TW200306963A - Dielectric ceramic - Google Patents
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- TW200306963A TW200306963A TW92102639A TW92102639A TW200306963A TW 200306963 A TW200306963 A TW 200306963A TW 92102639 A TW92102639 A TW 92102639A TW 92102639 A TW92102639 A TW 92102639A TW 200306963 A TW200306963 A TW 200306963A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 177
- 239000011521 glass Substances 0.000 claims abstract description 150
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 49
- 238000005245 sintering Methods 0.000 claims abstract description 46
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000011256 inorganic filler Substances 0.000 claims abstract description 23
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 23
- 229910052796 boron Inorganic materials 0.000 claims abstract description 21
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 17
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 17
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 239000011701 zinc Substances 0.000 claims description 52
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 43
- 239000011029 spinel Substances 0.000 claims description 39
- 229910052596 spinel Inorganic materials 0.000 claims description 39
- 239000013589 supplement Substances 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 33
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 25
- 229910010272 inorganic material Inorganic materials 0.000 claims description 22
- 239000011147 inorganic material Substances 0.000 claims description 22
- 239000011575 calcium Substances 0.000 claims description 21
- 238000005452 bending Methods 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 230000009477 glass transition Effects 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 3
- 239000011368 organic material Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 73
- 239000004020 conductor Substances 0.000 abstract description 22
- 229910052751 metal Inorganic materials 0.000 abstract description 15
- 239000002184 metal Substances 0.000 abstract description 15
- 150000002739 metals Chemical class 0.000 abstract description 7
- 239000011812 mixed powder Substances 0.000 abstract description 6
- 239000011230 binding agent Substances 0.000 abstract description 4
- 239000000945 filler Substances 0.000 abstract description 4
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 229910001676 gahnite Inorganic materials 0.000 abstract 1
- 238000005259 measurement Methods 0.000 description 54
- 238000004519 manufacturing process Methods 0.000 description 25
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 19
- 239000004332 silver Substances 0.000 description 19
- 229910052709 silver Inorganic materials 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 12
- 230000005012 migration Effects 0.000 description 9
- 238000013508 migration Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 229910001316 Ag alloy Inorganic materials 0.000 description 5
- 229910011255 B2O3 Inorganic materials 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 239000010433 feldspar Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000010345 tape casting Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052839 forsterite Inorganic materials 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 241000270295 Serpentes Species 0.000 description 1
- 229910010269 TiOb Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 239000005407 aluminoborosilicate glass Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052849 andalusite Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910052637 diopside Inorganic materials 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- KUVFGOLWQIXGBP-UHFFFAOYSA-N hafnium(4+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[Ti+4].[Hf+4] KUVFGOLWQIXGBP-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229910001720 Åkermanite Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
200306963 玫、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 GHz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 之電子元件、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 5〇〇至8 00°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： 隹呂氧、富銘紅柱石、堇青石、欽氧、鎂橄欖石、錯氧及石 英）。 此等介電陶瓷係揭示於JP-A-53-60914、JP-A-60-235744 、JP-A-63-239892、 JP-A-3-33026、 JP-A-7-135379 及 JP-A-9-20 8 2 5 8。此等介電陶瓷之介電耗損於百萬赫茲（MHz)爲6 X 1 0 ·4 至 2 0 X 1 (T4。 312/發明說明書(補件)/92-04/92102639 200306963 近年來特別要求於使用逐漸增加之GHz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 G Η z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G Η ζ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 00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 及含有至少一種鹼金屬Li、Na及K總量爲0.2至5 wt%。 此外，本發明之介電陶瓷可讓於3 GHz之介電耗損爲50 X 10_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 ppm/°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 200306963 (2) 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（亦即介電陶瓷組成物），該組成物 含有無機塡料及玻璃，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80 wt%;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: 10 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1〇〇 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 30wt%，A1: 20 至 30wt%，Ca: 10 至 20wt%， 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100 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%，Zn: 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 10_4 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 200306963 本發明之介電陶瓷可讓於25至40(TC之熱膨脹係數爲5 至 1 0 p p m / °C。 本發明之介電陶瓷可獲得抗彎強度爲185 MPa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Tg與彎曲溫度Mg間之差異爲30至45 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。 前述「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、鎂橄攬石、瓦碟石（wallastonite)、銘灰長石、頑灰 石、透輝石、鎂黃長石（akermanite)、錦黃長石及尖晶石。 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“ δ 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、銷氧及鋁 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 200306963 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7： 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+鋁 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（G Η z區段）獲得大ε r以及獲得小絕對値 r f 〇 當無機塡料與玻璃之總量爲100 wt%時，無機塡料含量 爲20至60wt%(更佳30至60wt%及又更佳40至55wt%)。 若無機塡料之含量低於20 wt%，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 〇〇〇。<3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 〇〇 wt%)。當總 量低於5 0 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m T (以質量（亦即重量）表示）對鋅尖晶 石含量mG(以重量表示）之比，mT/mG比較佳爲〇. 1至1 .5， 更佳爲0 · 4至1 _ 0 ’又更佳爲0 · 6至0 · 9。若m T / m G比小於 〇· 1，則難以獲得將τ 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 200306963 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、尖晶石及鋅尖晶石）。 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 wt%時，玻璃爲40至80 wt%(較佳40至70 wt%，又更佳 5 0至ό 0 w t % )。若玻璃含量低於4 0 w t %，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 i•非期望地過小。 本發明之一具體實施例，玻璃含有驗金屬元素，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Si，B， Al，Ca及Zn以及X化合物獨立無關，si係以Si〇2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 200306963 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。 本發明之一具體貫施例中’當玻璃不含驗金屬元素時， 目U述以「以氧化物表不」一詞係與玻璃中存在何種S i, B， Al，Ca及Zn獨立無關，Si係以Si02計算，B係以B2〇3計 昇’ A1係以AI2O3S十算，Ca係以CaO計算，Zn係以ZnO 計算。 若玻璃總量爲1 〇 〇 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ε 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 200306963 特別不利，因而可有效防止發生扭曲。經由含有2 0至3 0 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，可有效避免 介電陶瓷熔化及溶蝕。 此外，以氧化物表示，銘含量爲2 〇至3 0 w t % (更佳2 1 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1〇至20 wt%(更佳12至20 wt%，以及又更佳15至18 wt%)。鈣含量低於10 wt%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1〇至20 wt%(更佳10至18 wt%，及又更佳1 1至16 wt%)。鋅含量低於10 wt%，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含量爲〇·2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 200306963 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 w t % (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， 石夕含量爲20至27wt%，硼爲10至30wt%，錦爲21至29 wt%，銘爲12至20wt%，鋅爲10至18wt%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 wt%，鋁爲 22 至 26 wt%，鈣爲 1 5 至 1 8 wt°/〇，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27wt %，硼爲10至30 wt%，鋁爲21至29 wt%，鈣爲12至20 wt%以及鋅爲10至1 8 wt%。此外，也 可矽含量爲21至25 wt%，硼爲15至30 wt%，鋁爲22至 312/發明說明書(補件)/92-〇4/92102639 200306963 2 6 w t %，鈣爲1 5至1 8 w t %以及鋅爲1 1至1 6 w t %。 根據本發明之介電陶瓷，於1至15 GHz(特別3至10 GHz) 之介電耗損爲50 X 10·4或以下（此外爲40 X 1(Γ4或以下， 特別爲30 X 1(Γ4或以下以及通常爲20 X 1(Γ4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er 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 1*變低。若ε I·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 10ppm/°C (此外-10 至 l〇ppm/°C，特別-10 至5 ppmTC )。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 312/發明說明書(補件)/92·04/92102639 200306963 通濾波器，因而電性可靠度降低。因此考慮於GHz區段之 應用，τ 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G Η z區段。 