11 types of glass frit (glasses 1 to Π) having an average diameter of 3 micrometers. 312 / Invention Specification (Supplement) / 92-04 / 92102639 1243805 Dielectric ceramics Secret M ^ < a \ w (wt%) 诚 (wt%) Η Ν 1 1 1 1 sd 1 1 1 1 r, mm < 〇1 d r- d \ PQ m m 1 1 inch om … O (N r—H alkali metal 1 1 1 1 * 1 Na20 1 1 * O 1 * 1 * Na20 1 * T—H r〇〇inch〇 (N cn (N 1 * 1 * 1 * 1 * 1 * r— ^ 1 * U BU 00 BU 1 * 1 * | * 0.15 | BU rH v〇1 * ON 00 Al2〇3 CN Ό (N (Ν Os v〇cn rn 〇 \ * (N 00 CN CN oo (N Β2〇3 \ 〇 (Ν 口 1 * 45.5 1 r- rH Ό m * v〇00 inch CN (N CN 00 ND (N CN ^ Τ) (N 00 (N jn (N rn (N rn (N < N Os rn * glass number (Ν m up v〇r- 00 Os o T—H * r—H rH * < rH (Ν m ip v〇ST 00 On o * rH ▼ -H *
s舞fc: V 。「匪編^郜餾讲_#」长嗽纟，，9撇 9 9 6e9(N0I(N6/寸 0-36/ffsi)_^^^s/(Nle 1243805 (2 )玻璃粉之τ g及M g之測量 如上（1 )製造之1 1種玻璃粉之Tg及Mg係藉差異熱測量 裝置（型號「塞莫夫雷特斯（THERMOFLEX TAS) 300 TG810D」埋學國際公司製造）測量，Tg、Mg及Mg-Tg之 個別値顯τκ於表7。 表7 玻璃 玻璃之熱特性 編號 Tg(°c ) Mg(°C ) Mg-Tg(°C ) 1 623 657 34 2 63 1 67 1 40 3 63 1 67 1 40 * 4 535 650 115 *5 520 640 120 *6 63 8 675 37 *7 686 73 1 45 * 8 65 5 695 40 * 9 549 5 80 3 1 * 1 0 683 722 39 * 1 1 7 18 765 47 “ ”於表7表示「非屬本發明之範圍」。 (3 )生片材之製造（介電陶瓷組成物） 1 1種至前述（2)製造之個別玻璃粉末以及作爲無機塡料 粉末之鋁氧粉末經稱重而具有如表6所示之5 0 w t %比率， 且於球磨機混合而製造混合粉末。製造的混合粉末加入黏 結劑（丙烯酸系樹脂）、增塑劑{鄰苯二甲酸二丁酯（DBP)} 33 312/發明說明書(補件)/92-04/92102639 1243805 及溶劑（甲苯），且混合而製備1 1種料漿。個別料漿藉著刀 塗法成形爲片材，燒結後片材厚度爲1 〇 〇微米’因而獲得 1 1種生片材。 (4)供第一測量（供測量介電特性）之陶瓷之製造以及介電 特性之測量 1 1種於如上（3)製造之生片材被沖壓成爲預定組態，多 塊片材透過熱壓連結共堆疊11片，於900 °C燒結15分鐘 而製造陶瓷。陶瓷接受拋光處理成爲50毫米x50毫米X 0.6 3 5毫米片材，製造1 1種供第一測量之陶瓷。經由使用 供第一測量用之陶瓷，透過介電陶瓷之介電共振器-擾動方 法，測定於2 5 °C於3 GHz之介電耗損及e r。結果顯示於 表8。 34 312/發明說明書(補件)/92-04/92102639 1243805 uni 8撇 介電陶瓷特性 抗彎強度 (MPa) 〇 (N 〇 〇 (N 1 <180 1 1 1 1 1 1 1 ◎ ◎ ◎ ◎ ◎ ◎ X ◎ X X X 熱膨脹係數 (25-400°〇 (ppm/°C) 寸 trl 寸 m uS iri v〇 uS O v〇 寸 vd ON 寸· 寸 iri £ T (3GHz) K Ό 卜： (N uS vd ON v〇 C) 寸 v〇 vd (N 卜· 3¾ ^ ^ Iff X ^ 佘WW G\ m ΠΊ o T-H o 00 r-H 3 m v〇 Os 〇 實施例 CN m l〇 vp r- 00 o * ▼—H *s 舞 fc: V. "Bandit ^ 郜 grading talk_ #" Long coughing, 9 9 9 6e9 (N0I (N6 / inch 0-36 / ffsi) _ ^^^ s / (Nle 1243805 (2) τ g of glass powder and The measurement of M g is as above (1). The Tg and Mg of 11 glass powders are measured by a differential thermal measuring device (model "THERMOFLEX TAS 300 TG810D" manufactured by Buried International Corporation). Tg The individual τκ of Mg, Mg and Mg-Tg are shown in Table 7. Table 7 Thermal characteristics of glass glass Tg (° c) Mg (° C) Mg-Tg (° C) 1 623 657 34 2 63 1 67 1 40 3 63 1 67 1 40 * 4 535 650 115 * 5 520 640 120 * 6 63 8 675 37 * 7 686 73 1 45 * 8 65 5 695 40 * 9 549 5 80 3 1 * 1 0 683 722 39 * 1 1 7 18 765 47 "" is shown in Table 7 as "not within the scope of the present invention". (3) Manufacturing of green sheets (dielectric ceramic composition) 1 to individual glass powders manufactured as described in (2) above and as inorganic The aluminum oxide powder of the