WO2003045864A1 - Composition de scellement et materiau de scellement - Google Patents

Composition de scellement et materiau de scellement Download PDF

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Publication number
WO2003045864A1
WO2003045864A1 PCT/JP2002/012346 JP0212346W WO03045864A1 WO 2003045864 A1 WO2003045864 A1 WO 2003045864A1 JP 0212346 W JP0212346 W JP 0212346W WO 03045864 A1 WO03045864 A1 WO 03045864A1
Authority
WO
WIPO (PCT)
Prior art keywords
sealing
mass
sealing composition
binder
glass
Prior art date
Application number
PCT/JP2002/012346
Other languages
English (en)
Japanese (ja)
Inventor
Naoshi Irisawa
Jiro Chiba
Original Assignee
Asahi Glass Company, Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Company, Limited filed Critical Asahi Glass Company, Limited
Priority to AU2002354062A priority Critical patent/AU2002354062A1/en
Priority to JP2003547324A priority patent/JP4155194B2/ja
Publication of WO2003045864A1 publication Critical patent/WO2003045864A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders

Definitions

  • the present invention relates to a sealing composition and a sealing material used for joining or sealing glass, metal, ceramics, and the like.
  • the joining or sealing of glass, metal, ceramics, and the like is usually performed by turning a powder material into a slurry or a paste, applying it to the joint, and firing it.
  • a binder is added to the powder material, a pressed body is formed by press molding, and calcination is performed in the air for the purpose of removing the binder and imparting strength.
  • the preliminarily fired press body is set up at the joint portion of the adherend to be joined or sealed, and then baked (finally baked) to join or seal the adherend.
  • An object of the present invention is to provide a sealing composition and a sealing material that can solve the above problems. Disclosure of the invention
  • the present invention is expressed in terms of mass percentage (percentages in the present invention are unless otherwise specified.
  • a sealing composition consisting essentially of 70 to 100% of glass powder, 0 to 30% of refractory filler, and 0 to 5% of heat-resistant pigment; Powder by mass percentage based on the following oxides, S i 0 2: 7 17 %, B 2 0 3: 1 7 ⁇ 27%, ZnO: 55 ⁇ 65%, Ce_ ⁇ 2: 0. 01 5%, MgO + C a
  • the sealing composition consists essentially of the sealing composition, a binder, and a release agent.
  • the binder is 1 to 6 parts by mass, and the release agent is 0.05 to 2 parts by mass with respect to 100 parts by mass of the sealing composition.
  • the binder is at least one resin selected from the group consisting of polyethylene glycol, polyethylene oxide and an acrylic resin, and the release agent is stearic acid.
  • a sealing material characterized by being at least one organic compound selected from the group consisting of lauric acid, metal salts of stearic acid, metal salts of lauric acid, liquid paraffin and paraffin wax.
  • the sealing composition of the present invention is usually added with a binder such as polyethylene glycol and a release agent such as stearic acid, and, if necessary, further added with a dispersant, a plasticizer, an antifoaming agent and the like to form a slurry, It is dried by a spray dryer or the like to obtain granulated powder.
  • the granulated powder is dry-pressed into a desired shape to form a pressed body, and then subjected to calcination (binder removal treatment) in which the powder is held at 500 to 650 in air for the purpose of burning out the binder in the pressed body.
  • calcination bin removal treatment
  • the pre-baked press body is incorporated into a jig together with the adherend to be joined or sealed, and is fully fired at 750 to 850 to form a joined body or a sealed body.
  • the adherend is, for example, glass, metal or ceramic.
  • the atmosphere in which the main firing is performed is not limited, and the main firing is performed in the air, in a neutral atmosphere such as nitrogen gas, or the like, if necessary.
  • Glass powder is an essential component for bonding or sealing. Bondability at less than 70% Or, the sealing property decreases. Preferably it is 90% or more.
  • the mass average particle size of the glass powder is typically between 5 and 20 im.
  • S i 0 2 is essential is a network former. If it is less than 7%, there is a risk of devitrification at the time of melting the glass, or the crystallization rate at the time of main firing is increased, and the fluidity is reduced. It is preferably at least 10%. If it exceeds 17%, the softening point increases and the fluidity decreases. Preferably it is 14% or less.
  • B 2 ⁇ 3 is a flux component for vitrification and is essential. If it is less than 17%, the softening point will be high and the fluidity will decrease. It is preferably at least 20%. If it exceeds 27%, the softening point is low, and a bonded or sealed body having a desired shape cannot be obtained. It is preferably at most 24%.
