JP7577959B2 - Glass composition and sealing material - Google Patents
Glass composition and sealing material Download PDFInfo
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- JP7577959B2 JP7577959B2 JP2020166642A JP2020166642A JP7577959B2 JP 7577959 B2 JP7577959 B2 JP 7577959B2 JP 2020166642 A JP2020166642 A JP 2020166642A JP 2020166642 A JP2020166642 A JP 2020166642A JP 7577959 B2 JP7577959 B2 JP 7577959B2
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- 239000011521 glass Substances 0.000 title claims description 47
- 239000003566 sealing material Substances 0.000 title claims description 40
- 239000002131 composite material Substances 0.000 title description 4
- 239000000843 powder Substances 0.000 claims description 42
- 239000000919 ceramic Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 9
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 5
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 description 35
- 239000002184 metal Substances 0.000 description 35
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229910003069 TeO2 Inorganic materials 0.000 description 4
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 3
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 3
- 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 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 239000006066 glass batch Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- DMFGNRRURHSENX-UHFFFAOYSA-N beryllium copper Chemical compound [Be].[Cu] DMFGNRRURHSENX-UHFFFAOYSA-N 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Description
本発明は、ガラス組成物及び封着材料に関し、特に通信用途等に使用される同軸コネクタ端子の封着に好適なガラス組成物及び封着材料に関する。 The present invention relates to a glass composition and a sealing material, and in particular to a glass composition and a sealing material suitable for sealing coaxial connector terminals used in communication applications, etc.
通信用途の同軸コネクタ端子は、外殻と中心導体の絶縁性を維持するために、金属シェルと金属ピンを樹脂やガラス等の絶縁体で封着することにより作製される。特に、高い信頼性や耐熱性を求められる品種では、絶縁体にガラス粉末を含む封着材料が用いられる。 Coaxial connector terminals for communication applications are manufactured by sealing a metal shell and a metal pin with an insulator such as resin or glass to maintain the insulation between the outer shell and the central conductor. In particular, for products that require high reliability and heat resistance, sealing materials containing glass powder as an insulator are used.
封着材料は、以下のようにして作製、使用される。まずガラス原料を溶融、成形し、成形後のガラスをボールミルで粉砕した後、所定の篩を通過させることによって微粉のガラス粉末にし、得られたガラス粉末に対して、必要に応じてセラミック粉末を添加、混合して、粉末材料（封着材料）とする。次いで、この粉末材料をバインダーと混合して造粒し、顆粒を作製する。その後、この顆粒を打錠成型して貫通孔を有する圧粉体を作製し、これを常温から昇温して、バインダーの分解除去と焼結を行い、焼結体とする。次に、得られた焼結体の貫通孔に金属ピンを挿入し、更にこの焼結体を環状の金属シェル内に収容した後、電気炉に投入し、不活性雰囲気下において、作業点より高い温度で固着した後、室温まで冷却する。 The sealing material is produced and used as follows. First, glass raw materials are melted and molded, and the molded glass is pulverized in a ball mill and passed through a specified sieve to produce fine glass powder. Ceramic powder is added to the obtained glass powder as necessary and mixed to produce a powder material (sealing material). Next, this powder material is mixed with a binder and granulated to produce granules. After that, these granules are compressed into tablets to produce a green compact with through holes, which is heated from room temperature to decompose and remove the binder and sinter to produce a sintered body. Next, a metal pin is inserted into the through hole of the obtained sintered body, and the sintered body is placed in a ring-shaped metal shell, then placed in an electric furnace, and fixed at a temperature higher than the working point in an inert atmosphere, and then cooled to room temperature.