此外，由25 °C至4 00 °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厂C，作爲1C之半導體元件之熱膨脹係 數爲約3至4 p p m广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 Γ爲6至13， τ f爲-20至10 PPm/°C，於25至40 0°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“或以下，ε 1爲7至13, r f爲-10至10 ppm/ °C，於25至40(TC之熱膨脹係數爲5至10 PPm/°C以及抗 彎強度爲180 MPa或以上。 312/發明說明書(補件)/92-04/92102639 200306963 特別若含有鋅尖晶石塡料及鈦氧塡料二者作爲 時，可獲得介電陶瓷，此處於3至1 〇 GHz之ε r怎 τ f爲-15至Oppm广C以及抗彎強度爲i80MPa。 有鋅尖晶石塡料及鈦氧塡料二者，且無機塡料與 量爲1 0 0 w t %，讓無機塡料爲3 0至6 0 w t %，則 電陶瓷，此處於3至10 GHz之ε r爲1〇至13， 至0 ppm/°C以及抗彎強度爲190 MPa或以上。 若含有鋅尖晶石塡料及鈦氧塡料二者作爲無機 無機塡料與玻璃之總量爲1 00 wt%，讓無機塡料 60 wt%，以及mT/mG爲0.6或以上，則可獲得介 此處於3至10 GHz之er爲10至13，τί*爲-3 °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 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， 用下列方法。換言之，本發明之一具體實施例中 含有鹼金屬元素時，介電陶瓷組成物之獲得方式 料無機塡料粉末與玻璃粉末，以及於100(TC或以 燒結，其中當玻璃粉末總量爲100 wt%時，分別 表示，Si:20 至 30wt%，B:5 至 30wt%，Al:20 至 Ca: 1 0 至 20 wt%，Zn: 10 至 20 wt%，以及至少 屬：Li、Na及K總量爲0.2至5 wt% ;當無機塡 玻璃粉末總量爲1〇〇 wt %時，無機塡料粉末占20 : 以及玻璃粉末占40至80 wt%。 312/發明說明書(補件)/92-04/92102639 |無機塡料 ! 9 至 13， 此外若含 玻璃之總 可獲得介 τ f 爲-1 5 塡料，且 •爲30至 ‘電陶瓷， 至 0 ppm/ 抗彎強度 例如可採 ，當玻璃 係經由混 下之溫度 以氧化物 3 0 w t %， 一種驗金 料粉末與 至 6 0 w t % 200306963 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 0 0 0 °c或以下之溫度燒結，其中 當玻璃粉末總量爲1 0 0 wt %時，分別以氧化物表示，s i: 2 0 至 30 wt%，B: 5 至 30 wt%，A1: 20 至 30 Wt%，Ca: 1〇 至 20wt°/。，Ζιι: 10至20wt%，以及鹼金屬不含Li、Na或K; 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 〇微米爲 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 〇微米’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 200306963 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5 70至660°C，又更佳爲5 7 0至640t)。 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 0至7 0 w t %)。較佳希望其混合 量爲無機塡料粉末占4 0至6 0 w t % (玻璃粉末占4 0至6 0 wt%) ’及更佳占45至55 wt°/〇(玻璃粉末占45至55 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、發液及 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 200306963 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1 000°C或以下之溫度進行（通常爲7 5 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980°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 Si02、B2〇3、Al2〇3、CaO、ZnO、Na2C03& K2c〇3 粉末外，MgO、BaO、SrO及ZrO粉末以表i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，投挪入 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 0種玻璃粉（1至i 0號玻璃），具有 平均直徑爲3微米。 312/發明說明書(補件)/92-(M/92102639 200306963 £ 介電陶瓷 % m 銘氧 (wt%) 玻璃 (wt%) 組成(Wt%) Η Zr02 I 1 1 cn 1 s d 1 I 1 1 r-H Ο ΌΟ I d r- d 1 9 PQ 卜 ό m 〇\ MgO 1 1 寸 d ΠΊ d (N T—H 鹼金屬 Na20 Na2〇 o 1 * Na20 慕 * 〇 (N 1 * 1 * Na20 1 * CN rn m (N T-H m d 寸 T~( 〇 r-H r-H t—H 1 * 1 * 1 * 1 * 1 * 1 * U v〇 1 * 1 * | *0.15 | 卜 r-H r-H 1 * C\ 00 Al2〇3 艺 Os VO 5Γ· m rn r—H * <N oo (N CN 00 (N Β2〇3 00 … (N | *45.5 1 卜 Ό rn 00 CN (N 卜· 00 <Ν ο 另 to 00 <N JO (N ro (N cn (N (N ΓΟ * 玻璃 編號 r-H (N fp up vp tp 00 Cs o f—^ * < r-H (N rp 7 OO o r-H * ττ MSN^鏹讲釀铢」长^iL螩 ί0 .· < 6e9s l(N6l-(N6/ffsi)_w^咳sii/ZI e 200306963 (2)玻璃粉之Tg及Mg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 TG810D」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 "生 編號 Tg(°c ) MgfC ) Mg-Tg(t：) 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（DBP)} 及溶劑（甲苯），且混合而製備1 0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 23200306963 Description of 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 GHz region. 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 as electronic components, packages or multilayers for high-frequency use in the GHz band 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 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 as The main aluminoborosilicate glass powder) and (inorganic materials: Pyrox, Fuming Andalusite, Cordierite, Qin Oxygen, Forsterite, Oxygen and Quartz). These dielectric ceramics are 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-9-20 8 2 5 8. The dielectric loss of these dielectric ceramics is in the range of 6 X 1 0 · 4 to 2 X 1 (T4. 312 / Invention (Supplement) / 92-04 / 92102639 200306963 in recent years. Dielectric loss reduction in the use of gradually increasing GHz bands. Therefore, dielectric ceramics are required which can be sintered simultaneously with low resistance conductors of silver-based metals or copper-based metals, high mechanical strength, and sintered products Less distortion, bending or warping (occasionally referred to as "distortion" in this description) (reduction of distortion will improve dimensional stability and suppress transmission loss during use in the GHz band). However, it is difficult to achieve low temperature insulation at the same time. Advantages of good sintering properties and mechanical strength, as well as excellent dielectric properties in the G 区段 z section. [Summary of the Invention] The present invention is to solve the aforementioned problems, so one object of the present invention is to provide simultaneous sintering, mainly silver. Low-resistance conductors of metals and copper-based metals, dielectric ceramics with excellent mechanical strength and excellent dielectric properties in the G Η ζ section. (1) The dielectric ceramics of the present invention contain an inorganic 塡Glass and glass The characteristic is that when the total amount of inorganic filler and glass is 100% by mass (ie, weight percentage), 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 At 100 wt%, it contains (expressed as oxides) 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 0.2 to 5 wt% containing at least one alkali metal Li, Na, and K. In addition, the dielectric ceramic of the present invention allows the dielectric loss at 3 GHz to be 50 X 10_4 Or below, the relative dielectric constant at 3 GHz is 6 to 13, and the coefficient of thermal expansion at 25 to 400 ° C is 5 to 10 ppm / ° C, and the flexural strength (or flexural strength) is 185 MPa or more 312 / Invention Specification (Supplement) / 92-04 / 92102639 200306963 (2) The dielectric ceramic of the present invention is a composition for a dielectric ceramic (that is, a dielectric ceramic) which is sintered at 1 000 ° C or below Composition), the composition contains 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 the inorganic filler 20 to 6 0 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 wt%, B: 5 to 30 wt%, A1: 20 to 30 wt%, Ca: 10 to 20 wt%, Zn: 10 to 20 wt% and a total content of at least one alkali metal Li, Na, and K of 0.2 to 5 wt%. (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 The glass is 40 to 8 Owt%; and when the total amount of the glass is 100 wt%, it contains (represented by oxides respectively) Si: 20 to 30 wt ° /. , B: 5 to 30% by weight, A1: 20 to 30% by weight, Ca: 10 to 20% by weight, Zn: 10 to 20% by weight without Li, Na, and 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 (represented by oxides, respectively) ) Si: 20 to 30% by weight, B: 5 to 30% by weight, and Al: 20 to 30% by weight. , Ca: 10 to 20 wt%, Zn: 10 to 20 wt% and does not contain Li, Na, K. The dielectric ceramic of the present invention can obtain a dielectric loss at 3 GHz of 50 × 10_4 or less. The dielectric ceramic of the present invention can obtain a relative dielectric constant of 6 to 13 at 3 GHz. 312 / Instruction of the Invention (Supplement) / 92-04 / 92102639 200306963 The dielectric ceramic of the present invention can be made to 25 to 40 (the coefficient of thermal expansion of TC is 5 to 10 ppm / ° C. The dielectric ceramic of the present invention can be obtained The flexural strength is 185 MPa or more. The inorganic aggregate may contain zinc spinel aggregate (an aggregate consisting of spinel) and titanium oxide aggregate (an aggregate containing titanium oxide). Glass transition temperature Tg and bending temperature The difference between Mg is 30 to 45 t. The dielectric ceramic according to the present invention can provide a low-resistance conductor with a dielectric property and can simultaneously sinter a silver-based metal and a copper-based metal, and has excellent mechanical properties. Strength and excellent dielectric properties. [Embodiment] The present invention will be described in detail. The aforementioned "inorganic filler" depends on the type and content of the filler, and the dielectric and mechanical characteristics of the dielectric ceramic can be changed. As for the composition The material properties of inorganic materials include, for example, zinc spinel, titanium oxide, aluminum oxide, titanates (magnesium titanate, calcium titanate, hafnium titanate, barium titanate), mullite, chromium oxide, quartz, Cordierite, forsterite, waltite ( wallastonite), ash feldspar, refractory feldspar, diopside, akermanite, golden yellow feldspar and spinel. Among them, in order to change the relative permittivity of the high frequency section (particularly