TW202244026A - Porcelain Composition - Google Patents

Porcelain Composition Download PDF

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TW202244026A
TW202244026A TW111104947A TW111104947A TW202244026A TW 202244026 A TW202244026 A TW 202244026A TW 111104947 A TW111104947 A TW 111104947A TW 111104947 A TW111104947 A TW 111104947A TW 202244026 A TW202244026 A TW 202244026A
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mass
porcelain
porcelain composition
composition
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池田拓朗
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日商日本山村硝子股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/20—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in magnesium oxide, e.g. forsterite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Inorganic Insulating Materials (AREA)

Abstract

The present invention provides a porcelain composition in which the generation and growth of Ag colloids is suppressed, and an increase in the dielectric loss tangent due to co-firing with Ag is suppressed. The present invention provides a porcelain composition that contains, in terms of oxide equivalent mass%, 46-68 mass% of SiO2, 20-49 mass% of MgO, 0.3-5 mass% of Li2O, 0.6-15 mass% of Bi2O3, and 0.3-12 mass% of B2O3, wherein the mass ratio of Bi2O3 to B2O3 (Bi2O3/B2O3) is 10 or less.

Description

瓷器組成物Porcelain Composition

發明領域 本發明關於一種瓷器組成物，特別係關於一種透過低溫燒成而成為高頻用介電體瓷器的瓷器組成物。 field of invention The present invention relates to a porcelain composition, in particular to a porcelain composition that becomes dielectric porcelain for high frequency through low-temperature firing.

發明背景 已知氧化鋁、結晶化玻璃陶瓷等作為在高頻(特別係頻率10GHz以上)有用的介電體材料，該等被使用來作為電路基板材料。再者，為了與Ag、Au等金屬配線材料同時進行燒成，使用了會於接近該金屬配線材料熔點之800~1000℃左右的溫度下燒結的瓷器組成物來作為電路基板材料。 Background of the invention Alumina, crystallized glass ceramics, and the like are known as dielectric materials useful at high frequencies (particularly at frequencies above 10 GHz), and these are used as circuit board materials. In addition, in order to simultaneously fire metal wiring materials such as Ag and Au, a ceramic composition that is sintered at a temperature of about 800 to 1000° C. close to the melting point of the metal wiring materials is used as the circuit board material.

作為在高頻係低損失且會於800~1000℃左右的溫度燒結的瓷器組成物，例如於專利文獻1有記載一種含有結晶化玻璃粉末與氧化鋁粉末等的瓷器組成物。再者，於專利文獻2則有記載一種含有MgO、SiO 2及燒結助劑成分的瓷器組成物。 As a ceramic composition that has low loss in high frequency systems and can be sintered at a temperature of about 800-1000° C., for example, Patent Document 1 describes a ceramic composition containing crystallized glass powder, alumina powder, and the like. Furthermore, in Patent Document 2, there is a description of a porcelain composition containing MgO, SiO 2 and sintering aid components.

先前技術文獻 專利文獻 專利文獻1：日本專利4470392號公報 專利文獻2：日本專利4202117號公報 prior art literature patent documents Patent Document 1: Japanese Patent No. 4470392 Patent Document 2: Japanese Patent No. 4202117

發明概要 發明欲解決的課題 本發明人深入探討，結果發現：若將燒成後之主結晶相為鎂橄欖石(forsterite，Mg 2SiO 4)及/或頑火輝石(enstatite，MgSiO 3)的瓷器組成物，與作為配線材料的Ag同時進行燒成，則在燒成中Ag元素會擴散至瓷器中，且在冷卻後以Ag膠體的形式析出，而提高了瓷器的介電正切。使用了這種瓷器組成物的電路基板會有下述問題：特性會變成大大偏離所設計的電路特性。 Summary of the Invention Problems to be Solved by the Invention The present inventors conducted in-depth studies and found that: if the main crystal phase after firing is forsterite (forsterite, Mg 2 SiO 4 ) and/or enstatite (enstatite, MgSiO 3 ) porcelain If the composition is fired simultaneously with Ag as the wiring material, the Ag element will diffuse into the porcelain during firing, and precipitate in the form of Ag colloid after cooling, thereby increasing the dielectric tangent of the porcelain. A circuit board using such a ceramic composition has a problem in that the characteristics greatly deviate from the designed circuit characteristics.

因此，期望開發一種瓷器組成物，其中Ag膠體的產生及成長受到抑制，且其與作為配線材料的Ag同時燒成所致之介電正切的上升受到抑制。Therefore, it is desired to develop a ceramic composition in which the generation and growth of Ag colloid are suppressed, and the increase in dielectric tangent due to simultaneous firing with Ag as a wiring material is suppressed.