ガラス粉末を作業点以上まで加熱すると、十分な流動性が得られる。これにより、金属部材と封着材料の間に過分な空隙を生ずることなく密着させることができ、同軸コネクタ端子の気密信頼性を高めることができる。なお、ガラス粉末の作業点は一般的に９００℃以上であるため、封着時の焼成温度は一般的に９００℃以上である。また、金属シェル及び金属ピンの融点は一般的に１４００℃以上である。 When glass powder is heated to above its working point, it is able to obtain sufficient fluidity. This allows the metal member and the sealing material to be tightly attached without creating excessive gaps between them, improving the airtight reliability of the coaxial connector terminal. Since the working point of glass powder is generally 900°C or higher, the firing temperature during sealing is generally 900°C or higher. In addition, the melting points of the metal shell and metal pin are generally 1400°C or higher.
図１（ａ）は、同軸コネクタ端子１を示す概念図であり、同軸コネクタ端子１は、金属シェル１１、金属ピン１２及び封着材料１３を有している。図１（ｂ）は、図１（ａ）の同軸コネクタ端子１の要部について、焼成前の金属シェル１１、金属ピン１２及び封着材料１３の状態を示す概念図であり、図１（ｃ）は、図１（ａ）の同軸コネクタ端子１の要部について、焼成後の金属ステム１１、金属ピン１２及び封着材料１３の状態を示す概念図である。 Figure 1(a) is a conceptual diagram showing a coaxial connector terminal 1, which has a metal shell 11, a metal pin 12, and a sealing material 13. Figure 1(b) is a conceptual diagram showing the state of the metal shell 11, the metal pin 12, and the sealing material 13 before firing for the main part of the coaxial connector terminal 1 in Figure 1(a), and Figure 1(c) is a conceptual diagram showing the state of the metal stem 11, the metal pin 12, and the sealing material 13 after firing for the main part of the coaxial connector terminal 1 in Figure 1(a).
近年、通信用の同軸コネクタでは嵌合時の密着度を向上させて信号の伝達効率を高めるために、金属ピンに対して高いバネ性が求められることがある。この場合、金属ピンには、一般的に、リン青銅、黄銅、ベリリウム銅等が用いられる。そして、これらの金属の融点は通常９００℃以下であり、また熱膨張係数は１６０～１９０×１０－７／℃である。 In recent years, in coaxial connectors for communication, metal pins are required to have high spring properties in order to improve the degree of adhesion when mated and increase the efficiency of signal transmission. In this case, phosphor bronze, brass, beryllium copper, etc. are generally used for the metal pins. The melting points of these metals are usually 900°C or less, and the thermal expansion coefficient is 160 to 190× 10-7 /°C.
しかし、従来の封着材料では、９００℃以下の温度で流動性が低く、これらの金属を金属ピンに用いた場合に気密信頼性を確保できなかった。このため、絶縁体として樹脂を用いなければならず、耐熱性や気密信頼性を確保が困難であった。 However, conventional sealing materials have low fluidity at temperatures below 900°C, and when these metals are used in metal pins, airtight reliability cannot be ensured. For this reason, resin must be used as an insulator, making it difficult to ensure heat resistance and airtight reliability.
本発明は、上記事情に鑑みなされたものであり、その技術的課題は、９００℃以下の温度で良好に流動し得るガラス組成物及び封着材料を提供することにより、通信用同軸コネクタ端子等の気密信頼性を高めることである。 The present invention was made in consideration of the above circumstances, and its technical objective is to improve the airtight reliability of communication coaxial connector terminals and the like by providing a glass composition and sealing material that can flow well at temperatures of 900°C or less.