  • Zn_ ⁇ is Zetaita_ ⁇ ⁇ beta 2 0 3 based crystal, a component for depositing Zn_ ⁇ 'S I_ ⁇ 2 crystal, ZnO' a Z n O containing crystals of MgO-based crystal or the like during the firing, an essential is there. If it is less than 55%, the precipitation of Zn ⁇ -containing crystals becomes insufficient, and the heat resistance decreases. It is preferably at least 58%. If it exceeds 65%, devitrification may occur when the glass is melted. It is preferably at most 62%.
  • CeO 2 is an essential component for preventing or suppressing carbon residue in the preliminary firing or the main firing. If it is less than 0.01%, the prevention or suppression of carbon residue becomes insufficient. It is preferably at least 0.03%. If it exceeds 5%, the softening point increases and the fluidity decreases. Preferably it is 2% or less.
  • MgO, Ca ⁇ , 31 ′′ ⁇ or 8 & ⁇ are to be constituents of the ZnO-containing crystal, and at least one of them must be contained. If the total MgO + CaO + S1 "0 + 8 & 0 is less than 0.5%, the precipitation of 2110-containing crystals will be insufficient and the heat resistance will decrease. It is preferably at least 3%. If it exceeds 10%, the softening point increases and the fluidity decreases. Preferably it is 7% or less.
  • Al 2 ⁇ 3 has an effect of adjusting the crystal deposition rate or an effect of improving water resistance, and is essential. If it is less than 0.1%, the effect is small. It is preferably at least 0.3%. If it exceeds 5%, the softening point of the glass increases, and the fluidity decreases. Preferably it is less than 2%.
  • Sn_ ⁇ 2 T i 0 2 and Z r 0 2 has the effect of improving the water resistance, or One or more must be contained.
  • These 3 In total S n0 2 + T I_ ⁇ 2 + Z R_ ⁇ less than 2 0.01% of the content of the component, the effect is small. It is preferably at least 0.01%. If it exceeds 3%, the glass may have a high softening point or may be devitrified when the glass is melted. It is preferably at most 2%.
  • the glass powder used in the sealing composition of the present invention consists essentially of the above components, but may contain other components as long as the object of the present invention is not impaired.
  • the total content of the other components is preferably 5% or less.
  • Examples other components may contain L a 2 ⁇ 3, P 2 ⁇ 5, V 2 0 5 and the like for adjusting viscosity upon melting.
  • the refractory filler is not essential, but the strength of the fired body is improved, the thermal expansion coefficient is adjusted, or the crystallization rate is adjusted. For example, it may be contained up to 30%. If it exceeds 30%, the sinterability decreases. Preferably it is 20% or less. When the refractory filler is contained, its preferable content is 0.1% or more.
  • the refractory filler is preferably an oxide powder of one or more elements selected from the group consisting of Ce, Zn, Mg, Zr, A1 and Si.
  • the heat-resistant pigment is not essential, but may be contained up to 5% for coloring the fired body. If it exceeds 5%, changes in thermal properties such as the coefficient of thermal expansion, electrical properties such as the dielectric loss tangent, and the like become large. Preferably it is 2% or less. When a heat-resistant pigment is contained, the preferred content is 0.5% or more.
  • the heat-resistant pigment is preferably an oxide powder of one or more elements selected from the group consisting of Fe, Mn, Cu, Cr and Co.
  • powders of chromium-based oxide, iron-manganese-based oxide, copper-chromium-based oxide, and cobalt-based oxide can be used.
  • the sealing composition of the present invention consists essentially of the above components, but may contain other components as long as the object of the present invention is not impaired.
  • the sum of the contents of the other components is It is preferably at most 5%.
  • the sealing material of the present invention will be described below with the content of the sealing composition of the present invention being 100 parts by mass.
  • the sealing composition of the present invention is an essential component for bonding or sealing.
  • a binder which is at least one resin selected from the group consisting of polyethylene glycol, polyethylene oxide and acrylic resin, is indispensable, and it is possible to remove the binder at a relatively low temperature and obtain a molded product having high strength. It has the following characteristics. If the amount of the binder is less than 1 part by mass, the strength of the formed body is reduced. If it exceeds 6 parts by mass, the binder removal will be insufficient. Above all, the preferred content of the binder is 2 to 5.5 parts by mass.
  • the release agent which is an organic compound, is a component for preventing adhesion to a molding die during press molding or for improving the density of a pressed body obtained by press molding, and is essential.
  • the amount of the release agent is less than 0.05 parts by mass, the prevention of the adhesion or the improvement of the density becomes insufficient. At 2 parts by mass, the binder removal becomes insufficient.