本發明目的係在於提供一種瓷器組成物，其中Ag膠體的產生及成長受到抑制，且其與Ag同時燒成所致之介電正切的上升受到抑制。The object of the present invention is to provide a porcelain composition, in which the generation and growth of Ag colloid are suppressed, and the rise of the dielectric tangent caused by simultaneous firing of Ag colloid is suppressed.

用以解決課題之手段 本發明人進一步反覆深入研究，結果發現：主結晶相為鎂橄欖石(Mg 2SiO 4)及/或頑火輝石(MgSiO 3)的瓷器在製造上，若瓷器組成物以SiO 2、MgO、Li 2O、Bi 2O 3、及B 2O 3作為必要成分，且各成分的氧化物換算的含量在特定範圍，則能夠藉此抑制Ag膠體的產生及成長，並且能夠抑制其與作為配線材料的Ag同時燒成所致之介電正切的上升，終至完成本發明。 Means for Solving the Problems The present inventors conducted further in-depth studies and found that: in the manufacture of porcelain whose main crystal phase is forsterite (Mg 2 SiO 4 ) and/or enstatite (MgSiO 3 ), if the composition of the porcelain is SiO 2 , MgO, Li 2 O, Bi 2 O 3 , and B 2 O 3 are essential components, and the content of each component in terms of oxides is within a specific range, which can suppress the generation and growth of Ag colloids, and can Suppressing the increase in dielectric tangent due to simultaneous firing with Ag as a wiring material has finally completed the present invention.

即，本發明關於下述的瓷器組成物。 1.一種瓷器組成物，其以氧化物換算的質量%計，含有： 46~68質量%SiO 2、 20~49質量%MgO、 0.3~5質量%Li 2O、 0.6~15質量%Bi 2O 3、 0.3~12質量%B 2O 3，且 Bi 2O 3與B 2O 3的質量比(Bi 2O 3/B 2O 3)係10以下。 2.如項1記載之瓷器組成物，其以氧化物換算的質量%計，含有： 50~64質量%SiO 2、 24~45質量%MgO、 0.5~3質量%Li 2O、 0.8~8質量%Bi 2O 3、 0.5~4質量%B 2O 3，且 Bi 2O 3與B 2O 3的質量比(Bi 2O 3/B 2O 3)係6以下。 3.如項1或2記載之瓷器組成物，其中SiO 2、MgO、CaO、ZnO、MnO、NiO及CoO含量的合計係80質量%以上。 4.如項1~3中任一者記載之瓷器組成物，其係與Ag同時燒成來使用。 That is, the present invention relates to the following porcelain composition. 1. A porcelain composition comprising: 46-68 mass % SiO 2 , 20-49 mass % MgO, 0.3-5 mass % Li 2 O, 0.6-15 mass % Bi 2 in terms of oxide conversion mass % O 3 , 0.3-12% by mass of B 2 O 3 , and the mass ratio of Bi 2 O 3 to B 2 O 3 (Bi 2 O 3 /B 2 O 3 ) is 10 or less. 2. The porcelain composition as described in Item 1, which contains, in terms of mass % in terms of oxides: 50-64 mass % SiO 2 , 24-45 mass % MgO, 0.5-3 mass % Li 2 O, 0.8-8 mass % Mass % Bi 2 O 3 , 0.5~4 mass % B 2 O 3 , and the mass ratio of Bi 2 O 3 to B 2 O 3 (Bi 2 O 3 /B 2 O 3 ) is 6 or less. 3. The porcelain composition according to item 1 or 2, wherein the total content of SiO 2 , MgO, CaO, ZnO, MnO, NiO and CoO is 80% by mass or more. 4. The porcelain composition described in any one of Items 1 to 3, which is fired simultaneously with Ag and used.

發明效果 本發明之瓷器組成物，其中Ag膠體的產生及成長受到抑制，且其與Ag同時燒成所致之介電正切的上升受到抑制。 Invention effect In the porcelain composition of the present invention, the generation and growth of Ag colloids are suppressed, and the rise of the dielectric tangent caused by simultaneous firing of Ag colloids is suppressed.