本発明者は、種々の実験を繰り返した結果、ＴｅＯ２を主成分とするガラスを用いることにより、上記技術的課題を解決し得ることを見出し、本発明として、提案するものである。本発明のガラス組成物は、ガラス組成として、下記酸化物基準のモル％で、ＴｅＯ２ ４０～８５％、ＭｏＯ３ ０～２０％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ １～２０％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ １～２０％、ＭｎＯ＋Ｃｒ２Ｏ３＋Ｆｅ２Ｏ３＋Ｃｏ３Ｏ４ ０．１～８％を含有することを特徴とする。このようにすれば、作業点が９００℃以下、特に８５０℃以下に低下させることができる。その結果、バネ性が高い金属部材の封着材料として好適に用いることができる。ここで、「下記酸化物基準」とは、多価酸化物の場合に、成分の価数に依らず、表記の酸化物に換算して表記するものとする。例えば、酸化鉄は、ＦｅＯやＦｅ２Ｏ３等があるが、本発明では、Ｆｅの価数に依らず、「Ｆｅ２Ｏ３」に換算して表記するものとする。「Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ」は、Ｌｉ２Ｏ、Ｎａ２Ｏ及びＫ２Ｏの合量を指す。「ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ」は、ＭｇＯ、ＣａＯ、ＳｒＯ及びＢａＯの合量を指す。「ＭｎＯ＋Ｃｒ２Ｏ３＋Ｆｅ２Ｏ３＋Ｃｏ３Ｏ４」は、ＭｎＯ、Ｃｒ２Ｏ３、Ｆｅ２Ｏ３及びＣｏ３Ｏ４の合量を指す。 As a result of repeated experiments, the inventors found that the above technical problems can be solved by using a glass mainly composed of TeO 2 , and propose this invention. The glass composition of the present invention is characterized by containing, as a glass composition, 40-85% TeO 2 , 0-20% MoO 3 , 1-20% Li 2 O + Na 2 O + K 2 O , 1-20% MgO + CaO + SrO + BaO , and 0.1-8% MnO + Cr 2 O 3 + Fe 2 O 3 + Co 3 O 4 in mole percent based on the following oxides. In this way, the working point can be lowered to 900 ° C or less, particularly 850 ° C or less. As a result, it can be suitably used as a sealing material for metal members with high spring properties. Here, "based on the following oxides" means that in the case of polyvalent oxides, the expression is expressed in terms of the oxides shown, regardless of the valence of the components. For example, iron oxide includes FeO and Fe2O3 , but in the present invention, it is expressed in terms of " Fe2O3 " regardless of the valence of Fe. " Li2O + Na2O + K2O " refers to the total amount of Li2O , Na2O , and K2O . "MgO+CaO+SrO+BaO" refers to the total amount of MgO, CaO , SrO, and BaO. "MnO+Cr2O3+Fe2O3+Co3O4 " refers to the total amount of MnO, Cr2O3 , Fe2O3 , and Co3O4 .
本発明の封着材料は、上記のガラス組成物からなるガラス粉末とセラミック粉末とを含有する封着材料であって、ガラス粉末の含有量が６０～１００質量％、セラミック粉末の含有量が０～４０質量％であることを特徴とする。 The sealing material of the present invention is a sealing material containing glass powder made of the above-mentioned glass composition and ceramic powder, and is characterized in that the glass powder content is 60 to 100 mass % and the ceramic powder content is 0 to 40 mass %.
また、本発明の封着材料では、実質的にセラミック粉末を含まないことが好ましい。ここで、「実質的にセラミック粉末を含まない」は、封着材料中のセラミック粉末の含有量が０．１質量％未満であることを意味する。 In addition, it is preferable that the sealing material of the present invention is substantially free of ceramic powder. Here, "substantially free of ceramic powder" means that the content of ceramic powder in the sealing material is less than 0.1 mass%.
また、本発明の封着材料では、顆粒形状であることが好ましい。 The sealing material of the present invention is preferably in a granular form.
また、本発明の封着材料では、焼結体であることが好ましい。 The sealing material of the present invention is preferably a sintered body.
本発明のガラス組成物は、ガラス組成として、下記酸化物基準のモル％で、ＴｅＯ２ ４０～８５％、ＭｏＯ３ ０～２０％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ １～２０％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ １～２０％、ＭｎＯ＋Ｃｒ２Ｏ３＋Ｆｅ２Ｏ３＋Ｃｏ３Ｏ４ ０．１～８％を含有する。上記のように各成分の含有量を限定した理由を下記に説明する。なお、各成分の含有量の説明箇所において、％表示は、モル％を指す。 The glass composition of the present invention contains, as a glass composition, in mole percent based on the following oxides, 40-85% TeO2 , 0-20 % MoO3, 1-20 % Li2O + Na2O +K2O, 1-20% MgO+CaO+ SrO +BaO, and 0.1-8% MnO + Cr2O3 + Fe2O3 + Co3O4 . The reasons for limiting the content of each component as described above are explained below . In the description of the content of each component, the % indicates mol%.
