CN1914129A - Sealing composition - Google Patents

Sealing composition Download PDF

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Publication number
CN1914129A
CN1914129A CNA2005800034755A CN200580003475A CN1914129A CN 1914129 A CN1914129 A CN 1914129A CN A2005800034755 A CNA2005800034755 A CN A2005800034755A CN 200580003475 A CN200580003475 A CN 200580003475A CN 1914129 A CN1914129 A CN 1914129A
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Prior art keywords
weight
sealing
sealing composition
glass
thermal expansivity
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CNA2005800034755A
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Inventor
真弓祯隆
藤本刚
田口智之
谷上嘉规
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Nihon Yamamura Glass Co Ltd
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Nihon Yamamura Glass Co Ltd
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Publication of CN1914129A publication Critical patent/CN1914129A/en
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes

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

Abstract

Disclosed is a sealing composition containing no lead which enables sealing at low temperatures and has a smaller coefficient of thermal expansion (thermal expansivity). The sealing composition does not substantially contain Pb and is composed of 80-98 % by weight of a glass powder and 2-20 % by weight of an inorganic filler containing a zirconium phosphate compound. The glass powder contains 70-85 % by weight of Bi2O3, 4.5-10 % by weight of B2O3, 8.0-20 % by weight of ZnO and 0.1-1 % by weight of Al2O3 in terms of oxides.