用以實施發明之形態 1.瓷器組成物 將本發明之瓷器組成物進行燒成所製造之瓷器，其係以鎂橄欖石(Mg 2SiO 4)及/或頑火輝石(MgSiO 3)的結晶相作為主結晶相。以下，在表現瓷器組成物之組成時，為方便起見，表示為單一元素的元素氧化物。本發明之瓷器組成物含有SiO 2、MgO、Li 2O、Bi 2O 3、B 2O 3。以下針對各成分及其含量進行說明。此外，在本說明書中，瓷器組成物各成分的含量係以氧化物換算的質量%來表示。 Modes for Carrying Out the Invention 1. Porcelain Composition The porcelain produced by firing the porcelain composition of the present invention is based on the crystal phase of forsterite (Mg 2 SiO 4 ) and/or enstatite (MgSiO 3 ) as the main crystalline phase. Hereinafter, when expressing the composition of the porcelain composition, it is expressed as an elemental oxide of a single element for convenience. The porcelain composition of the present invention contains SiO 2 , MgO, Li 2 O, Bi 2 O 3 and B 2 O 3 . Each component and its content are demonstrated below. In addition, in this specification, content of each component of a porcelain composition is represented by the mass % of oxide conversion.

本發明之瓷器組成物，以氧化物換算的質量%計，含有： 46~68質量%SiO 2、 20~49質量%MgO、 0.3~5質量%Li 2O、 0.6~15質量%Bi 2O 3、 0.3~12質量%B 2O 3，且 Bi 2O 3與B 2O 3的質量比(Bi 2O 3/B 2O 3)係10以下。 The porcelain composition of the present invention contains: 46-68 mass % SiO 2 , 20-49 mass % MgO, 0.3-5 mass % Li 2 O, 0.6-15 mass % Bi 2 O in terms of oxide conversion mass % 3. 0.3-12% by mass of B 2 O 3 , and the mass ratio of Bi 2 O 3 to B 2 O 3 (Bi 2 O 3 /B 2 O 3 ) is 10 or less.

具備上述構成的本發明之瓷器組成物，係分別以特定範圍的含量來含有：SiO 2、MgO、Li 2O、Bi 2O 3、及B 2O 3，且Bi 2O 3與B 2O 3的質量比(Bi 2O 3/B 2O 3)係10以下，藉此Ag膠體的生成受到抑制，且其與作為配線材料的Ag同時燒成所致之介電正切的上升能夠加以抑制。 The porcelain composition of the present invention having the above-mentioned constitution contains: SiO 2 , MgO, Li 2 O, Bi 2 O 3 , and B 2 O 3 in specific ranges, and Bi 2 O 3 and B 2 O The mass ratio of 3 (Bi 2 O 3 /B 2 O 3 ) is 10 or less, whereby the formation of Ag colloids is suppressed, and the increase in dielectric tangent caused by simultaneous firing with Ag as a wiring material can be suppressed .

(SiO 2) 在本發明之瓷器組成物中，SiO 2係瓷器的主成分。瓷器組成物定為100質量%，則SiO 2的含量係46~68質量%。若SiO 2的含量係上述範圍外，則在低溫下的燒結會變得困難。SiO 2的含量較佳為48~66質量%，更佳為50~64質量%。 (SiO 2 ) In the porcelain composition of the present invention, SiO 2 is a main component of porcelain. Assuming that the porcelain composition is 100% by mass, the content of SiO 2 is 46-68% by mass. If the content of SiO 2 is outside the above range, sintering at low temperature will become difficult. The content of SiO 2 is preferably from 48 to 66% by mass, more preferably from 50 to 64% by mass.

(MgO) 在本發明之瓷器組成物中，MgO係瓷器的主成分。瓷器組成物定為100質量%，則MgO的含量係20~49質量%。若MgO的含量係上述範圍外，則在低溫下的燒結會變得困難。MgO的含量係較佳為22~47質量%，更佳為24~45質量%。 (MgO) In the porcelain composition of the present invention, MgO is the main component of porcelain. Assuming that the porcelain composition is 100% by mass, the content of MgO is 20 to 49% by mass. When the content of MgO is outside the above-mentioned range, sintering at low temperature will become difficult. The content of MgO is preferably from 22 to 47% by mass, more preferably from 24 to 45% by mass.

(Li 2O) 在本發明之瓷器組成物中，Li 2O係促進瓷器燒結的副成分。瓷器組成物定為100質量%，則Li 2O的含量係0.3~5質量%。Li 2O的含量係較佳為0.4~4質量%，更佳為0.5~3質量%。 (Li 2 O) In the porcelain composition of the present invention, Li 2 O is an auxiliary component that promotes sintering of porcelain. Assuming that the porcelain composition is 100% by mass, the content of Li 2 O is 0.3 to 5% by mass. The content of Li 2 O is preferably from 0.4 to 4% by mass, more preferably from 0.5 to 3% by mass.