ＴｅＯ２は、ガラス骨格を形成するための主成分であり、その含有量は４０～８５％であり、好ましくは５５～８０％、より好ましく６０～７５％である。ＴｅＯ２の含有量が少なくなると、作業点が高くなり過ぎる虞がある。一方、ＴｅＯ２の含有量が多くなると、ガラスの安定性を維持し難くなる。 TeO2 is the main component for forming the glass skeleton, and its content is 40 to 85%, preferably 55 to 80%, and more preferably 60 to 75%. If the content of TeO2 is low, the working point may become too high. On the other hand, if the content of TeO2 is high, it becomes difficult to maintain the stability of the glass.
ＭｏＯ３は、ガラスを安定化させる成分であり、その含有量は０～２０％であり、好ましくは６～１５％、より好ましくは８～１２％である。ＭｏＯ３の含有量が多くなると、溶融時にガラス化し難くなる。 MoO3 is a component that stabilizes glass, and its content is 0 to 20%, preferably 6 to 15%, and more preferably 8 to 12%. If the MoO3 content is high, it becomes difficult to vitrify the glass during melting.
アルカリ金属酸化物（Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ）は、溶融性を高めると共に、固着温度を低下させる成分である。Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏの含有量は１～２０％であり、好ましくは２～１７％、より好ましくは３～１３％である。Ｌｉ２Ｏの含有量は、好ましくは０～１０％、より好ましくは０．１～８％、更に好ましくは１～５％である。Ｎａ２Ｏの含有量は、好ましくは０～１０％、より好ましくは０．１～８％、更に好ましくは１～５％である。Ｋ２Ｏの含有量は、好ましくは０～１０％、より好ましくは０．１～８％、更に好ましくは１～５％である。アルカリ金属酸化物の含有量が少なくなると、溶融性が低下し、また固着温度が高くなり、封着時に金属部材との間に応力が残留し易くなる。一方、アルカリ金属酸化物の含有量が多くなると、耐水性が低下し易くなる。 Alkali metal oxides (Li 2 O, Na 2 O, K 2 O) are components that increase melting property and decrease the bonding temperature. The content of Li 2 O + Na 2 O + K 2 O is 1 to 20%, preferably 2 to 17%, more preferably 3 to 13%. The content of Li 2 O is preferably 0 to 10%, more preferably 0.1 to 8%, and even more preferably 1 to 5%. The content of Na 2 O is preferably 0 to 10%, more preferably 0.1 to 8%, and even more preferably 1 to 5%. The content of K 2 O is preferably 0 to 10%, more preferably 0.1 to 8%, and even more preferably 1 to 5%. When the content of alkali metal oxides is reduced, melting property decreases, and the bonding temperature increases, and stress tends to remain between the metal member during sealing. On the other hand, when the content of alkali metal oxides is increased, water resistance tends to decrease.