  • the preferable content of the release agent is 0.05 to 1.5 parts by mass.
  • the sealing material of the present invention consists essentially of the above components, but may contain other components as long as the object of the present invention is not impaired.
  • the total content of the other components is preferably 5% or less in the sealing material.
  • the sealing material of the present invention is used in a method in which the pre-fired pressed body is baked and joined or sealed, it is preferably granulated powder that has been granulated.
  • the average particle size of the granulated powder is typically 50 to 300 am.
  • composition containing the glass powder, the refractory filler and the heat-resistant pigment in a ratio indicated by mass percentage in the column from the glass to the heat-resistant pigment in the table contains a binder and a release agent.
  • Examples 1 to 8 are working examples, and Examples 9 and 10 are comparative examples.
  • ZnO powder was used as the refractory filler
  • cobalt-based oxide powder was used as the heat-resistant pigment
  • polyethylene glycol was used as the binder
  • stearic acid was used as the release agent.
  • the slurry was dried and granulated by a spray dryer to obtain granulated powder having an average particle diameter of 110 to 120.
  • the granulated product is put into a mold and dry-pressed to form a 15 mm X 7.5 mm X 3 mm pressed body.
  • the binder is removed by pre-baking (removal of binder) by holding the pressed body at 60 O in the atmosphere for 15 minutes.
  • the calcined product (13.5mmX6.8mmX2.7mm) was obtained.
  • the calcined body was placed in a rectangular cylindrical Kovar metal frame with a height of 5 mm and a size of 14 mm x 7 mm, and the upper and lower surfaces were 6 mm thick and a 13.5 mm x 6.5 mm carbon plate. Two pieces were sandwiched and fixed to the metal frame.
  • the coloring property, the joining strength, the foaming property, the carbon adhering property, the gas releasing property, and the molding workability were evaluated as follows.
  • Colorability The surface of the calcined body was visually observed, and those without coloring or discoloration were rated good, and those with slight coloring or discoloration were rated poor. This coloring or discoloration is caused by the lack of binder removal, and it is considered that the effect of the binder removal in the calcined body cannot be removed by the main firing.
  • Bonding strength The Kovar metal frame of the bonded body was fixed with a jig, and a force of 147 N was applied to the glass molded body of the bonded body. A glass molded body that did not peel from the Kovar metal frame was rated good, and a peeled glass molded body was rated poor.
  • Foaming property The bonded body was left standing for 1 hour under a reduced pressure atmosphere with a pressure of 3 OTorr (4000 Pa) and a temperature of 800, and was taken out. Those that were not acceptable were rated good, and those that were recognized were rated poor.
  • Carbon adhesion When the carbon plate is removed after cooling after completion of the main firing, the carbon plate is not fused to the glass molded body and can be easily removed, and there is no carbon bond on the surface of the glass molded body. Good, otherwise bad.
  • Outgassing The joined body was heated from room temperature to 800, and the type and amount of gas generated in the process were examined using a gas mass spectrometer. A case where remarkable gas release was observed was regarded as bad, and a case where it was not noticeable was regarded as good.
  • Molding workability If granulated powder adheres to the inner surface of the mold during the production of the pressed body, problems such as a decrease in the dimensional accuracy of the pressed body and a decrease in the strength of the pressed body will occur. In order to prevent this granulation powder from sticking, the inside of the mold is cleaned to remove deposits on the mold, but the frequency should be once or less every 200 dry presses. Is preferred. The cleaning frequency was good if the cleaning frequency was less than or equal to once every 2000 times, and poor if it was not.
  • Example J 1 Example 2 Example 3 Example 4 Example 5
  • the sealing part or joining part of glass, metal, ceramics, etc. is not colored or discolored, its strength is high, there is no bleeding of glass, No or little gas is released, and there is no sticking to the carbon jig used at the time of sealing or joining, so that a sealing material having good press body molding workability can be obtained.
  • the method of bonding and sealing the pre-fired press body by firing and bonding or sealing it depends on the shape or size of the press body. In many cases, it had to be contained, and there was a problem of insufficient binder removal. If the binder removal is insufficient, carbon remains in the fired body that has been finally fired, and the fired body is colored. And other problems may occur.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