the GHz section) (Referred to as "δ r") becomes larger, preferably zinc spinel, titanium oxide, titanate, and aluminum oxide. In order to improve mechanical strength, zinc spinel, titanium oxide, pin oxygen, 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 200306963 Make it low (control rf absolute 値 to be small) number 値 ' Inorganic materials with negative 値 rf and inorganic materials with positive 値 7: f can be used. The combinations are, for example, spinel + titanium oxide, spinel + titanate, alumina + titanate, and spinel. Stone + aluminum oxide + titanate. The combination of spinel and titanium oxide materials shows sufficient mechanical strength. Large ε r and small absolute 値 rf can be obtained in the high-frequency region (G Η z section). When the total amount of inorganic filler and glass is 100 wt%, the content of inorganic filler is 20 to 60 wt% (more 30 to 60 wt% and more preferably 40 to 55 wt%). If the content of the inorganic aggregate is less than 20 wt%, the glass melts 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. ≪ 3, and it is impossible to complete sintering together with the low-temperature resistance conductor at the same time. When the spinel aggregate and the titanate aggregate are used in combination, the total amount of the spinel aggregate and the titanate aggregate accounts for 50% or more of the total amount of the inorganic aggregate (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 titanium oxide content m T (expressed by mass (that is, weight)) to the zinc spinel content mG (expressed by weight), mT / mG is preferably from 0.1 to 1.5, and more preferably 0 · 4 to 1 _ 0 'and more preferably 0 · 6 to 0 · 9. When the m T / m G ratio is less than 0.1, it is difficult to obtain the effect of suppressing the absolute value of τ f to a smaller value. 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 200306963 is 1 to 10 microns (taking granular inorganic aggregate as an example, using average diameter). 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 during the manufacture of the dielectric ceramics when they are added, including the inorganics precipitated as crystals when they are added in the form of glass powder during manufacture. Concrete (calcium feldspar, spinel and zinc 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 6 wt%). If the glass content is less than 40 wt%, it is difficult to reduce the sintering temperature to less than 1000 ° C. When it exceeds 80 wt%, the mechanical strength is reduced, and the dielectric characteristics in the high-frequency region are also insufficient. . In particular, ε i is undesirably too small. In a specific embodiment of the present invention, the glass contains a metal detection element, and the glass contains at least one of silicon, boron, aluminum, calcium, and zinc, and at least one alkali metal element of lithium, sodium, and potassium (after (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 term "expressed as an oxide" is independent of what Si, B, Al, Ca, Zn, and X compounds are present in the glass, si The calculation is based on SiO2, the B calculation is based on B203, the A1 calculation is based on Al203, the Ca calculation is based on CaO, the Zn calculation is based on ZnO, and the X system is calculated as χ20. In a specific embodiment of the present invention, when the glass does not contain an alkali metal element, 312 / Invention Specification (Supplement) / 92-04 / 92102639 200306963 The glass contains at least silicon element, boron element, aluminum element, calcium element and zinc element . 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 metal detection elements, the term "represented by oxides" is independent of what Si, B, Al, Ca, and Zn are present in the glass. Regardless, the Si system is calculated as SiO2, the B system is calculated as B203, the A1 system is calculated as AI2O3S, the Ca system is calculated as CaO, and the Zn system is calculated as ZnO. 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%, and 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 simultaneous sintering with the low-resistance conductor are insufficient, which may cause undesired distortion, and ε r 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, it becomes difficult to sinter at the same time as a low-resistance wire. 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 at the same time as the low-resistance conductor are insufficient, 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 of 750 ° C to 95 ° C during manufacturing. In addition, in addition to the foregoing, the simultaneous sintering properties with low-resistance conductors by containing 15 to 30 wt% of boron become particularly disadvantageous 312 / Invention Specification (Supplement) / 92-04 / 92102639 200306963, which can effectively prevent distortion. By containing 20 to 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, the dielectric ceramic can be effectively avoided from melting and dissolving. . In addition, the oxide content is 20 to 30 wt% (more preferably 21 to 29 wt% and still more preferably 22 to 26 wt%). If the aluminum content is less than 20 wt%, the mechanical strength of the dielectric ceramic cannot be sufficiently obtained, and especially when the aluminum content is less than 10 wt%, the stability of the glass is undesirably destroyed. On the other hand, when it exceeds 30 wt%, the sintering temperature becomes excessively 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 calcium 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 too 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 damaged. On the other hand, when the content exceeds 5 wt%, the glass transition temperature may be lowered, 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 200306963 However, if a low-resistance conductor of a multilayer wiring substrate is used as a metal mainly composed of silver, it is desirable that it does not contain lithium. Therefore, the migration of silver can be extremely effectively suppressed. The fact that "the glass in one embodiment of the present invention does not contain an alkali metal element" 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 the 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 extremely thin, it is preferable 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 stone content is 20 to 27 wt%, boron is 10 to 30 wt%, brocade is 21 to 29 wt%, and the inscription 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 ° / 〇, 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%, boron is 10 to 30 wt%, aluminum is 21 to 29 wt%, calcium is 12 to 20 wt%, and Zinc is 10 to 18 wt%. In addition, the silicon content is 21 to 25 wt%, boron is 15 to 30 wt%, aluminum is 22 to 312 / Invention Specification (Supplement) / 92-〇4 / 92102639 200306963 2 6 wt%, and calcium is 1 5 To 18 wt% and zinc to 11 to 16 wt%. According to the dielectric ceramic of the present invention, the dielectric loss at 1 to 15 GHz (particularly 3 to 10 GHz) is 50 X 10 · 4 or less (otherwise 40 X 1 (Γ4 or less, especially 30 X 1 (Γ4 Or below and usually 20 X 1 (Γ4 or above). Generally, the dielectric loss becomes larger as the frequency of use becomes higher. However, in the dielectric ceramic of the present invention, the dielectric loss of the GHz section can be controlled as described above. Is small. This dielectric loss can be changed not only by the glass composition, but also by the inorganic material. In this way, the dielectric loss can be changed by the composition, the amount of the inorganic material added during manufacture, and the sintering conditions such as temperature adjustment. In the present invention, As the evaluation of high-frequency dielectric characteristics, the dielectric characteristics obtained at 3 GHz are representative of the measurement and evaluation of dielectric characteristics. The reason for choosing 3 GHz is that 3 GHz is a commonly used segment in wireless sector networks (LANs). (Such as 2.4 to 2.5 GHz), and it is easy to compare and evaluate with existing products. In addition, it is possible that the er is 1 to 15 GHz (usually 3 to 10 GHz) is 6 to 13 (in addition, 7 to 13, especially 9) To 13). Generally, ε 1 * becomes lower as the use frequency becomes higher. If ε I is too small, the dielectric ceramic must be It can only be used in the GHz section if it is made into a large size, which makes it difficult to reduce the size. Therefore, considering the use of the GHz section, it is better to make ε r larger, so the miniaturization of various electronic components can also be applied to the GHz Segment. Rf (temperature range: 25 to 80 ° C) at 1 to 15 GHz (especially 3 to 10 GHz) is -20 to 10 ppm / ° C (other than -10 to 10 ppm / ° C, especially -10 Up to 5 ppmTC). Generally, as the frequency of use increases, the absolute value of the temperature coefficient of the resonance frequency increases toward the negative direction. If the absolute value increases toward the negative direction, it is difficult to support the substrate when used as a package substrate. The 312 / Invention Specification (Supplement) / 92 · 04/92102639 200306963 pass filter is included therein, so the electrical reliability is reduced. Therefore, considering the application in the GHz range, the absolute value of τ f is preferably small, so The stable operation of a variety of electronic components can also be applied to the G Η z section. In addition, it is possible to increase the coefficient of thermal expansion from 25 ° C to 400 ° C to 5 to 10 ppm / ° C. Usually used in recent years The thermal expansion coefficient of the printed wiring board is about 13 to 14 ppm factory C, as the thermal expansion of 1C semiconductor components The coefficient is about 3 to 4 ppm wide 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, and the dielectric ceramic of the present invention can satisfy this In addition, the flexural strength is 160 MPa or more (other than 180 MPa or more, especially 190 MPa or more). If the flexural strength is 160 MPa or more, the problem of cracking due to impact can be overcome when the multilayer wiring board or electronic component product made of the dielectric ceramic of the present invention is dropped. Multilayer wiring Substrates or electronic components are brazed with metal (such as sealing rings for electromagnetic shielding) to overcome cracks 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 Γ is 6 to 13, and τ f is -20 to 10 PPm / ° C, with a thermal expansion coefficient of 5 to 10 ppm / ° C at 25 to 40 ° C and a flexural strength of 160 MPa or more. In addition, dielectric ceramics available here with a dielectric loss of 40 X 10 "or less at 1 to 15 GHz (especially 3 to 10 GHz), ε 1 is 7 to 13, rf is -10 to 10 ppm / ° C, 25 to 40 (TC has a thermal expansion coefficient of 5 to 10 PPm / ° C and a flexural strength of 180 MPa or more. 312 / Invention Specification (Supplement) / 92-04 / 92102639 200306963 Especially if it contains zinc spinel 塡Dielectric ceramics can be obtained when both the materials and titanium oxide materials are used, where the ε r at 3 to 10 GHz is -15 to 0 ppm wide C and the bending strength is i80 MPa. There are zinc spinel materials and For both titanium oxide materials, and the amount of inorganic materials is 100 wt%, and the inorganic materials are 30 to 60 wt%, then the ceramics, here ε r at 3 to 10 GHz is 10 to 13, to 0 ppm / ° C and flexural strength of 190 MPa or more. If both zinc spinel aggregate and titanate aggregate are used as the inorganic inorganic aggregate and glass, the total amount is 100 wt%. If the material is 60 wt%, and mT / mG is 0.6 or more, the er at 3 to 10 GHz is 10 to 13, τί * is -3 ° C, and the bending strength is 190 MPa or more. Dielectric loss of the invention, ε r τ f, the coefficient of thermal expansion and the same method are determined according to the measurement methods of the foregoing embodiments. The method for obtaining the dielectric ceramic of the present invention is not particularly limited, and the following methods are used. In other words, an embodiment of the present invention contains an alkali metal element At the time, the dielectric ceramic composition was obtained from inorganic powder and glass powder, and at 100 ° C or sintered, where when the total amount of glass powder was 100 wt%, respectively, Si: 20 to 30 wt%, B: 5 to 30% by weight, Al: 20 to Ca: 10 to 20% by weight, Zn: 10 to 20% by weight, and at least: Li, Na, and K total 0.2 to 5% by weight; when inorganic glass When the total amount of powder is 100 wt%, inorganic powder accounts for 20: and glass powder accounts for 40 to 80 wt%. 312 / Invention Specification (Supplement) / 92-04 / 92102639 | Inorganic materials! 9 to 13 In addition, if the total available media containing glass τ f is -1 5 塡, and • is 30 to 'electric ceramics, to 0 ppm / flexural strength can be used, for example, when the glass is mixed with the 30 wt%, a gold test powder with up to 60 wt% 200306963 In other words, one of the invention In a specific embodiment, when the glass does not contain 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 100 ° C or below. When the total amount of glass powder is 100 wt%, it is expressed as oxide, si: 20 to 30 wt%, B: 5 to 30 wt%, A1: 20 to 30 Wt%, and Ca: 10 to 20 wt °. /. , Zιι: 10 to 20% by weight, and the alkali metal does not contain Li, Na or K; when the total amount of the inorganic powder and glass powder is 100% by weight, the inorganic powder contains 20 to 60% by weight and the glass powder accounts for 40% To 80 wt%. As for the inorganic agglomerate powders mentioned in the present manufacturing method, the titanium oxide, aluminum oxide and chromium oxide powders made by sintering are respectively. They can be used individually or in combination. There is no particular limitation 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 present 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 the 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 smaller 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 there is a 312 / Invention Specification (Supplement) / 92-04 / 92102639 200306963 part of the powder precipitates in the dielectric ceramic and thus exists as glass. The glass transition temperature Tg of the glass powder is not particularly limited, but is preferably 560 to 670 ° C (more preferably 5 70 to 660 ° C, and still more preferably 5 70 to 640 t). In this range, the following properties can be advantageously maintained, and at the same time with low resistance conductors such as silver-based metals (single silver, Ag / Pd alloy, Ag / Pt alloy, Ag / Cu alloy, or Ag / Au alloy, etc.) Or the copper-based metal (copper alone 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, still 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 desirable 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 preferred 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 ° / 〇 (45 to 55 of glass powder wt%). The dielectric ceramic composition may be composed of inorganic powder and glass powder, and may contain, for example, a binder, a solvent, a plasticizer, and a dispersant in addition to these components. There are no particular restrictions on the properties of the dielectric ceramic composition, such as powders, hair fluids, and pastes. In addition, the dielectric ceramic composition can be formed from such powders, slurries, and 312 / Instruction Sheets (Supplements) / 92-04 / 92102639 200306963 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 performed at a temperature of 1 000 ° C or lower (usually 750 ° C or higher, more preferably 800 to 990 ° C, still more preferably 850 to 990 ° C, and particularly preferably 900 to 980 ° C). Above 1 000 ° C it is undesirably difficult to sinter with other low resistance conductors at the same time. 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 except SiO2, B2O3, Al2O3, CaO, ZnO, Na2C03 & K2c〇3 powder , MgO, BaO, SrO and ZrO powders were mixed at the ratios shown in Table i to prepare raw material powders. The prepared raw material powder is heated and melted, poured into water for rapid cooling, and granulated in water to obtain a glass frit. The glass frit was pulverized in a ball mill to produce 10 types of glass powder (glasses No. 1 to No. 0), having an average diameter of 3 microns. 312 / Instruction of the Invention (Supplement) / 92- (M / 92102639 200306963 £ Dielectric ceramic% m Ming oxygen (wt%) Glass (wt%) Composition (Wt%) Η Zr02 I 1 1 cn 1 sd 1 I 1 1 rH Ο ΌΟ I d r- d 1 9 PQ m m 〇 \ MgO 1 1 inch d Π d (NT—H alkali metal Na20 Na2〇o 1 * Na20 Mu * 〇 (N 1 * 1 * Na20 1 * CN rn m (N TH md inch T ~ (〇rH rH t—H 1 * 1 * 1 * 1 * 1 * 1 * U v〇1 * 1 * | * 0.15 | BU rH rH 1 * C \ 00 Al2〇3 art Os VO 5Γ · m rn r—H * < N oo (N CN 00 (N Β2〇3 00… (N | * 45.5 1 Ό rn 00 CN (N ·· 00 < N ο another to 00 < N JO (N ro (N cn (N (N ΓΟ * glass number rH (N fp up vp tp 00 Cs of— ^ * &r; rH (N rp 7 OO o rH * ττ MSN ^ 镪 Speaking of brewing baht) long ^ iL 螩 ί0. < 6e9s l (N6l- (N6 / ffsi) _w ^ sii / ZI e 200306963 (2) Measurement of Tg and Mg of glass powder as above (1) Tg and Mg of 10 glass powders manufactured It is measured by a differential thermal measuring device (model "THERMOFLEX TAS 300 TG810D" manufactured by Rigaku International Co., Ltd.), and individual 値 of Tg, Mg and Mg-Tg are shown in the table 2. Table 2 Thermal characteristics of glass dielectric ceramics Tg (° c) MgfC) Mg-Tg (t :) 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 Table 2 indicates "not within the scope of the present invention." (3) Health Manufacture of sheet material (dielectric ceramic composition) 10 to individual glass powders manufactured in the above (2) and aluminum oxide powders as inorganic aggregate powders were weighed to have a ratio of 50 wt% as shown in Table 1, And it mixes 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 knife coating method. The sintered sheet had a thickness of 1000 microns, and thus obtained 23