powder is weighed to have a ratio of 50 wt% as shown in Table 6, and is mixed in a ball mill to produce a mixed powder. The produced mixed powder is added with a binder (acrylic resin) and a plasticizer { Dibutyl phthalate (DBP)} 33 312 / Invention Manual (Supplement) / 92-04 / 92102639 1243805 and solvent (toluene), and mixed to prepare 11 kinds of slurry. Individual slurry is formed into a sheet by knife coating method, and the thickness of the sheet after sintering For 100 micrometers', 11 kinds of green sheets were obtained. (4) The manufacture of ceramics for the first measurement (for the measurement of dielectric properties) and the measurement of dielectric properties. The sheet was punched into a predetermined configuration, and a plurality of sheets were stacked by heat pressing to form a total of 11 pieces, which were sintered at 900 ° C for 15 minutes to produce ceramics. The ceramics were polished to become 50 mm x 50 mm X 0.6 3 5 mm sheets. 11 types of ceramics for the first measurement were manufactured. By using the ceramics for the first measurement, the dielectric loss and er at 25 ° C and 3 GHz were measured through the dielectric resonator-disturbance method of the dielectric ceramic. The results are shown in Table 8. 34 312 / Invention Specification (Supplements) / 92-04 / 92102639 1243805 uni 8 Dielectric Ceramics Characteristics Flexural Strength (MPa) 〇 (N 〇〇 (N 1 < 180 1 1 1 1 1 1 1 ◎ ◎ ◎ ◎ ◎ X ◎ XXX Coefficient of thermal expansion (25-400 °° (ppm / ° C) inch trl inch m uS iri v〇uS O v〇inch vd ON inch · inch iri £ T (3GHz) K 卜 bu: (N uS vd ON v〇C) inch v〇vd (N 卜 3¾ ^ ^ Iff X ^ 佘 WW G \ m ΠΊ o TH o 00 rH 3 mv〇Os 〇 Example CN ml〇vp r- 00 o * ▼ -H *
’画爝*NS餾讲_#」长嗽OO^^L 6e9s l<N6/s-(N6/ff}si)_s^^^/(Nl e 1243805 (5 )/第=沏J量（供測量熱膨脹係數）用陶瓷之製造以及熱膨 脹係數之測量 如± (3 )製造之11種生片材被沖壓成爲預定構形，2 〇塊 片材透過熱壓連結法堆疊，於9 0 (TC燒結1 5分鐘而製造陶 瓷。陶瓷接受拋光處理成爲3毫米X 3毫米X 1 . 6毫米管柱， 製造1 1種供第二測量用之陶瓷。使用供第二測量用之陶 瓷’藉差異膨脹熱機器分析裝置（型號“TMA8 140D”理學國 際公司製造）測定由25 t;升高至40(rc之熱膨脹係數。結果 共同顯示於表8。 (6)第三測量（供測量同時燒結性質）用陶瓷之製造以及同 時燒結性質之評比 I 1種如上（3 )製造之生片材使用厚1 5微米之銀糊劑印刷 於其預定位置。於銀糊層上，藉熱壓連結而層疊其它生片 材’同樣地銀糊也印刷於其它生片材上，重複進行此項工 作’共層疊5片生片材，獲得未經燒結之層疊物，於各層 間於預定圖案使用銀糊印刷。未經燒結之層疊物沖壓成4 厘米直徑，以及於9 0 0 °C燒結1 5分鐘。如此製造1丨種配 置有低電阻導體之供第三測量用之陶瓷。 1 1種供第三測量用之陶瓷鋪於平面上，測定距離平面最 大位置與最小位置（與平面接觸位置）間之差異，若差異小 於50微米（未扭曲至實際程度）或未出現扭曲，則標示爲 ’扭曲超過50微米標示爲“ X”且分別顯示於表8。 (7 )供第四測量（抗彎強度測量）用陶瓷之製造及抗彎強度 之評比 如上（3 )製造之生片材中，對應於實施例1、2、3及4之 312/發明說明書(補件)/92-04/92102639 36 1243805 生片材沖壓成爲預定組態，透過熱壓連結法堆疊11片生片 材，且於9 0 0 °c燒結1 5分鐘而製造陶瓷。陶瓷接受拋光處 理成爲4毫米X 3毫米X 36毫米管柱，製造3種供第四 測量用之陶瓷。經由使用供第四測量用之陶瓷，測量其抗 彎強度（3點彎曲）。結果共同示於表8。 (8 )實施例1至1 0之效果 由表6至8結果，實施例4至n各自可於9 〇 (TC之低溫 燒結，且顯示某種程度的介電特性。但有部分顯示因玻璃 粉之熱特性不佳造成介電陶瓷扭曲，有些未能提供充分介 電特性，另有些因燒結而造成低電阻導體之遷移，或有些 無法提供充分抗彎強度。此等實施例皆未能帶有個別特性 之充分良好平衡。另一方面，本發明產物實施例1至3可 與低電阻導體或於9 0 0 °C同時燒結，且顯示良好介電特性 (介電耗損：30至39 X 1 Ο·4，ε r ·· 7.5至7.6，以及抗彎強 度：2 60至2 70 MPa)。