Cette invention concerne une composition de scellement renfermant entre 70 et 100 % en masse de poudre de verre, entre 0 et 30 % en masse de charge réfractaire et entre 0 et 5 % en masse d'un pigment thermorésistant, le verre présentant la composition chimique suivante : entre 7 et 17 % de SiO2, entre 17 et 27 % de B2O3, entre 55 et 65 % de ZnO, entre 0,01 et 5 % de CeO2, entre 0,5 et 10 % de MgO+CaO+SrO+BaO, entre 0,1 et 0,5 % de Al2O3, entre 0,01 et 3 % de SnO2+TiO2+ZrO2. Cette composition est exempte de plomb, de bismuth, de cadmium et de métal alcalin.
PCT/JP2002/012346 2001-11-30 2002-11-27 Composition de scellement et materiau de scellement WO2003045864A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2002354062A AU2002354062A1 (en) 2001-11-30 2002-11-27 Sealing composition and sealing material
JP2003547324A JP4155194B2 (ja) 2001-11-30 2002-11-27 封着用組成物および封着材

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001366680 2001-11-30
JP2001-366680 2001-11-30

Publications (1)

Publication Number Publication Date
WO2003045864A1 true WO2003045864A1 (fr) 2003-06-05

Family

ID=19176543

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2002/012346 WO2003045864A1 (fr) 2001-11-30 2002-11-27 Composition de scellement et materiau de scellement

Country Status (4)

Country Link
JP (1) JP4155194B2 (fr)
CN (1) CN100355684C (fr)
AU (1) AU2002354062A1 (fr)
WO (1) WO2003045864A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008007596A1 (fr) * 2006-07-14 2008-01-17 Central Glass Company, Limited VERRE SANS PLOMB à bas point de fusion
JP2008511527A (ja) * 2004-08-28 2008-04-17 ヘレウス・クアルツグラース・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・ウント・コンパニー・コマンディット・ゲゼルシャフト 構成部品の接合のための接合剤、高ケイ酸含量を有する材料で作製される構成部品の接合方法、及びその方法により得られる構成部品アセンブリ
EP2703454A1 (fr) * 2012-08-29 2014-03-05 Pemco Brugge BVBA Compositions de revêtement
JPWO2016208671A1 (ja) * 2015-06-23 2018-04-12 旭硝子株式会社 焼成成形体およびその製造方法、焼成成形体を備える物品、焼成成形体用材料、ならびに、焼成前成形体およびその製造方法