アルカリ土類金属酸化物（ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ）は、ガラスを安定化させる成分であり、その含有量の合量は１～２０％、好ましくは３～１５％、特に好ましくは５～１２％である。ＭｇＯの含有量は、好ましくは０～１０％、より好ましくは０～５％、更に好ましくは０～２％である。ＣａＯの含有量は、好ましくは０～１２％、より好ましくは１～９％、更に好ましくは３～７％である。ＳｒＯの含有量は、好ましくは０～１０％、より好ましくは０～５％、更に好ましくは０～２％である。ＢａＯの含有量は、好ましくは０～１２％、より好ましくは０．１～７％、更に好ましくは１～５％である。アルカリ土類金属酸化物の含有量が少なくなると、不安定なガラス構造になり、ガラスを溶融し難くなる。一方、アルカリ土類金属酸化物の含有量が多くなると、溶融時にガラス化し難くなる。 Alkaline earth metal oxides (MgO, CaO, SrO, BaO) are components that stabilize glass, and their total content is 1 to 20%, preferably 3 to 15%, and particularly preferably 5 to 12%. The content of MgO is preferably 0 to 10%, more preferably 0 to 5%, and even more preferably 0 to 2%. The content of CaO is preferably 0 to 12%, more preferably 1 to 9%, and even more preferably 3 to 7%. The content of SrO is preferably 0 to 10%, more preferably 0 to 5%, and even more preferably 0 to 2%. The content of BaO is preferably 0 to 12%, more preferably 0.1 to 7%, and even more preferably 1 to 5%. If the content of alkaline earth metal oxides is low, the glass structure becomes unstable and it becomes difficult to melt the glass. On the other hand, if the content of alkaline earth metal oxides is high, it becomes difficult to vitrify during melting.
ＭｎＯ、Ｃｒ２Ｏ３、Ｆｅ２Ｏ３及びＣｏ２Ｏ３は、ガラスと金属部材の密着性を高める成分である。ＭｎＯ＋Ｃｒ２Ｏ３＋Ｆｅ２Ｏ３＋Ｃｏ３Ｏ４の含有量は０．１～８％、好ましくは０．３～７％、より好ましくは０．５～６％、更に好ましくは１．５～５％である。ＭｎＯの含有量は、好ましくは０～７％、より好ましくは０～５％、更に好ましくは０．１～３％である。Ｃｒ２Ｏ３の含有量は、好ましくは０～７％、より好ましくは０～５％、更に好ましくは０．１～３％である。Ｆｅ２Ｏ３の含有量は、好ましくは０～７％、より好ましくは０～５％、更に好ましくは０．１～３％である。Ｃｏ３Ｏ４の含有量は、好ましくは０～７％、より好ましくは０～５％、更に好ましくは０．１～３％である。これらの成分の含有量が少なくなると、ガラスと金属部材の密着性が不足して、同軸コネクタ端子等の気密信頼性が低下し易くなる。一方、これらの成分の含有量が多くなると、ガラス中に失透ブツが発生する虞がある。 MnO, Cr 2 O 3 , Fe 2 O 3 and Co 2 O 3 are components that enhance the adhesion between glass and metal members. The content of MnO+Cr 2 O 3 +Fe 2 O 3 +Co 3 O 4 is 0.1-8%, preferably 0.3-7%, more preferably 0.5-6%, and even more preferably 1.5-5%. The content of MnO is preferably 0-7%, more preferably 0-5%, and even more preferably 0.1-3%. The content of Cr 2 O 3 is preferably 0-7%, more preferably 0-5%, and even more preferably 0.1-3%. The content of Fe 2 O 3 is preferably 0-7%, more preferably 0-5%, and even more preferably 0.1-3%. The content of Co 3 O 4 is preferably 0 to 7%, more preferably 0 to 5%, and even more preferably 0.1 to 3%. If the content of these components is low, the adhesion between the glass and the metal member is insufficient, and the airtight reliability of the coaxial connector terminal, etc. is likely to decrease. On the other hand, if the content of these components is high, there is a risk of devitrification particles occurring in the glass.
本発明の封着材料は、上記のガラス組成物からなるガラス粉末とセラミック粉末とを含有する封着材料であって、ガラス粉末の含有量が６０～１００質量％、セラミック粉末の含有量が０～４０質量％であることが好ましく、ガラス粉末の含有量が８０～１００質量％、セラミック粉末の含有量が０～２０質量％であることがより好ましく、ガラス粉末の含有量が９５～１００質量％、セラミック粉末の含有量が０～５質量％であることが更に好ましく、ガラス粉末の含有量が９９．９超～１００質量％、セラミック粉末の含有量が０～０．１質量％未満であること、つまりセラミック粉末を実質的に含まないことが特に好ましい。ガラス粉末が少なくなると、焼成時に封着材料が流動し難くなる。 The sealing material of the present invention is a sealing material containing glass powder made of the above glass composition and ceramic powder, and the glass powder content is preferably 60 to 100 mass % and the ceramic powder content is 0 to 40 mass %, more preferably the glass powder content is 80 to 100 mass % and the ceramic powder content is 0 to 20 mass %, further preferably the glass powder content is 95 to 100 mass % and the ceramic powder content is 0 to 5 mass %, and it is particularly preferable that the glass powder content is more than 99.9 to 100 mass % and the ceramic powder content is 0 to less than 0.1 mass %, that is, the sealing material is substantially free of ceramic powder. If the amount of glass powder is small, the sealing material will not flow easily during firing.