此外未發現組成低電阻導體成分的 遷移、也未見基板的扭曲，可知可獲得夠高抗彎強度。此 外，熱膨脹係數爲5 . 3至5 · 4 p p m / °C，顯示作爲佈線基板 之適當特性。 [4]使用不含鹼金屬元素以及含有鋅尖晶石塡料之玻璃之 介電陶瓷 (1 )供第五測量（測量介電特性）用之陶瓷之製造以及介電 特性之測量 使用如上[1 ]，（ 1 )製造之1、2及3號玻璃作爲玻璃粉， 以及使用鋅尖晶石粉末、鈦氧粉末及碳酸鈣粉末作爲無機 塡料，該等物質係以表9所示比率組合且混合，如上[1 ]， 37 312/發明說明書(補件)/92-04/92102639 1243805 (3)所示製造生片材。隨後類似如上[1]，（4)進行燒結以及 進行拋光處理，共製造9種供第五測量用之陶瓷。製造得 之介電陶瓷中，除了實施例1 2於燒結時冒氣泡外，其餘8 種介電陶瓷，以類似前述[1]，（4)之方式測定於3 GHz之 相對介電常數ε r以及於2 5至8 0 °C之共振頻率溫度係數r f。結果共同顯示於表9。 38 312/發明說明書(補件)/92-04/92102639 1243805 6嗽 介電陶瓷特性 Β 1 (MPa) 1 丨 燒結時冒泡 180 (N r-H m 〇\ r—^ r—< 222 r—H 5： 扭曲 1 ◎! Ο ◎ ◎ ◎ ◎ ◎ ◎ V- S 〇, 3 00 cn (N uo r-H 1 卜 to a r (3GHz) I _ 10·4 1 Ll0·4 J L·!0.1 J Os 10.7 1 10.5 r-H 〇 介電陶瓷組成 無機塡料 (wt%) t-H * r-H (N r-H 種類•比例(重量） mT/mG 0.86 1 °·91 1 1 °·71 1 0.76 0.74 丨 0·42 1 1 0.75 1蛇1 1 CaTi03 20 鈦氧 卜 o ▼—4 On t—i 寸 1 〇〇 辞尖晶石 00 f—^ in (N m m Ό (N 玻璃 (wt%) 00 * Os ON m to m 芝 00 in 玻璃 編號 r-H r-H ▼—H r-H t—H r-H <N < (N r-H * m 寸 r-H in ▼—H Ό 卜 00 r-H Cn II ώ 1-< 。「匪§|^浮微讲晒铢」长術.纟，6« 1243805 (2)供第六測量（測量同時燒結性質）用之陶瓷之製造以及 同時燒結性質之評比 類似前述[1 ]，（ 6 )測定扭曲，根據相同評比參考，“ ◎” 或“ X ”顯示於表9。 (3 )供第七測量（測量抗彎強度）用之陶瓷之製造以及抗彎 強度之評比 除了使用前述[2 ]，（ 1 )之生片材（此處可製造於如上[2 ]， (1 )不會冒氣泡或扭曲之陶瓷）外，8種供第七測量用之陶瓷 係以前述[1 ]，（ 7)之相同方式製造。然後遵照相同方式測 量抗彎強度，結果共同顯示於表9。 (4 )實施例1 2至2 0之效果 由表9結果可知，實施例1 3至2 0各自可於低抵9 0 0 °C 之低溫燒結。另一方面，於實施例1 2中，因玻璃與無機塡 料之比値非屬本發明之範圍，故於燒結期間出現氣泡，實 施例1 1之產物無法用作爲介電陶瓷。 只含玻璃之情況下，ε I*通常約爲6。相反地，無機塡料 爲鋅尖晶石塡料及鈦氧塡料製成之介電陶瓷（實施例〗3至 1 7、1 9及2 0)之ε 1·高達9.3至1 0.5。此外，r f之絕對値 小，-16至-2 ppm/°C。另一方面，於無機塡料爲鋅尖晶石 塡料及鈦酸鈣塡料之介電陶瓷（實施例18)之例中，ε r高 達1 0.7，同時r f也具有7 p p m / °C之小絕對値。 於無機塡料爲鋅尖晶石塡料以及鈦酸鈣塡料之介電陶 瓷案例，可提供1 65 MPa之抗彎強度。特別，於無機塡料 爲鋅尖晶石塡料及鈦氧塡料之介電陶瓷案例，可提供1 8 0 至2 2 0 MPa之絕佳抗彎強度。 40 312/發明說明書(補件)/92-04/92102639 1243805 以陶瓷總量爲1 0 0 w t %爲例’鉢尖晶石塡料以及纟太氧士冒 料之含量共計41至47 wt% ;此外於鋅尖晶石塡料（mG)及 欽氧塡料（m T )之m T / m G爲0 · 7 1至0 · 7 6之例中，可見陶瓷 可維持ε r高達1 〇 · 1至1 〇 ·4，而τ f被壓抑至極小値，_ 5 至-2 ppm/°C，同時仍維持抗彎強度高達190至193 MPa。 本案係基於日本專利申請案 JP 2002- 1 4 5 406，申請日 2002 年 5 月 20 日、JP 2002-145407，申請日 2002 年 5 月'画 爝 * NS 馏 讲 _ # 」Chang OO ^^ L 6e9s l &N; N6 / s- (N6 / ff) si) _s ^^^ / (Nl e 1243805 (5) / 第 = Measurement of thermal expansion coefficient) Manufacture of ceramics and measurement of thermal expansion coefficient such as ± (3) 11 kinds of green sheets manufactured by stamping into a predetermined configuration, 20 sheets are stacked by thermocompression bonding method, sintered at 9 0 (TC 15 minutes to manufacture ceramics. The ceramics are polished to become 3 mm X 3 mm X 1.6 mm pipe columns, and 11 types of ceramics for the second measurement are manufactured. The ceramics for the second measurement are used to take advantage of differential expansion heat The machine analysis device (model "TMA8 140D" manufactured by Rigaku International Co., Ltd.) measured the thermal expansion coefficient from 25 t to 40 (rc. The results are shown in Table 8.) (6) The third measurement (for measuring simultaneous