(Bi 2O 3) 在本發明之瓷器組成物中，Bi 2O 3係促進瓷器燒結的副成分。瓷器組成物定為100質量%，則Bi 2O 3的含量係0.6~15質量%。Bi 2O 3的含量若超過15質量%，則會促進Ag膠體的產生、成長，且介電正切會因與Ag同時燒成而上升。Bi 2O 3的含量較佳為0.7~11質量%，更佳為0.8~8質量%。 (Bi 2 O 3 ) In the porcelain composition of the present invention, Bi 2 O 3 is an auxiliary component that promotes sintering of porcelain. Assuming that the porcelain composition is 100% by mass, the content of Bi 2 O 3 is 0.6 to 15% by mass. If the content of Bi 2 O 3 exceeds 15% by mass, the generation and growth of Ag colloids will be promoted, and the dielectric tangent will increase due to simultaneous firing with Ag. The content of Bi 2 O 3 is preferably from 0.7 to 11% by mass, more preferably from 0.8 to 8% by mass.

(B 2O 3) 在本發明之瓷器組成物中，B 2O 3係一副成分，其在瓷器與Ag同時燒成時會抑制瓷器中Ag膠體的產生及成長。瓷器組成物定為100質量%，則B 2O 3的含量係0.3~12質量%。若B 2O 3的含量係上述範圍外，則瓷器與Ag同時進行燒成時，不會充分抑制瓷器中Ag膠體的產生及成長。再者，B 2O 3的含量若超過12，則所燒結出之瓷器的耐水性有降低之虞。B 2O 3的含量較佳為0.4~6質量%，更佳為0.5~4質量%。 (B 2 O 3 ) In the porcelain composition of the present invention, B 2 O 3 is an auxiliary component, which can inhibit the generation and growth of Ag colloid in the porcelain when the porcelain and Ag are fired at the same time. Assuming that the porcelain composition is 100% by mass, the content of B 2 O 3 is 0.3 to 12% by mass. If the content of B 2 O 3 is outside the above range, the generation and growth of Ag colloids in the porcelain cannot be sufficiently suppressed when the porcelain and Ag are simultaneously fired. Furthermore, if the content of B 2 O 3 exceeds 12, the water resistance of the sintered porcelain may decrease. The content of B 2 O 3 is preferably from 0.4 to 6% by mass, more preferably from 0.5 to 4% by mass.

在本發明之瓷器組成物來說，Bi 2O 3與B 2O 3的質量比(Bi 2O 3/B 2O 3)係10以下。上述質量比若超過10，則不會充分抑制瓷器中Ag膠體的產生及成長，且與Ag同時燒成所致之介電正切的上升便無法加以抑制。上述質量比較佳為7以下，更佳為6以下。 In the porcelain composition of the present invention, the mass ratio of Bi 2 O 3 to B 2 O 3 (Bi 2 O 3 /B 2 O 3 ) is 10 or less. If the mass ratio exceeds 10, the generation and growth of Ag colloid in porcelain cannot be sufficiently suppressed, and the increase in dielectric tangent caused by simultaneous firing with Ag cannot be suppressed. The above-mentioned quality ratio is preferably 7 or less, more preferably 6 or less.

(任意成分) 本發明之瓷器組成物亦可含有任意成分。就任意成分而言，可舉：選自於由CaO、ZnO、MnO、NiO及CoO構成之群組之至少1種任意成分。上述任意成分顯示與作為瓷器主成分之MgO類似的作用，並能夠調整各種特性：調整瓷器之介電常數的溫度依賴性等。當上述任意成分係選自於由CaO、ZnO、MnO、NiO及CoO構成之群組之至少1種成分的情況，瓷器組成物定為100質量%，則上述成分的含量，即CaO、ZnO、MnO、NiO及CoO含量的合計較佳為30質量%以下，更佳為20質量%以下，進一步較佳為10質量%以下。 (optional ingredient) The porcelain composition of the present invention may also contain optional components. Examples of optional components include at least one optional component selected from the group consisting of CaO, ZnO, MnO, NiO, and CoO. Any of the above-mentioned components exhibits an action similar to that of MgO, which is a main component of porcelain, and can adjust various characteristics: adjustment of temperature dependence of dielectric constant of porcelain, and the like. When the above arbitrary components are at least one component selected from the group consisting of CaO, ZnO, MnO, NiO and CoO, the porcelain composition is defined as 100% by mass, then the content of the above components, that is, CaO, ZnO, The total content of MnO, NiO, and CoO is preferably at most 30% by mass, more preferably at most 20% by mass, further preferably at most 10% by mass.