312/發明說明書(補件)/92-04/92102639 200306963 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 10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 0.63 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2 5 °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 (χ1(Γ4) (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 氺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)/92-〇4/92102639 200306963 如上（3)製造之10種生片材被沖壓成爲預定構形，20塊 片材透過熱壓連結法堆疊，於900 °C燒結15分鐘而製造陶 瓷。陶瓷接受拋光處理成爲3毫米x3毫米χ1·6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400t之熱膨脹係數。結 果共同顯不於表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 1〇種如上（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900 °C燒結15分鐘。如此製造10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 W發明說明書(補件)/92-〇4/921〇2639 200306963 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。312 / Invention Specification (Supplement) / 92-04 / 92102639 200306963 10 kinds of green sheets. (4) Manufacturing of ceramics for the first measurement (for measuring the dielectric characteristics) and measurement of the dielectric characteristics 10 kinds of green sheets manufactured as above (3) are punched into a predetermined configuration, and multiple sheets are passed through hot pressing A total of 10 pieces were connected and 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 Example of dielectric ceramic characteristics Dielectric loss (χ1 (Γ4) (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 氺 9 19 6.6 4.9 * 1 0 40 7.2 5.4 "" "is shown in Table 3 "Not within 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 / Invention (Supplement) / 92-〇4 / 92102639 200306963 As above (3 The 10 kinds of green sheets manufactured were stamped into a predetermined configuration. 20 sheets were stacked by thermocompression bonding and sintered at 900 ° C for 15 minutes to produce ceramics. The ceramics were polished to become 3 mm x 3 mm x 1.6 mm 10 kinds of ceramics for the second measurement were made in the column. Using the ceramics for the second measurement, the temperature was increased from 25 ° C to 400t by a differential expansion thermal machine analysis device (model "TMA8140D" Rigaku International Co., Ltd.) Thermal expansion coefficient. The results are not shown in Table 3. (6) The third measurement (for the same measurement Sintering properties) Evaluation of the use of ceramics and simultaneous sintering properties 10 kinds of green sheets manufactured as above (3) are printed at a predetermined position using a silver paste with a thickness of 15 micrometers. On the silver paste layer, it is connected by hot pressing. Laminate other green sheets, and similarly print silver paste on other green sheets. Repeat this operation. Five green sheets are laminated in total to obtain an unsintered laminate. Silver paste is used to print in a predetermined pattern between each layer. .The unsintered laminate was punched into a diameter of 4 cm and sintered at 900 ° C for 15 minutes. In this way, 10 kinds of ceramics equipped with low resistance conductors for the third measurement were manufactured. ① Evaluation of 10 kinds of distortion caused by sintering The third measurement of the manufactured ceramics is laid on a plane, and the difference between the maximum position and the minimum position (the position in contact with the plane) from the plane is measured. If the difference is less than 50 microns (not twisted to a practical degree) or no distortion occurs, it is marked as "◎", twisted more than 50 microns are marked as "X" and shown in Table 4. ② Silver migration due to sintering 10 kinds of ceramics manufactured for the third measurement are stacked in the stacking direction The cut and cut surfaces were analyzed by EPMA (electron probe microanalyzer). The result was found in the 25 W invention manual (Supplement) / 92-〇4 / 921〇2639 200306963 inside the ceramic. The migration of silver was found. "" The migration distance is 5 to 10 microns as "0", and the migration distance is more than 10 microns as "X", which are shown in Table 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 0片生片 材，且於900 °C燒結15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 60 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 200306963 (8)實施例1至10之效果 由表1至4結果，實施例3至1 〇各自可於9 〇 〇 °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〗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 1(Γ4，7.2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 ppm/°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[丨]，（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i 1於燒結時冒氣泡以及 貫施例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 200306963 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Table 4 Characteristics of the dielectric ceramics in the examples. Ag migration twisting 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 "outside the scope of the present invention". (7) For the manufacture of ceramics for the fourth measurement (bending strength measurement) and evaluation of the bending strength, for example, in the green sheet manufactured in (3) above, the green sheets corresponding to Examples 1, 2 and 4 are punched to be scheduled 10 ceramic sheets were stacked by thermocompression bonding and sintered at 900 ° C for 15 minutes to produce ceramics. The ceramics were polished to form 4 mm X 3 mm X 3 6 mm tubing columns, making 3 types of ceramics for the fourth measurement. By using ceramics for the fourth measurement and in accordance with JIS R 1 60 1, the flexural strength (3-point bending) was measured. The results are collectively shown in Table 4. 26 312 / Invention Specification (Supplement) / 92-04 / 92102639 200306963 (8) Effects of Examples 1 to 10 From the results of Tables 1 to 4, Examples 3 to 10 can each be sintered at a low temperature of 900 ° C. 'And shows a certain degree of dielectric characteristics. However, some of them show that the dielectric ceramics are distorted due to the poor thermal characteristics of the glass powder, some fail to provide sufficient dielectric properties, others migrate due to sintering and cause low-resistance conductors, or some do not provide sufficient bending strength. None of these embodiments is sufficiently well balanced with individual characteristics. On the other hand, the product embodiments of the present invention and 2 can be sintered at the same time as a low-resistance conductor at 900 ° C and show good dielectric properties (dielectric loss: 38 to 40 X 1 (Γ4, 7.2 to 7.4, and bending resistance) (Strength: 210 to 260 MPa). In addition, no migration of low-resistance conductor components was found, and no distortion of the substrate was observed. It was found that a sufficiently high flexural strength was obtained. In addition, the coefficient of thermal expansion was 6.1 to 6.2 ppm / ° C, indicating Appropriate characteristics as a wiring substrate. [2] Manufacturing of dielectric ceramics using dielectric ceramics containing glass containing alkali metal elements and zinc spinel (1) for the fifth measurement (measurement of dielectric properties) and manufacture of dielectrics The characteristics were measured using [1] '1, 2, 4, 6 and 9 glass manufactured as (1) above as glass powder' and zinc spinel powder, titanium oxide powder, and calcium carbonate powder were used as inorganic materials. The other materials are combined and mixed in the ratio shown in Table 5, and green sheets are manufactured as shown in [1] '(3) above. Then, similar to the above [丨], (4) are sintered and polished to produce 11 types. Ceramic for fifth measurement. "Except for Example i 1 when bubbling during sintering and distortion caused by Examples 1 to 9 and 21", the remaining 7 types of dielectric ceramics are similar to 27 312 / Invention Specification (Supplement) / 92-04 / 92102639 200306963 The methods of [1] and (4) above are used to measure the relative permittivity ε r at 3 GHz and the temperature coefficient rf of the resonance frequency at 25 to 80 ° C. The results are shown in the table together
28 312/發明說明書(補件)/92-04/92102639 200306963 ς«28 312 / Invention Specification (Supplement) / 92-04 / 92102639 200306963