セラミック粉末は、種々の材料を使用可能であるが、封着材料を高膨張化する観点から、コーディエライト、クリストバライト、トリジマイト、フッ化カルシウムの何れが好ましい。 Various materials can be used as the ceramic powder, but cordierite, cristobalite, tridymite, or calcium fluoride are preferred from the viewpoint of increasing the expansion of the sealing material.
本発明の封着材料において、温度範囲３０℃～３８０℃での熱膨張係数は、好ましくは１５０×１０－７～２００×１０－７／℃、より好ましくは１６０×１０－７～１９０×１０－７／℃、更に好ましくは１６５×１０－７～１８５×１０－７／℃である。熱膨張係数が高過ぎると、同軸コネクタ端子の作製後に、封着材料が金属シェルによって十分に圧縮された状態にならず、封着強度を維持し難くなる。一方、熱膨張係数が低過ぎると、同軸コネクタ端子の作製後に、封着材料が金属ピンによって過度に引っ張られた状態になり、金属ピンとの界面において、封着材料にクラックが発生し易くなる。なお、「熱膨張係数」は、押棒式熱膨張係数測定装置（ＴＭＡ）で測定した平均線熱膨張係数を指す。 In the sealing material of the present invention, the thermal expansion coefficient in the temperature range of 30°C to 380°C is preferably 150 x 10 -7 to 200 x 10 -7 /°C, more preferably 160 x 10 -7 to 190 x 10 -7 /°C, and even more preferably 165 x 10 -7 to 185 x 10 -7 /°C. If the thermal expansion coefficient is too high, the sealing material is not sufficiently compressed by the metal shell after the coaxial connector terminal is produced, making it difficult to maintain the sealing strength. On the other hand, if the thermal expansion coefficient is too low, the sealing material is excessively pulled by the metal pin after the coaxial connector terminal is produced, making it easy for cracks to occur in the sealing material at the interface with the metal pin. The "thermal expansion coefficient" refers to the average linear thermal expansion coefficient measured by a push rod type thermal expansion coefficient measuring device (TMA).
本発明の封着材料において、作業温度は、好ましくは９００℃以下、より好ましくは８５０℃以下、更に好ましくは８２０℃以下、特に好ましくは８００℃以下である。作業温度が高過ぎると、バネ性が高い金属部材の融点を上回る温度で封着しなければ流動性を確保できず、同軸コネクタ端子の気密信頼性が低下し易くなる。なお、「作業温度」は、高温粘度が１×１０７．６ｐｏｉｓｅになる温度を指す。 In the sealing material of the present invention, the working temperature is preferably 900° C. or less, more preferably 850° C. or less, even more preferably 820° C. or less, and particularly preferably 800° C. or less. If the working temperature is too high, the fluidity cannot be ensured unless sealing is performed at a temperature above the melting point of the metal member with high spring properties, and the airtight reliability of the coaxial connector terminal is likely to decrease. The "working temperature" refers to the temperature at which the high-temperature viscosity becomes 1×10 7.6 poise.
本発明の封着材料は、顆粒形状であることが好ましい。このようにすれば、打錠成型により、所定形状の圧粉体、特に金属ピンを通すための貫通孔を有する圧粉体を容易に作製することができる。 The sealing material of the present invention is preferably in a granular form. In this way, a powder compact of a predetermined shape, particularly a powder compact having a through hole for passing a metal pin, can be easily produced by tableting.