在本發明之瓷器組成物含有任意成分的情況下，瓷器組成物定為100質量%，則可使用來作為上述瓷器之主成分的成分，即SiO 2、MgO、CaO、ZnO、MnO、NiO及CoO含量的合計較佳為80質量%以上，更佳為83質量%以上，進一步較佳為86質量%以上。此外，在本發明之瓷器組成物含有上述列舉之任意成分中僅一部分之情況下，SiO 2及MgO的含量，與該所含有僅一部分之任意成分含量，兩者的合計較佳為上述範圍。再者，在本發明之瓷器組成物不含有上述任意成分之情況下，SiO 2及MgO含量的合計亦較佳為上述範圍。 In the case where the porcelain composition of the present invention contains any component, the porcelain composition is defined as 100% by mass, and the components that can be used as the main components of the above-mentioned porcelain, namely SiO 2 , MgO, CaO, ZnO, MnO, NiO and The total of the CoO content is preferably at least 80% by mass, more preferably at least 83% by mass, further preferably at least 86% by mass. In addition, when the porcelain composition of the present invention contains only a part of the above-mentioned optional components, the total of the content of SiO 2 and MgO and the content of the only part of the optional components contained is preferably within the above-mentioned range. Furthermore, when the porcelain composition of the present invention does not contain any of the above-mentioned components, the total content of SiO 2 and MgO is also preferably within the above-mentioned range.

本發明之瓷器組成物，以氧化物換算的質量%計，含有： 50~64質量%SiO 2、 24~45質量%MgO、 0.5~3質量%Li 2O、 0.8~8質量%Bi 2O 3、 0.5~4質量%B 2O 3、 且Bi 2O 3與B 2O 3的質量比(Bi 2O 3/B 2O 3)較佳為6以下。藉由本發明之瓷器組成物滿足上述要件，Ag膠體的產生及成長越發受到抑制，且其與作為配線材料的Ag同時燒成所致之介電正切的上升能越發加以抑制。 The porcelain composition of the present invention contains: 50-64 mass % SiO 2 , 24-45 mass % MgO, 0.5-3 mass % Li 2 O, 0.8-8 mass % Bi 2 O in terms of oxide conversion mass % 3. 0.5-4% by mass of B 2 O 3 , and the mass ratio of Bi 2 O 3 to B 2 O 3 (Bi 2 O 3 /B 2 O 3 ) is preferably 6 or less. When the ceramic composition of the present invention satisfies the above requirements, the generation and growth of Ag colloid can be further suppressed, and the rise of the dielectric tangent caused by simultaneous firing with Ag as the wiring material can be further suppressed.

若能夠將本發明之瓷器組成物作成上述構成，則不特別限定原料的種類。例如：能夠使用SiO 2、MgO等單一元素之元素氧化物的混合物。再者，亦可使用MgSiO 3、Li 2B 4O 7等複氧化物。再者，亦可使用作為氧化物供給源的化合物(各種氫氧化物、碳酸鹽等)。 The types of raw materials are not particularly limited as long as the porcelain composition of the present invention can be configured as described above. For example, a mixture of element oxides of a single element such as SiO 2 and MgO can be used. Furthermore, multiple oxides such as MgSiO 3 and Li 2 B 4 O 7 can also be used. Furthermore, compounds (various hydroxides, carbonates, etc.) that are sources of oxides can also be used.

本發明之瓷器組成物之形態並無特別限定，較佳為將上述氧化物等的粉末混合，並進行預燒而預先使其反應之後，再度進行粉碎而獲得的粉末。The form of the porcelain composition of the present invention is not particularly limited, but it is preferably a powder obtained by mixing powders of the above-mentioned oxides and the like, preliminarily firing and reacting in advance, and then pulverizing again.

本發明之瓷器組成物的50%粒徑(中值粒徑(median size))並無特別限定，例如：50%粒徑(D 50)可為0.01~10μm。50%粒徑(D 50)越小，就越能夠在低的燒成溫度顯示充分的燒結性，基於此點，50%粒徑(D 50)較佳為0.1~5.0μm，更佳為0.2~1.0μm。 The 50% particle size (median size) of the porcelain composition of the present invention is not particularly limited, for example, the 50% particle size (D 50 ) may be 0.01-10 μm. The smaller the 50% particle size (D 50 ), the more sufficient sinterability can be exhibited at a low firing temperature. Based on this point, the 50% particle size (D 50 ) is preferably 0.1~5.0 μm, more preferably 0.2 ~1.0 μm.