sintering properties) Evaluation of ceramic manufacturing and simultaneous sintering properties I. A kind of green sheet manufactured as above (3) is printed at a predetermined position using a silver paste with a thickness of 15 microns. On the silver paste layer, other green sheets are laminated by thermocompression bonding. Sheets 'Similarly, silver paste is printed on other green sheets, and this process is repeated' A total of 5 green sheets are laminated, An unsintered laminate was obtained and printed with a silver paste in a predetermined pattern between the layers. The unsintered laminate was punched to a diameter of 4 cm and sintered at 900 ° C for 15 minutes. This was done in 1 configuration Low-resistance conductor ceramic for third measurement. 1 1 Ceramic for third measurement is laid on the plane, and the difference between the maximum position and the minimum position (contact position with the plane) from the plane is measured, if the difference is less than 50 microns (Not distorted to a practical level) or no distortion occurs, it is marked as' distortion exceeding 50 microns and marked as' X 'and shown in Table 8. (7) Manufacture of ceramics for the fourth measurement (bending strength measurement) and As for the bending strength evaluation, for example, in the green sheet manufactured in (3) above, corresponding to 312 / Invention Specification (Supplement) / 92-04 / 92102639 36 1243805 of the green sheet in accordance with Examples 1, 2, 3, and 4 is scheduled to be punched. Configuration, 11 pieces of green sheets were stacked by thermocompression bonding method, and sintered at 900 ° C for 15 minutes to produce ceramics. The ceramics were polished to become 4 mm X 3 mm X 36 mm tube columns, and 3 kinds of supply were made. The fourth measuring ceramic. By using The fourth measurement ceramic was used to measure its flexural strength (3-point bending). The results are shown in Table 8. (8) Effects of Examples 1 to 10 The results are shown in Tables 6 to 8. Each of Examples 4 to n can be measured. Sintered at a low temperature of 90 ° C and showed a certain degree of dielectric properties. However, some showed that the dielectric ceramics were distorted due to poor thermal properties of glass frit, some failed to provide sufficient dielectric properties, and others were due to sintering. As a result, migration of low-resistance conductors, or some of them fail to provide sufficient bending strength. None of these embodiments has a sufficiently good balance with individual characteristics. On the other hand, Examples 1 to 3 of the product of the present invention can be sintered at the same time as a low-resistance conductor or at 900 ° C, and show good dielectric properties (dielectric loss: 30 to 39 X 1 0 · 4, ε r · · 7.5 to 7.6, and flexural strength: 2 60 to 2 