介電陶瓷特性 PQ (MPa) r—H o ON 192 190 220 ^T) v〇 r-H 1 扭曲 ◎ ◎ ◎ ◎ ◎ ◎ ◎ X V〇 〇◦ ε Cu 3* I皿 盤 m C\ T-H 1 r-H rn r—^ 1 卜 ro 1 to (3GHz) r- G\ 1 10.6 | 1 10.6 | 10.3 | ^T) cK 11.2 I 10.7 I 1 介電陶瓷 無機塡料 (wt%) v-H * t-H (N r—H 寸 3 種類•比例(重量） mT/mG 1 0.86 1 0·91 1 I 0.71 1 0.76 1 0·74 1 1 0·42 1 1 1 0·74 1 0.72 丨蛇1 1 CaTi03 20 鈦氧 卜 o 卜 r-H On t-H 寸 t-H 1 00 鋅尖晶石 00 r-H r—^ 寸 (N <N m (N <N 玻璃 (wt%) 00 * On ON m m cn to 玻璃 編號 r-Ή r-H ▼-H t—H r-H (N Jt* < r—Η r—H * <N r—^ r-H 寸 r—^ 卜 00 ON T*H 1 *20 t-H CN II-w ls-< 6'··6e9SI_I/(義)wi··/^ 200306963 (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11至21之效果 由表5結果可知，實施例1 2至1 8各自可於如90(TC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〗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er高達9.5至10.7。此外，rf有一在-15至1 ppmrc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17)之例中，ε r高達 1 1 .2，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165 MPa之抗彎強度。特別，於無機塡料爲 30 312/發明說明書(補件)/92-〇4/921〇2639 200306963 鋅尖晶石塡料及鈦氧塡料之介電陶瓷案例，可提供1 8 〇至 22〇 MPa之絕佳抗彎強度。 以陶瓷總量爲1 0 0 w t %爲例，鋅尖晶石塡料及鈦氧塡料 之含量共計41至47 wt% ;此外於鋅尖晶石塡料（mG)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 / °C，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、AI2O3、CaO 以及 ΖιιΟ 粉末外，MgO、 BaO、Si*Ο及Zr〇2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1 1號玻璃），具有平均直徑爲3微米。 31 312/發明說明書(補件)/92-04/92102639 200306963 9漱 介電陶瓷 隹呂氧 (wt%) 玻璃 (wt%) 誠(wt%) 其它 N 1 1 1 1 rn IT) 0 d 1 1 1 1 r-^ 〇 1 d 卜 d 1 9 PQ 卜 m MgO 1 1 寸 d cn r-H d (N T—H 鹼金屬 1 1 1 1 * Na20 1 * 〇 <N 1 * » * Na20 1 * m d 寸 〇 N (N (N 1 * 1 * 1 * 1 * 1 * T—H r-H 1 * U 卜 00 卜 1 * 1 * 1 *0.15 1 卜 r-H VO 1 * C\ 00 Al2〇3 (N v〇 (N CN σ\ Ό m cn * 〇\ r-H * (N 00 CN (N 00 (N B203 VO CN 1 *45.5 1 卜 T—H cn * VO 06 艺 (N (N 卜: 00 (N (N ^Ti CN 06 (N JO (N rn (N rp (N <N 〇\ rp * 玻璃 編號 r—4 (N 5P VO 00 Os 〇 ▼—H * T—^ r-H * < r-H CN ΡΊ 7 00 Q\ 〇 * r-H t-H *Dielectric ceramic characteristics PQ (MPa) r—H o ON 192 190 220 ^ T) v〇rH 1 Twisted ◎ ◎ ◎ ◎ ◎ ◎ XV〇〇◦ ε Cu 3 * I dish m C \ TH 1 rH rn r — ^ 1 Br 1 to (3GHz) r- G \ 1 10.6 | 1 10.6 | 10.3 | ^ T) cK 11.2 I 10.7 I 1 Dielectric ceramic inorganic material (wt%) vH * tH (N r—H inch 3 Type • Proportion (weight) mT / mG 1 0.86 1 0 · 91 1 I 0.71 1 0.76 1 0 · 74 1 1 0 · 42 1 1 1 0 · 74 1 0.72 丨 Snake 1 1 CaTi03 20 TiOb On tH inch tH 1 00 zinc spinel 00 rH r— ^ inch (N < N m (N < N glass (wt%) 00 * On ON mm cn to glass number r-Ή rH ▼ -H t— H rH (N Jt * < r—Η r—H * < N r— ^ rH inch r— ^ bu 00 ON T * H 1 * 20 tH CN II-w ls- < 6 '·· 6e9SI_I / (Meaning) wi ·· / ^ 200306963 (2) The manufacturing of ceramics used for the sixth measurement (measurement of simultaneous sintering properties) and the evaluation of simultaneous sintering properties are similar to the aforementioned [1], (6) the measurement of distortion, according to the same reference, "◎" or "X" is shown in Table 5. (3) For the seventh test Manufacture of ceramics for measuring (bending strength measurement) and evaluation of bending strength in addition to using the aforementioned green sheets [2], (1) (here can be manufactured as above [2], (1) and (2) In addition to ceramics that do not bubble or warp), 7 types of ceramics for the seventh measurement are manufactured in the same way as in [1], (7) above. Then the flexural strength is measured in the same way. The results are shown in Table 5. (4) Effects of Examples 11 to 21 From the results in Table 5, it can be seen that Examples 12 to 18 can be sintered at a low temperature such as 90 ° C. On the other hand, in Example 11, due to glass and inorganic The ratio of the materials is not within the scope of the present invention, so air bubbles appear during sintering. The product of Example 1 cannot be used as a dielectric ceramic. Examples 1 to 2 are distorted. In the case of only glass, ε r is usually about 6. In contrast, the dielectric ceramics (Examples 12 to 16 and 18) made of zinc spinel ceramics and titanium oxide ceramics have an er of 9.5 to 10.7. In addition, rf has a small absolute chirp between -15 and 1 ppmrc. On the other hand, in the case of the dielectric ceramic (Example 17) in which the inorganic material was zinc spinel material and calcium titanate material, ε r was as high as 1 1.2, and rf also had 7 ppm / ° C. It's so small. In the case of dielectric ceramics in which the inorganic material is zinc spinel material and calcium titanate material, it can provide bending strength of 165 MPa. In particular, in the case of dielectric ceramics with inorganic materials of 30 312 / Invention Specification (Supplement) / 92-〇4 / 921〇2639 200306963 zinc spinel materials and titanium oxide materials, we can provide 1 800 to 22 Excellent flexural strength in MPa. Taking the total ceramic content as 100 wt% as an example, the content of zinc spinel aggregate and titanium oxide aggregate is 41 to 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 10 · 6, while rf is suppressed to a minimum 値, -3 to 1 ppm / ° C, while still maintaining The flexural strength is as high as 190 to 192 M Pa. [3] Dielectric ceramics use alkali-free glass and zinc spinel-free glass (1) Preparation of glass powders In addition to Si02, B2O3, AI2O3, CaO, and zinc powders, MgO, BaO , Si * 0 and ZrO2 powders were mixed at the ratios shown in Table 6 to prepare raw material powders. The prepared raw material powder is heated and melted, thrown into water to be rapidly cooled, and simultaneously granulated in water to obtain a glass frit. The glass frit was pulverized in a ball mill to produce 11 types of glass powder (glasses No. 1 to No. 1) having an average diameter of 3 microns. 31 312 / Invention Specification (Supplement) / 92-04 / 92102639 200306963 9 Dielectric Ceramics (wt%) Glass (wt%) Sincerity (wt%) Other N 1 1 1 1 rn IT) 0 d 1 1 1 1 r- ^ 〇1 d b d 1 9 PQ b m MgO 1 1 inch d cn rH d (NT—H alkali metal 1 1 1 1 * Na20 1 * 〇 < N 1 * »* Na20 1 * md Inch 〇N (N (N 1 * 1 * 1 * 1 * 1 * T-H rH 1 * U BU 00 BU 1 * 1 * 1 * 0.15 1 BU rH VO 1 * C \ 00 Al2〇3 (N v〇 (N CN σ \ Ό m cn * 〇 \ rH * (N 00 CN (N 00 (N B203 VO CN 1 * 45.5 1 T-H cn * VO 06 art (N (N B: 00 (N (N ^ Ti CN 06 (N JO (N rn (N rp (N < N 〇 \ rp * glass number r—4 (N 5P VO 00 Os 〇 ▼ —H * T— ^ rH * < rH CN ΡΊ 7 00 Q \ 〇 * rH tH *
Π : V 。「醒編忉盔餾柃_#」长嗽螩 ze， * ❿ 鲁 6e9slzl/ffsi)il-s蕾-ie 200306963 (2 )玻璃粉之T g及M g之測量 如上（1 )製造之1 1種玻璃粉之T g及M g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 個別値顯示於表7。 表7 玻璃 玻璃之熱特性 編號 Tg(°c ) Mg(°C ) Mg-Tg(°C ) 1 623 65 7 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 6 5 5 695 40 * 9 549 580 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（DBP)} 33Π: V. "Wake up 忉 helmet distilling 柃 _ #" long cough 螩 ze, * ❿ Lu 6e9slzl / ffsi) il-slei-ie 200306963 (2) The measurement of T g and M g of glass powder is as above (1) Manufacturing 1 1 The T g and M g of various glass powders are measured by a differential thermal measurement device (model "THERMOFLEX TAS 300 TG810D" manufactured by Buried International), and the individual display of Tg, Mg and Mg-Tg于 表 7。 In Table 7. Table 7 Thermal characteristics of glass: Tg (° c) Mg (° C) Mg-Tg (° C) 1 623 65 7 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 6 5 5 695 40 * 9 549 580 3 1 * 1 0 683 722 39 * 1 1 7 18 765 47 * "" in Table 7 means The scope of the invention. " (3) Manufacture of green sheet (dielectric ceramic composition) 1 1 to the individual glass powders manufactured in the above (2) and aluminum oxide powders as inorganic aggregate powders are weighed to have 50 as shown in Table 6 A wt% ratio is mixed with a ball mill to produce a mixed powder. Manufactured mixed powder with binder (acrylic resin), plasticizer {dibutyl phthalate (DBP)} 33
312/發明說明書(補件V92-〇4/921 〇2639 200306963 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 0 0微米’因而獲得 11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1 1片，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50毫米χ50毫米χ 〇 · 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ε r。結果顯禾於 表8。312 / Invention Specification (Supplement V92-〇4 / 921 〇2639 200306963 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) Manufacture of ceramics for the first measurement (for measuring dielectric properties) and measurement of dielectric properties 1 1 kinds of green sheets manufactured as above (3) The material is punched into a predetermined configuration, and a plurality of sheets are stacked 11 pieces by thermocompression bonding, and sintered at 900 ° C for 15 minutes to produce ceramics. The ceramics are polished to 50 mm x 50 mm x 〇 · 6 3 5 mm sheet to produce 11 ceramics for the first measurement. By using the ceramics for the first measurement, the dielectric resonator-perturbation method of the dielectric ceramic was used to measure the dielectric at 2 5 ° C at 3 GHz. Power loss and ε r. The results are shown in Table 8.