關於本發明之瓷器組成物，即便在Ag離子擴散了的情況下，Ag膠體的產生及成長也會受到抑制，且其與Ag同時燒成所致之介電正切的上升也能加以抑制。即本發明之瓷器組成物較佳係與Ag同時燒成來使用。Regarding the porcelain composition of the present invention, even when Ag ions are diffused, the generation and growth of Ag colloids are suppressed, and the increase in dielectric tangent due to simultaneous firing with Ag is also suppressed. That is, the porcelain composition of the present invention is preferably used by firing simultaneously with Ag.

若瓷器是於本發明之瓷器組成物中添加1質量%Ag 2O，並於800~1000℃的溫度進行燒成而使其變得緻密，則該瓷器在10GHz下的介電正切較佳為0.0015以下，更佳為0.0010以下，進一步較佳為0.0008以下。 If the porcelain is made by adding 1 mass % Ag 2 O to the porcelain composition of the present invention and firing at a temperature of 800-1000°C to make it dense, the dielectric tangent of the porcelain at 10 GHz is preferably 0.0015 or less, more preferably 0.0010 or less, further preferably 0.0008 or less.

Ag膠體會強烈吸收波長400~500nm的光，因此關於Ag膠體的產生及成長，除了透過將Ag 2O添加於瓷器組成物而燒成瓷器，並測定瓷器的介電正切之方法以外，還能夠透過瓷器的色調而簡便地進行評價。例如：在波長450nm的漫反射率(diffuse reflectance)越低，則能評價為Ag膠體的量越多，能夠使得本指標有助於瓷器組成物的組成設計。不過，因瓷器組成物含有許多MnO、CoO、NiO等著色成分而已呈現較Ag膠體所帶來的著色更深的顏色，此情況時，透過色調的評價並不適切，而需要透過測定介電正切的評價。 Ag colloids will strongly absorb light with a wavelength of 400-500nm. Therefore, for the generation and growth of Ag colloids, in addition to firing porcelain by adding Ag 2 O to the porcelain composition, and measuring the dielectric tangent of the porcelain, it can also be Evaluate easily through the color tone of the porcelain. For example, the lower the diffuse reflectance (diffuse reflectance) at a wavelength of 450nm, the greater the amount of Ag colloid can be evaluated, which can make this index helpful for composition design of porcelain compositions. However, because the porcelain composition contains many coloring components such as MnO, CoO, and NiO, it presents a deeper color than the coloring brought by Ag colloid. Evaluation.

本發明之瓷器組成物能利用已知方法而使用於積層基板的製造中。例如：進行透過刮刀法等成形生胚片材、往片材表面印刷導體用糊、片材的積層、壓接等後，以800~1000℃的溫度進行燒成，藉此能夠獲得積層基板。The porcelain composition of the present invention can be used in the manufacture of laminated substrates by known methods. For example, after forming a green sheet by doctor blade method, printing conductor paste on the surface of the sheet, laminating the sheet, crimping, etc., firing at a temperature of 800~1000°C can obtain a laminated substrate.

2.瓷器組成物的製造方法 就製造本發明之瓷器組成物之製造方法而言，並無特別限定，例如：如上述般將作為原料的氧化物等粉末予以混合，並進行預燒而預先使其反應之後，再度進行粉碎，藉此能夠以粉末的形態製造本發明的瓷器組成物。 2. Manufacturing method of porcelain composition The method for producing the porcelain composition of the present invention is not particularly limited. For example, powders such as oxides used as raw materials are mixed as described above, calcined and reacted in advance, and then pulverized again. Thereby, the porcelain composition of this invention can be manufactured in the powder form.

若預燒溫度是能使作為原料的氧化物等發生反應的溫度，則不特別限定，較佳為700~1000℃，更佳為750~900℃。Although the calcining temperature is not particularly limited as long as it is a temperature at which oxides or the like as raw materials can react, it is preferably 700 to 1000°C, more preferably 750 to 900°C.

若預燒時間能使作為原料的氧化物等發生反應，則不特別限定，較佳為0.1~100小時，更佳為1~30小時。The calcining time is not particularly limited as long as the raw materials such as oxides can react, but is preferably 0.1 to 100 hours, more preferably 1 to 30 hours.

關於將預燒過後的氧化物等予以粉碎的方法，並無特別限定，能夠藉由例如：使用珠磨機、噴射磨機(Jet mill)等裝置來粉碎的方法進行粉碎。再者，於粉碎後亦可藉由氣流分級等方法來將粉末分級而調整粒度分布。The method of pulverizing the calcined oxides is not particularly limited, and can be pulverized by, for example, a method of pulverizing using a device such as a bead mill or a jet mill. Furthermore, after pulverization, the powder can also be classified by methods such as airflow classification to adjust the particle size distribution.