70 MPa). In addition, no migration of the components constituting the low-resistance conductor was observed, and no warping of the substrate was observed. It was found that a sufficiently high bending strength was obtained. In addition, the coefficient of thermal expansion is 5.3 to 5.4 p p m / ° C, which shows suitable characteristics as a wiring substrate. [4] The use of dielectric ceramics (1) without alkali metal elements and glass containing zinc spinel frit (1) The manufacture of ceramics for the fifth measurement (measurement of dielectric properties) and the measurement of dielectric properties are as above [ 1], (1) No. 1, 2 and 3 glass manufactured as glass powder, and zinc spinel powder, titanium oxide powder and calcium carbonate powder as inorganic filler, these materials are combined in the ratio shown in Table 9 And mixed, and made a green sheet as shown in [1], 37 312 / Invention Specification (Supplement) / 92-04 / 92102639 1243805 (3). Subsequently, similar to the above [1], (4) was sintered and polished to produce 9 ceramics for the fifth measurement. Among the manufactured dielectric ceramics, except for Example 12 where bubbles were generated during sintering, the remaining 8 types of dielectric ceramics were measured in a manner similar to the above [1], (4) at a relative dielectric constant ε r of 3 GHz. And the temperature coefficient of resonance frequency rf at 25 to 80 ° C. The results are collectively shown in Table 9. 38 312 / Instruction of the Invention (Supplement) / 92-04 / 92102639 1243805 6 Characteristics of dielectric ceramic B 1 (MPa) 1 丨 Bubble during sintering 180 (N rH m 〇 \ r— ^ r— < 222 r— H 5: Twist 1 ◎! 〇 ◎ ◎ ◎ ◎ ◎ V- S 〇, 3 00 cn (N uo rH 1 bu to ar (3GHz) I _ 10 · 4 1 Ll0 · 4 JL ·! 0.1 J Os 10.7 1 10.5 rH 〇 Dielectric ceramic composition inorganic filler (wt%) tH * rH (N rH Type • Proportion (weight) mT / mG 0.86 1 ° · 91 1 1 ° · 71 1 0.76 0.74 丨 0 · 42 1 1 0.75 1 Snake 1 1 CaTi03 20 Titanium Oxide ▼ —4 On t—i Inch 1 〇〇〇 Spinel 00 f— ^ in (N mm Ό (N glass (wt%) 00 * Os ON m to m) 00 in Glass number rH rH ▼ —H rH t—H rH < N < (N rH * m inch rH in ▼ —H Ό00 rH Cn II FREE 1- <. "Band § | "Changshu. 纟, 6« 1243805 (2) The manufacture of ceramics for the sixth measurement (measurement of simultaneous sintering properties) and the evaluation of simultaneous sintering properties are similar to the aforementioned [1], (6) measuring distortion, according to the same evaluation reference, "◎" or "X" is shown in Table 9. (3 ) For the manufacture of ceramics for the seventh measurement (measurement of flexural strength) and the comparison of flexural strength, in addition to using the aforementioned green sheets of [2], (1) (which can be manufactured as above [2], (1) In addition to ceramics that do not bubble or warp), 8 types of ceramics for the seventh