312/發明說明書(補件)/92-04/92102639 34 200306963 8撇 介電陶瓷特性 抗彎強度 (MPa) ο vo CN o (N 〇 (N 1 <180 1 1 1 1 1 1 扭曲 ◎ ◎ ◎ ◎ ◎ ◎ X ◎ X X X 熱膨脹係數 (25-400°〇 (ppm/°C) 寸 ui 寸 m uS v〇 寸 m K / o vd 寸 vd 寸 uS £ Y (3GHz) 1_ 卜： vo vq (N in vd Ch Ό On 寸 vd VO v〇 (N 卜· STbffi _Ί — CD ON m 沄 m o f-H o 00 r-H s ^sO 2 〇 實施例 i—H (N m r- oo Cn o T-H * T-H * 。「醒玀忉盔餾挎醒铢」长撇00撇¾. ςΓη、 · 9 Aw 6e9gIZ6/寸 0-ζ6/(φ}κ)_^^^^/ήΓΟ 200306963 (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 如上（3 )製造之1 1種生片材被沖壓成爲預定構形，2 0塊 片材透過熱壓連結法堆疊，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3毫米X 3毫米X 1 . 6毫米管柱， 製造Π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 1 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 01：燒結1 5分鐘。如此製造1 1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5 0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 36 312/發明說明書(補件)/92-04/92102639 200306963 生片材沖壓成爲預定組態，透過熱壓連結法堆疊1 1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11各自可於90 (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900 °C同時燒結，且顯示良好介電特性 (介電耗損：3 0至3 9 X 1 (Γ4，ε r : 7 · 5至7 · 6，以及抗彎強 度：2 6 0至2 7 0 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[丨]， 37 312/發明說明書(補件)/92-04/92102639 200306963 (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 G Η z之 相對介電常數ε r以及於2 5至8 (TC之共振頻率溫度係數τ f。結果共同顯示於表9。 38 312/發明說明書(補件)/92-04/92102639 200306963 £312 / Invention (Supplement) / 92-04 / 92102639 34 200306963 8 Characteristics of dielectric ceramics Bending strength (MPa) ο vo CN o (N 〇 (N 1 < 180 1 1 1 1 1 1 Twisted ◎ ◎ ◎ ◎ ◎ ◎ X ◎ XXX Coefficient of thermal expansion (25-400 ° 〇 (ppm / ° C) inch ui inch m uS v〇 inch m K / o vd inch vd inch uS £ Y (3GHz) 1_ Bu: vo vq (N in vd Ch Ό On inch vd VO v〇 (N Bu STbffi _Ί — CD ON m 沄 mo fH o 00 rH s ^ sO 2 〇 Example i—H (N m r- oo Cn o TH * TH *. " Awake helmet helmet dangles and awake baht "long write 00 00 ¾ ΓΓ, · 9 Aw 6e9gIZ6 / inch 0-ζ6 / (φ) κ) _ ^^^^ / ή Γ 200306963 (5) Second measurement (for measuring thermal expansion Coefficient) Manufacture of ceramics and the measurement of thermal expansion coefficient are as above (1) Manufactured 1 kinds of green sheets are punched into a predetermined configuration, 20 sheets are stacked by thermocompression bonding method, and sintered at 90 ° C1 5 minutes to manufacture ceramics. The ceramics were polished to become 3 mm X 3 mm X 1.6 mm pipe columns, and Π kinds of ceramics for the second measurement were manufactured. The ceramics for the second measurement were analyzed by differential expansion thermal machine Hold (Model "TMA8140D" manufactured by Rigaku International Co., Ltd.) The coefficient of thermal expansion was increased from 25 ° C to 400 ° C. The results are shown in Table 8. (6) The third measurement (for simultaneous measurement of sintering properties) for the manufacture of ceramics and Simultaneous evaluation of sintering properties 11 A 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. The ground silver paste is also printed on other green sheets, and the process is repeated. A total of 5 green sheets are laminated to obtain an unsintered laminate, and the silver paste is printed in a predetermined pattern between each layer. The unsintered laminate Stamped to a diameter of 4 cm, and sintered at 1501 for 15 minutes. This produced 11 types of ceramics with a low resistance conductor for the third measurement. 1 types of ceramics for the third measurement were laid on a flat surface. ， Measure the difference between the maximum position and the minimum position (contact position with the plane) from the plane. If the difference is less than 50 microns (not twisted to the actual level) or there is no distortion, it is marked as ", and the distortion exceeds 50 microns. "X, and are shown in Table 8. (7) For the fourth measurement (flexural strength measurement) of the manufacture and evaluation of the flexural strength of ceramics, as in the above (3) green sheet, corresponding to Example 1 , 2, 3, and 4 of 36 312 / Invention Specification (Supplement) / 92-04 / 92102639 200306963 The green sheet is punched into a predetermined configuration, and 1 1 green sheet is stacked by the thermocompression bonding method, and at 9 0 0 Sintered at 15 ° C for 15 minutes to produce ceramics. The ceramics were polished to form 4 mm x 3 mm x 36 mm tubing columns, and three types of ceramics were manufactured for the fourth measurement. By using ceramics for the fourth measurement, the bending strength (3-point bending) was measured. The results are collectively shown in Table 8. (8) Effects of Examples 1 to 10 From the results of Tables 6 to 8, Examples 4 to 11 can each be sintered at a low temperature of 90 ° C. and show a certain degree of dielectric properties. However, some of them show the effects due to glass frit. Poor thermal properties cause distortion of the dielectric ceramics, some fail to provide adequate dielectric properties, and others migrate due to sintering to low-resistance conductors, or some fail to provide sufficient flexural strength. None of these embodiments have Individual characteristics are sufficiently well balanced. On the other hand, Examples 1 to 3 of the product of the present invention can be sintered at the same time with a low-resistance conductor or at 900 ° C, and show good dielectric properties (dielectric loss: 3 0 to 3 9 X 1 (Γ4, ε r: 7 · 5 to 7 · 6 and flexural strength: 2 60 to 2 7 MPa). In addition, no migration of components constituting the low-resistance conductor was observed, and no distortion of the substrate was seen. High enough flexural strength. In addition, a coefficient of thermal expansion of 5.3 to 5.4 ppm / ° C 'shows appropriate characteristics as a wiring substrate. [4] Use of glass containing no alkali metal elements and zinc spinel filler Dielectric ceramic (1) for the fifth measurement (measurement of dielectric properties) The manufacturing of ceramics and the measurement of dielectric properties use the 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 gadolinium These materials are combined and mixed in the ratio shown in Table 9, as described above [丨], 37 312 / Invention Specification (Supplement) / 92-04 / 92102639 200306963 (3). [1], (4) Sintering and polishing were performed to produce a total of 9 ceramics for the fifth measurement. Among the manufactured dielectric ceramics, except for Example 12 where bubbles were generated during sintering, the remaining 8 ceramics The electrical ceramics were measured in a manner similar to the aforementioned [1], (4) at a relative dielectric constant ε r of 3 G 以及 z and a temperature coefficient of resonance frequency τ f at 25 to 8 (TC. The results are shown in Table 9 together. 38 312 / Invention Specification (Supplement) / 92-04 / 92102639 200306963 £