本発明の封着材料は、焼結体であることが好ましい。このようにすれば、金属ピンを挿入した後、金属シェル内に収容する際に、封着材料の欠けを防止することができる。 The sealing material of the present invention is preferably a sintered body. This makes it possible to prevent chipping of the sealing material when the metal pin is inserted and then housed in the metal shell.
焼結体の焼結密度は、好ましくは８２％以上、８５％以上、８８％以上、９２％以上、特に９５～９９％である。焼結体の封着密度は、焼結体中の泡の割合を反映している。焼結密度が小さい程、焼結体中の泡の割合が大きくなり、封着不良が発生し易くなる。ここで、「焼結密度」は、{（焼結体の密度）／（泡なしのガラスバルクの密度）}×１００の式で算出した値を指す。 The sintered density of the sintered body is preferably 82% or more, 85% or more, 88% or more, 92% or more, and particularly 95 to 99%. The sealing density of the sintered body reflects the proportion of bubbles in the sintered body. The smaller the sintered density, the greater the proportion of bubbles in the sintered body, making it more likely that poor sealing will occur. Here, "sintered density" refers to the value calculated using the formula {(density of sintered body)/(density of glass bulk without bubbles)} x 100.
以下、本発明を実施例に基づいて説明する。なお、以下の実施例は単なる例示である。本発明は、以下の実施例に何ら限定されない。 The present invention will be described below based on examples. Note that the following examples are merely illustrative. The present invention is not limited to the following examples in any way.
表１は、本発明の実施例（試料Ｎｏ．１～３）及び比較例（試料Ｎｏ．４、５）を示している。 Table 1 shows examples of the present invention (samples No. 1 to 3) and comparative examples (samples No. 4 and 5).
まず表中のガラス組成になるように、ガラス原料を調合したガラスバッチを白金坩堝に入れ、９００℃で２時間溶融した。ガラスバッチの溶解に際しては、白金スターラーを用いて攪拌し、均質化を行った。次いで、溶融ガラスをカーボン板上に流し出し、フィルム上または板状に成形した。板状試料については、徐冷点より２０℃程度高い温度から、３℃／分で常温まで徐冷した。 First, a glass batch containing glass raw materials mixed to obtain the glass composition shown in the table was placed in a platinum crucible and melted at 900°C for 2 hours. When melting the glass batch, it was stirred with a platinum stirrer to homogenize it. The molten glass was then poured onto a carbon plate and formed into a film or plate. The plate samples were slowly cooled from a temperature about 20°C higher than the annealing point to room temperature at a rate of 3°C/min.
熱膨張係数は、３０～３８０℃の温度範囲において、押棒式熱膨張係数測定装置（ＴＭＡ）で測定した平均線熱膨張係数である。 The thermal expansion coefficient is the average linear thermal expansion coefficient measured using a push rod type thermal expansion coefficient measuring device (TMA) in the temperature range of 30 to 380°C.
作業温度は、板状試料を用いて、白金球引き上げ法により測定されたガラス粘性より算出したものであり、高温粘性が１０７．６ｐｏｉｓｅになる温度である。 The working temperature was calculated from the glass viscosity measured by the platinum ball pull-up method using a plate-shaped sample, and was the temperature at which the high-temperature viscosity was 10 7.6 poise.
次に、フィルム状ガラス試料を平均粒径Ｄ５０＝２０～３０μｍに粉砕、分級して、ガラス粉末を得た。必要に応じて、セラミック粉末（試料Ｎｏ．３ではコーディエライトを使用）を表中に記載の割合で添加して、複合粉末を得た。 Next, the film-like glass sample was crushed to an average particle size D of 20 to 30 μm and classified to obtain a glass powder. If necessary, a ceramic powder (cordierite was used in sample No. 3) was added in the proportions shown in the table to obtain a composite powder.