measurement are manufactured in the same manner as in [1], (7) above. Then the flexural strength is measured in the same manner. The results are shown in Table 9 together. (4) Effect of Examples 12 to 20 From the results in Table 9, it can be known from Examples 9 to 20 that each of Examples 13 to 20 can be sintered at a low temperature as low as 900 ° C. On the other hand, in Example 12 Because the ratio of glass to inorganic materials is outside the scope of the present invention, bubbles appear during sintering, and the product of Example 11 cannot be used as a dielectric ceramic. In the case of glass only, ε I * is usually about 6. Conversely, the inorganic materials are dielectric ceramics (Examples 3 to 17, 19, and 20) made of zinc spinel materials and titanium oxide materials with ε 1 · up to 9.3 to 1 0.5. In addition, the absolute value of r f is small, from -16 to -2 ppm / ° C. On the other hand, in the case of a dielectric ceramic (Example 18) in which the inorganic material is a zinc spinel material and a calcium titanate material, ε r is as high as 10.7, and rf is also as small as 7 ppm / ° C. Definitely. In the case of dielectric ceramics in which the inorganic material is zinc spinel material and calcium titanate material, it can provide a bending strength of 1 65 MPa. In particular, in the case of dielectric ceramics in which the inorganic material is zinc spinel material and titanium oxide material, it can provide excellent bending strength of 180 to 220 MPa. 40 312 / Instruction of the Invention (Supplement) / 92-04 / 92102639 1243805 Take the total ceramic content as 100 wt% as an example. The content of the bowl spinel spice and the phoxite material are 41 to 47 wt%. In addition, in the case where the m T / m G of the zinc spinel aggregate (mG) and the zinc oxide aggregate (m T) is 0 · 7 1 to 0 · 76, it can be seen that the ceramic can maintain ε r as high as 1 〇 · 1 to 1 · 4, while τ f is suppressed to extremely small 値, 5 to -2 ppm / ° C, while still maintaining flexural strength as high as 190 to 193 MPa. This case is based on Japanese patent application JP 2002- 1 4 5 406, filed May 20, 2002, JP 2002-145407, filed May 2002
20 日、JP 2002-145408，申請日 2002 年 5 月 20 日、JP 2002-145409，申請日 2002 年 5 月 20 日、JP2001-232544, 申請日2001年7月31日、JP 2001-232545，申請日2001 年7月31日、JP2001-232546，申請日2001年7月31日 及JP 2001-232547，申請日2001年7月31日，各案內容 以引用方式倂入此處。 41 312/發明說明書(補件)/92-04/9210263920th, JP 2002-145408, application date May 20, 2002, JP 2002-145409, application date May 20, 2002, JP2001-232544, application date July 31, 2001, JP 2001-232545, application July 31, 2001, JP2001-232546, application date July 31, 2001 and JP 2001-232547, application date July 31, 2001, the contents of each case are hereby incorporated by reference. 41 312 / Invention Specification (Supplement) / 92-04 / 92102639