綱 遍： iff <- B (MPa) 燒結時冒泡 § T'11 i (N C\ f"' < r*H o Q\ 222 'sO r-H O 〇\ r-H C\ 扭曲 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Oh 3 00 rn (N uo 1 卜 £ r (3GHz) cK 1 10·4 1 10.4 L 10.1 I m Os 10.7 1 10.5 10.1 介電陶瓷組成 無機塡料 (wt%) r-H * r-H (N r-H 寸 種類•比例(重量） mT/mG | 0.86 0.91 1 °·71 1 0.76 1 °·74 1 0.42 t 0.75 1其它I 1 CaTi03 20 鈦氧 卜 o r-H 卜 τ—H Q\ 寸 1 00 |鋅尖晶石 | 00 r—^ 艺 (N cn m (N 玻璃 (wt%) 00 On On in VO m 5； 00 玻璃 編號 r-H r—H r-H r—< r-H r-H (N m < (N * m 1—ί 寸 T-H VO f-H 卜 00 〇\ ▼-H n-« l-< 6e ···6e9SII0-r6/ssl.i/lle 200306963 (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12至20之效果 由表9結果可知，實施例13至20各自可於低抵900 °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 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 3至 17、19及20)之er高達9.3至10.5。此外，rf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10.7，同時r f也具有7 ppm/°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 6 5 Μ P a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 〇 至22 0 MPa之絕佳抗彎強度。 40 312/發明說明書(補件)/92·04/92102639 200306963 以陶瓷總量爲1 00 wt%爲例，鋅尖晶石塡料以及鈦氧塡 料之含量共計41至47 wt% ;此外於鋅尖晶石塡料（mG)及 鈦氧塡料（mT)之mT/mG爲〇·7 1至0.76之例中，可見陶瓷 可維持ε r高達1 〇. 1至1 〇 · 4，而r 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 J P 2 0 0 2 - 1 4 5 4 0 6，申請日 2002 年 5 月 20 日、JP 2002-145407，申請日 2002 年 5 月Outline: iff <-B (MPa) blisters during sintering§ T'11 i (NC \ f " '< r * H o Q \ 222' sO rH O 〇 \ rH C \ distortion ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Oh 3 00 rn (N uo 1 Bu r (3GHz) cK 1 10 · 4 1 10.4 L 10.1 I m Os 10.7 1 10.5 10.1 Dielectric ceramic composition inorganic filler (wt%) rH * rH (N rH Inch Type • Proportion (Weight) mT / mG | 0.86 0.91 1 ° · 71 1 0.76 1 ° · 74 1 0.42 t 0.75 1 Other I 1 CaTi03 20 Titanium Oxide rH BU τ—HQ \ Inch 1 00 | Zinc Spinel Stone | 00 r— ^ art (N cn m (N glass (wt%) 00 On On in VO m 5; 00 glass number rH r—H rH r— < rH rH (N m < (N * m 1 —Ί inch TH VO fH bu00 〇 \ -H n- «l- < 6e ··· 6e9SII0-r6 / ssl.i / lle 200306963 (2) Ceramic for sixth measurement (measurement of simultaneous sintering properties) The evaluation of the manufacturing and simultaneous sintering properties is similar to the aforementioned [1], (6) the distortion is measured, and the reference "" ◎ "or" X "according to the same evaluation is shown in Table 9. (3) for the seventh measurement (measurement of bending strength) Manufacture of ceramics used and evaluation of flexural strength In addition to using the above-mentioned [2] '(1) green sheet (here can be manufactured as above [2], (1) ceramics that will not bubble or twist), 8 types of ceramics for the seventh measurement are based on the aforementioned [1], (7) Manufactured in the same way. Then the flexural strength was measured in accordance with the same way, and the results are shown in Table 9. (4) Effects of Examples 12 to 20 From the results in Table 9, it can be seen that Examples 13 to 20 were It can be sintered at a temperature as low as 900 ° C. On the other hand, in Example 12 because the ratio of glass to inorganic material is outside the scope of the present invention, bubbles appear during sintering. The product cannot be used as a dielectric ceramic. In the case of glass only, ε r is usually about 6. On the contrary, the inorganic material is a dielectric ceramic made of zinc spinel material and titanium oxide material (Example 1 3 (17, 19, and 20), er is as high as 9.3 to 10.5. In addition, the absolute value of rf is small, -16 to -2 ppm / ° C. On the other hand, the inorganic materials are zinc spinel materials and calcium titanate. In the example of the dielectric ceramic (Example 18), ε r was as high as 10.7, and rf also had a small absolute value of 7 ppm / ° C. In the case of dielectric ceramics, where the inorganic material is a zinc spinel material and a calcium titanate material, it can provide a bending strength of 165 MPa. In particular, in the case of dielectric ceramics in which the inorganic material is a zinc spinel material and a titanium oxide material, it can provide excellent bending strength of 180 to 22 MPa. 40 312 / Invention Specification (Supplement) / 92 · 04/92102639 200306963 Taking 100% by weight of ceramic as an example, the total content of zinc spinel and titanium oxide materials is 41 to 47% by weight; In the case where the mT / mG of zinc spinel aggregate (mG) and titanium oxide aggregate (mT) is 0.71 to 0.76, it can be seen that the ceramic can maintain ε r as high as 0.1 to 1 0.4, and The rf is suppressed to a very low 値, -5 to -2 ppm / ° C, while still maintaining a flexural strength as high as 190 to 193 MPa. This case is based on the Japanese patent application J P 2 0 0 2-1 4 5 4 0 6, application date May 20, 2002, JP 2002-145407, application date 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、JP 2001-232544, 申請日2001年7月31日、JP 2001-232545，申請日2001 年7月31曰、JP200卜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, JP 2001-232544, application date July 31, 2001, JP 2001-232545, The application date is July 31, 2001, JP200, 232546, the application date is July 31, 2001 and JP 2001-232547, and the application date is July 31, 2001. The contents of each case are hereby incorporated by reference. 41 312 / Invention Specification (Supplement) / 92-04 / 92102639
Claims (1)
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001232547 | 2001-07-31 | ||
| JP2002145409A JP2003112972A (en) | 2001-07-31 | 2002-05-20 | Dielectric porcelain |
| JP2002145408A JP2003112971A (en) | 2001-07-31 | 2002-05-20 | Dielectric porcelain |
| JP2002145406A JP4358479B2 (en) | 2001-07-31 | 2002-05-20 | Dielectric porcelain |
| JP2002145407A JP4358480B2 (en) | 2001-07-31 | 2002-05-20 | Dielectric porcelain |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW200306963A true TW200306963A (en) | 2003-12-01 |
| TWI243805B TWI243805B (en) | 2005-11-21 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW92102639A TWI243805B (en) | 2001-07-31 | 2003-01-30 | Dielectric ceramic |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI243805B (en) |
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| Publication number | Publication date |
|---|---|
| TWI243805B (en) | 2005-11-21 |
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| MM4A | Annulment or lapse of patent due to non-payment of fees |