藉由以上說明的製造方法，能夠製造本發明之瓷器組成物。The porcelain composition of the present invention can be produced by the production method described above.

實施例 於以下出示實施例及比較例而具體說明本發明。不過本發明並不限定於實施例的態樣。 Example The present invention will be specifically described below by showing Examples and Comparative Examples. However, this invention is not limited to the aspect of an Example.

(製造瓷器組成物) 準備了SiO 2、Mg(OH) 2 、Li 2CO 3、Bi 2O 3、及Li 2B 4O 7作為原料粉末。混合上述原料粉末，使氧化物換算的組成達到表1所示之值，並進行粉碎而獲得了原料混合粉末。於850℃下將原料混合粉末燒成24小時，並將燒成物再度進行粉碎而製造出50%粒徑(D 50)=0.5~0.6μm之瓷器組成物的粉末。此外，粉末的50%粒徑(D 50)是使用雷射繞射-散射式粒度分布測定機(型號名稱「MT-3300」，日機裝股份有限公司製)而進行了測定。 (Production of Porcelain Composition) SiO 2 , Mg(OH) 2 , Li 2 CO 3 , Bi 2 O 3 , and Li 2 B 4 O 7 were prepared as raw material powders. The above-mentioned raw material powders were mixed so that the composition in terms of oxides became the values shown in Table 1, and pulverized to obtain raw material mixed powders. The raw material mixed powder was fired at 850°C for 24 hours, and the fired product was pulverized again to produce a powder of the porcelain composition with a 50% particle size (D 50 )=0.5-0.6 μm. In addition, the 50% particle diameter (D 50 ) of the powder was measured using a laser diffraction-scattering particle size distribution measuring machine (model name "MT-3300", manufactured by Nikkiso Co., Ltd.).

[評價方法] 針對於實施例及比較例所製造出的瓷器組成物，製作試料並進行了下述測定。 [Evaluation method] About the ceramic composition manufactured in the Example and the comparative example, the sample was produced, and the following measurement was performed.

(製作試料) 將瓷器組成物的粉末壓縮成形為丸粒狀後，於900℃或950℃下燒成1小時，製備出燒結體。再者，另行製備下述粉末：是以瓷器組成物的粉末：Ag 2O=99：1的質量比來混合瓷器組成物的粉末與Ag 2O，並同樣壓縮成形為丸粒狀後進行燒成，製備了添加有Ag 2O之添加Ag 2O的燒結體。 (Preparation of Samples) The powder of the porcelain composition was compression-molded into pellets, and then fired at 900° C. or 950° C. for 1 hour to prepare a sintered body. Furthermore, the following powder was prepared separately: the powder of the porcelain composition and Ag 2 O were mixed with the powder of the porcelain composition:Ag 2 O=99:1 mass ratio, and similarly compression-molded into pellets and then fired As a result, an Ag 2 O-added sintered body containing Ag 2 O was prepared.

接著，分別研磨燒結體、及添加Ag 2O的燒結體的表面，而製備了漫反射率測定用試料。再者，另行將燒結體、及添加Ag 2O的燒結體分別進行研削及研磨，加工為直徑15.5mm、高度7.8mm而製備了介電特性測定用試料。 Next, the surfaces of the sintered body and the Ag 2 O-added sintered body were ground, respectively, to prepare samples for diffuse reflectance measurement. Furthermore, the sintered body and the sintered body to which Ag 2 O was added were ground and ground separately, and processed to a diameter of 15.5 mm and a height of 7.8 mm to prepare a sample for dielectric characteristic measurement.

(漫反射率) 使用於分光光度計(型號名稱「U-3010」，(股)日立先端科技(Hitachi High-Technologies製)附有積分球的裝置，並以入射光角度10度的測定條件測定了包含正反射的漫反射光。使用了由Al 2O 3構成的標準白色板作為標準樣本。於表1列示在450nm的測定值。 (Diffuse reflectance) Used in a spectrophotometer (model name "U-3010", manufactured by Hitachi High-Technologies Co., Ltd.) with an integrating sphere, and measured under the measurement conditions of an incident light angle of 10 degrees Diffuse reflection light including regular reflection was used. A standard white plate composed of Al 2 O 3 was used as a standard sample. The measured values at 450nm are listed in Table 1.