密着性は、得られた粉末試料を圧粉体としてボタン状に成型し、黄銅製の板の上に置いて作業温度で１５分間焼成した後に室温まで冷却し、得られた焼結体が指の力で剥がれない場合を「○」、剥がれる場合を「×」として、評価したものである。 The adhesion was evaluated by forming the obtained powder sample into a button-like compact, placing it on a brass plate, sintering it at the working temperature for 15 minutes, and then cooling it to room temperature. If the obtained sintered body could not be peeled off with the force of a finger, it was marked as "○", and if it could be peeled off, it was marked as "×".
表１から明らかなように、試料Ｎｏ．１～３は、作業温度が８１９℃以下であり、密着性の評価も良好であった。よって、試料Ｎｏ．１～３は、同軸コネクタ端子の封着に使用する際に良好な気密信頼性が得られるものと考えられる。一方、試料Ｎｏ．４では作業温度が８６８℃であった。試料Ｎｏ．５では密着性の評価で焼結体に失透が認められた。よって、試料Ｎｏ．４、５は、同軸コネクタ端子の封着に使用する際に良好な気密信頼性が得られないものと考えられる。 As is clear from Table 1, the working temperature for samples No. 1 to No. 3 was 819°C or less, and the adhesion evaluation was also good. Therefore, it is believed that samples No. 1 to No. 3 will provide good airtight reliability when used to seal coaxial connector terminals. On the other hand, the working temperature for sample No. 4 was 868°C. In sample No. 5, devitrification was observed in the sintered body during the adhesion evaluation. Therefore, it is believed that samples No. 4 and 5 will not provide good airtight reliability when used to seal coaxial connector terminals.
試料Ｎｏ．１に係るガラス粉末に対して、セラミック粉末（コーディエライトを使用）を表中に記載の割合で添加して、試料Ｎｏ．６に係る複合粉末を得た。試料Ｎｏ．６に対して、上記の通り、熱膨張係数、作業温度及び密着性の評価を行った。その結果を表２に示す。 Ceramic powder (cordierite used) was added to the glass powder of sample No. 1 in the ratio shown in the table to obtain the composite powder of sample No. 6. As described above, the thermal expansion coefficient, working temperature, and adhesion of sample No. 6 were evaluated. The results are shown in Table 2.
表２から明らかなように、試料Ｎｏ．１は、密着性の評価が良好であった。一方、試料Ｎｏ．６では密着性の評価で焼結体が流動しなかった。よって、試料Ｎｏ．６は、同軸コネクタ端子の封着に使用する際に良好な気密信頼性が得られないものと考えられる。 As is clear from Table 2, sample No. 1 was evaluated as having good adhesion. On the other hand, the sintered body of sample No. 6 did not flow during the adhesion evaluation. Therefore, it is believed that sample No. 6 does not provide good airtight reliability when used to seal coaxial connector terminals.
１ 同軸コネクタ端子
１１ 金属ステム
１２ 金属ピン
１３ 封着材料
1 Coaxial connector terminal 11 Metal stem 12 Metal pin 13 Sealing material
Claims (4)
ガラス粉末の含有量が６０～１００質量％、セラミック粉末の含有量が０～４０質量％であり、
通信用同軸コネクタ端子の封着に用いることを特徴とする封着材料。 A sealing material containing a glass powder made of a glass composition containing, in mole percent based on the following oxides, TeO 2 40-85%, MoO 3 0-20%, Li 2 O + Na 2 O + K 2 O 1-20%, MgO + CaO + SrO + BaO 1-20%, MnO + Cr 2 O 3 + Fe 2 O 3 + Co 3 O 4 0.1-8% , and a ceramic powder,
The content of the glass powder is 60 to 100% by mass, and the content of the ceramic powder is 0 to 40% by mass,
A sealing material characterized by being used for sealing coaxial connector terminals for communication .
3. The sealing material according to claim 1 , which is a sintered body.
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| JP2021035896A (en) | 2019-08-30 | 2021-03-04 | 昭和電工マテリアルズ株式会社 | Lead-free low melting point glass composition, low melting point glass composite material, glass paste and applied products |
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