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DE102006062428B4 (de) * 2006-12-27 2012-10-18 Schott Ag Verfahren zur Herstellung eines mit einem bleifreien Glas passiviertenelektronischen Bauelements sowie elektronisches Bauelement mit aufgebrachtem bleifreien Glas und dessen Verwendung
CN101774766A (zh) * 2010-01-15 2010-07-14 四川虹欧显示器件有限公司 介质用耐酸无铅玻璃粉
CN102781863B (zh) * 2010-02-24 2015-01-21 日本山村硝子株式会社 玻璃组合物以及密封材料
KR101162042B1 (ko) 2011-11-24 2012-07-04 대주전자재료 주식회사 산화 분위기에서 소성 가능한 봉착용 유리 조성물 및 이를 포함하는 디스플레이 패널
CN103420622A (zh) * 2012-05-17 2013-12-04 华硕电脑股份有限公司 金属与玻璃复层材料的制备方法及其系统
TWI477388B (zh) * 2012-07-04 2015-03-21 Darfon Materials Corp 製造殼體之方法及殼體
CN103253866B (zh) * 2013-05-24 2015-07-22 福州大学 一种含SnO2的玻璃封接材料制备及其使用方法
CN105502953B (zh) * 2016-01-14 2018-06-12 中澳科创（深圳）新材料有限公司 铁封玻璃粉浆料及其制备方法
CN105601118A (zh) * 2016-01-14 2016-05-25 中澳科创（深圳）新材料有限公司 压缩机接线端子用铁封玻璃及其制备工艺
CN109279781A (zh) * 2018-10-12 2019-01-29 沈阳建筑大学 用于氧化锆和二硅酸锂玻璃陶瓷的粘结剂及其制法和应用
CN114410149A (zh) * 2022-02-16 2022-04-29 中健特种玻璃科技有限公司 一种真空玻璃腔体支撑油墨及其制备方法和应用

Citations (4)

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Publication number Priority date Publication date Assignee Title
JPS58204837A (ja) * 1982-05-19 1983-11-29 Asahi Glass Co Ltd 封着用結晶性ガラス組成物
JPH02133336A (ja) * 1988-11-10 1990-05-22 Asahi Glass Co Ltd 封着用組成物
JPH02311330A (ja) * 1989-05-26 1990-12-26 Nippon Electric Glass Co Ltd セラミックスコンデンサー用バインダーガラス
JPH10236844A (ja) * 1997-02-26 1998-09-08 Iwaki Glass Kk 封着用組成物

Family Cites Families (3)

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US5114885A (en) * 1991-04-16 1992-05-19 E. I. Du Pont De Nemours And Company Encapsulant composition
US5753571A (en) * 1997-02-13 1998-05-19 E. I. Du Pont De Nemours And Company Lead and cadmium-free encapsulant composition
US6387833B1 (en) * 1999-08-13 2002-05-14 Asahi Glass Company, Limited Sealing composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58204837A (ja) * 1982-05-19 1983-11-29 Asahi Glass Co Ltd 封着用結晶性ガラス組成物
JPH02133336A (ja) * 1988-11-10 1990-05-22 Asahi Glass Co Ltd 封着用組成物
JPH02311330A (ja) * 1989-05-26 1990-12-26 Nippon Electric Glass Co Ltd セラミックスコンデンサー用バインダーガラス
JPH10236844A (ja) * 1997-02-26 1998-09-08 Iwaki Glass Kk 封着用組成物

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008511527A (ja) * 2004-08-28 2008-04-17 ヘレウス・クアルツグラース・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・ウント・コンパニー・コマンディット・ゲゼルシャフト 構成部品の接合のための接合剤、高ケイ酸含量を有する材料で作製される構成部品の接合方法、及びその方法により得られる構成部品アセンブリ
WO2008007596A1 (fr) * 2006-07-14 2008-01-17 Central Glass Company, Limited VERRE SANS PLOMB à bas point de fusion
EP2703454A1 (fr) * 2012-08-29 2014-03-05 Pemco Brugge BVBA Compositions de revêtement
WO2014033098A1 (fr) 2012-08-29 2014-03-06 Pemco Brugge Bvba Compositions de revêtement
JPWO2016208671A1 (ja) * 2015-06-23 2018-04-12 旭硝子株式会社 焼成成形体およびその製造方法、焼成成形体を備える物品、焼成成形体用材料、ならびに、焼成前成形体およびその製造方法

Also Published As

Publication number Publication date
AU2002354062A1 (en) 2003-06-10
CN100355684C (zh) 2007-12-19
CN1596228A (zh) 2005-03-16
JP4155194B2 (ja) 2008-09-24
JPWO2003045864A1 (ja) 2005-04-07

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