(介電特性(相對介電常數(relative permittivity)、介電正切)) 藉著依據JIS R1627「微波用精密陶瓷(fine ceramics)介電特性的試驗方法」的測定方法來測定在10GHz下之相對介電常數及介電正切作為介電特性。測定係使用是德科技(Keysight Technologies)公司製，PNA網路分析儀N5227A來進行。 (dielectric properties (relative permittivity, dielectric tangent)) The relative permittivity and dielectric tangent at 10 GHz were measured as dielectric properties by the measurement method based on JIS R1627 "Test method for dielectric properties of fine ceramics for microwave use". The measurement was performed using a PNA network analyzer N5227A manufactured by Keysight Technologies.

於表1列示實施例及比較例的組成與評價結果。Table 1 lists the compositions and evaluation results of Examples and Comparative Examples.

[表1]

Figure 02_image001
[Table 1]
Figure 02_image001

從表1之結果瞭解到：在比較例1及2來說，添加有1%Ag 2O之燒結體其漫反射率係22%或34%(即任一者皆低於50%)；相對於此，在實施例1~10來說，漫反射率係55~89%(即任一者皆50%以上)， Ag膠體的產生受到了抑制。 Understand from the result of table 1: for comparative example 1 and 2, its diffuse reflectance of the sintered body that adds 1%Ag 2 O is 22% or 34% (that is either all is lower than 50%); Relatively Here, in Examples 1 to 10, the diffuse reflectance is 55 to 89% (that is, any of them is more than 50%), and the generation of Ag colloid is suppressed.

再者，比較例1其添加有1%Ag 2O之燒結體的介電正切係高達0.0016的值。相對於此，在實施例1來說，介電正切係0.0006，顯示了低的值；瞭解到：在實施例1來說，Ag膠體的產生及成長受到抑制，且介電正切的上升受到了抑制。 Furthermore, in Comparative Example 1, the dielectric tangent of the sintered body added with 1% Ag 2 O is as high as 0.0016. On the other hand, in Example 1, the dielectric tangent system is 0.0006, which shows a low value; it is understood that in Example 1, the generation and growth of Ag colloids are suppressed, and the rise of the dielectric tangent is suppressed. inhibition.

產業上之可利用性 關於本發明之瓷器組成物，由於Ag膠體的產生及成長受到抑制，且其與Ag同時燒成所致之介電正切的上升受到抑制，因而作為與Ag同時燒成所使用的配線材料係有用的。 Industrial availability The porcelain composition of the present invention is useful as a wiring material used for co-firing with Ag because the generation and growth of Ag colloids are suppressed, and the increase in dielectric tangent due to simultaneous firing with Ag is suppressed. of.

Claims (4)

一種瓷器組成物，其以氧化物換算的質量%計，含有： 46~68質量%SiO 2、 20~49質量%MgO、 0.3~5質量%Li 2O、 0.6~15質量%Bi 2O 3、 0.3~12質量%B 2O 3，且 Bi 2O 3與B 2O 3的質量比(Bi 2O 3/B 2O 3)係10以下。 A porcelain composition comprising: 46-68 mass % SiO 2 , 20-49 mass % MgO, 0.3-5 mass % Li 2 O, 0.6-15 mass % Bi 2 O 3 in terms of oxide conversion mass % , 0.3~12 mass% B 2 O 3 , and the mass ratio of Bi 2 O 3 to B 2 O 3 (Bi 2 O 3 /B 2 O 3 ) is 10 or less. 如請求項1之瓷器組成物，其以氧化物換算的質量%計，含有： 50~64質量%SiO 2、 24~45質量%MgO、 0.5~3質量%Li 2O、 0.8~8質量%Bi 2O 3、 0.5~4質量%B 2O 3，且 Bi 2O 3與B 2O 3的質量比(Bi 2O 3/B 2O 3)係6以下。 For example, the porcelain composition of claim 1, in terms of mass % in terms of oxides, contains: 50-64 mass % SiO 2 , 24-45 mass % MgO, 0.5-3 mass % Li 2 O, 0.8-8 mass % Bi 2 O 3 , 0.5-4% by mass B 2 O 3 , and the mass ratio of Bi 2 O 3 to B 2 O 3 (Bi 2 O 3 /B 2 O 3 ) is 6 or less. 如請求項1或2之瓷器組成物，其中SiO 2、MgO、CaO、ZnO、MnO、NiO及CoO含量的合計係80質量%以上。 The porcelain composition according to claim 1 or 2, wherein the total content of SiO 2 , MgO, CaO, ZnO, MnO, NiO and CoO is more than 80% by mass. 如請求項1至3中任一項之瓷器組成物，其係與Ag同時燒成來使用。The porcelain composition according to any one of Claims 1 to 3, which is fired simultaneously with Ag.
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