Description

Sealing composition
Technical field
The present invention relates to sealing composition, furtherly, relate to the sealing composition that is substantially free of lead.
Background technology
Always, known as sealing composition by PbO-SiO 2-B 2O 3Be the lead glass powder and the PbTiO of glass etc. 3Deng the composition that constitutes of the ceramic packing with low-thermal-expansion rate.But sealing composition so always all contains lead in glass or the ceramic packing.
In recent years, from the viewpoint of environment aspect, have and avoid using the tendency that contains plumbous goods.
On the other hand, as not containing the plumbous glass that can be used for sealing composition, for example known have a P 2O 5-ZnO system, P 2O 5-SnO system, Bi 2O 3The glass of system wherein, from the viewpoint of chemical durability, uses Bi more 2O 3The glass of system.
As by Bi 2O 3The sealing composition that the glass of system and mineral filler constitute, the applicant for example provides that the spy opens 2003-95697.
Patent documentation 1: the spy opens the 2003-95697 communique
Summary of the invention
But, above-mentioned by Bi 2O 3The sealing composition that the glass of system and mineral filler constitute had been difficult to take into account not only sealing-in at low temperatures but also thermal expansivity is reduced.That is to say, contain filler for a long time, can make the thermal expansivity of sealing composition be reduced to ideal value, but on the other hand, but have to make sealing temperature to rise to nonideal high temperature.In addition, the quantitative change of filler after a little while, sealing temperature can reduce, but thermal expansivity raises, and is limited by the kind of sealing-in thing.For example, with always by Bi 2O 3The unleaded sealing composition that the glass of system and mineral filler constitute can make sealing temperature reach 520 ℃ or below it, but can not make thermal expansivity reach 80 * 10 -7(1/K) or below it.
In addition, when the sealing temperature of sealing composition necessity was risen, the high temperature during because of its sealing-in was given by sealing-in thing and other materials used deterioration and other bad influence remarkable.
Therefore, problem of the present invention is, eliminates the problem points of above-mentioned sealing composition always, provide be lead-free sealing composition, can be under lower temperature sealing-in and the littler sealing composition of thermal expansivity (coefficient of thermal expansion).Specifically, its problem is, but provide sealing temperature at 520 ℃ or below it, thermal expansivity is 80 * 10 -7(1/K) or its following sealing composition, its problem also is, provides sealing temperature at 480 ℃ or below it or even at 450 ℃ or sealing composition below it.
The inventor must solve found that above-mentioned problem studies with keen determination, uses little (comprising the mineral filler that shows negative value) the zirconium phosphate compound of thermal expansivity as mineral filler, as the Bi of glass use specific composition 2O 3-B 2O 3-ZnO-Al 2O 3The glass of system makes both form the unleaded sealing composition that cooperates with specified proportion, by this, just can carry out sealing-in well at low temperatures, can make thermal expansivity (coefficient of thermal expansion) little simultaneously; Also find in addition, but the thermal expansivity of sealing composition than by each thermal expansivity of zirconium phosphate compound and glass calculating thermal expansivity lower (little) according to its cooperation ratio Theoretical Calculation, thereby finished the present invention.
That is to say, finish the 1st being characterised in that of sealing composition of the present invention of above-mentioned problem, be substantially free of lead and constitute by the glass powder of 80～98 weight % and the mineral filler that contains the zirconium phosphate compound of 2～20 weight %, convert with oxide compound, above-mentioned glass powder is the Bi that contains 70～85 weight % 2O 3, 4.5～10 weight % B 2O 3, the ZnO of 8.0～20 weight % and the Al of 0.1～1 weight % 2O 3Composition.
In addition, sealing composition of the present invention is except above-mentioned the 1st feature, and it the 2nd is characterised in that, converts with oxide compound, and glass powder is the Bi that contains 80～83 weight % 2O 3, 4.5～8 weight % B 2O 3, the ZnO of 8.0～12 weight % and the Al of 0.1～0.5 weight % 2O 3Composition.
In addition, sealing composition of the present invention is except the above-mentioned the 1st or the 2nd feature, and it the 3rd is characterised in that, the zirconium phosphate compound that contains in mineral filler is 2 weight % or more than it with respect to the full dose of sealing composition.
In addition, sealing composition of the present invention is except each feature of the above-mentioned the 1st～3, and it the 4th is characterised in that, contains phosphoric acid wolframic acid zirconium as the zirconium phosphate compound.
In addition, sealing composition of the present invention is except each feature of the above-mentioned the 1st～3, and it the 5th is characterised in that the full dose of zirconium phosphate compound is a phosphoric acid wolframic acid zirconium.
According to invention 1 described sealing composition, constitute by the glass powder of 80～98 weight % and the mineral filler that contains the zirconium phosphate compound of 2～20 weight %, convert with oxide compound, above-mentioned glass powder is the Bi that contains 70～85 weight % 2O 3, 4.5～10 weight % B 2O 3, the ZnO of 8.0～20 weight % and the Al of 0.1～1 weight % 2O 3Composition constitute, therefore can be under low temperature fully and have under the situation of fully little thermal expansivity (fully low coefficient of thermal expansion) and carry out sealing-in.
Specifically, can make sealing temperature, and can make thermal expansivity 80 * 10 at 520 ℃ or below it -7Or below it.
In addition, because sealing composition of the present invention is not leaded, so be ideal from the viewpoint of environment aspect yet.
In addition, in sealing composition of the present invention, owing to use above-mentioned Bi as glass ingredient 2O 3-B 2O 3-ZnO-Al 2O 3Be glass, so with regard to can reducing melt temperature, glass is difficult to crystallization when sealing-in is burnt till.
In addition, according to invention 2 described sealing compositions, except by the described effect that constitutes generation of foregoing invention 1, further define the composition of glass powder, convert with oxide compound, above-mentioned glass powder is by the Bi that contains 80～83 weight % 2O 3, 4.5～8 weight % B 2O 3, the ZnO of 8.0～12 weight % and the Al of 0.1～0.5 weight % 2O 3Composition constitute, therefore, can reach well that the further eutectic of sealing composition melts and the glass crystalline effect when suppressing sealing-in and burning till.
In addition, according to invention 3 described sealing compositions, except by foregoing invention 1 or the 2 described effects that constitute generation, is 2 weight % or more than it by the zirconium phosphate compound that contains in the mineral filler with respect to the full dose of sealing composition, can make the thermal expansivity of sealing composition reach 80 * 10 really -7Or below it.
In addition, according to invention 4 described sealing compositions, except by the described effect that constitutes generation of each of foregoing invention 1～3, by contain phosphoric acid wolframic acid zirconium as the zirconium phosphate compound, the negative effect that thermal expansivity produced that is had by phosphoric acid wolframic acid zirconium can be given as all thermal expansivity of sealing composition, the sealing composition of low sealing temperature, low thermal coefficient of expansion just can be provided reliably with the amount of low filler.
Particularly the inventor finds following effect, makes phosphoric acid wolframic acid zirconium and Bi shown in 1,2 like that as inventing 2O 3It is the occasion that glass combination constitutes sealing composition, compare with the thermal expansivity of the sealing composition of calculating as calculated value by the cooperation ratio of phosphoric acid wolframic acid zirconium and glass, one side of the thermal expansivity of actual sealing composition is littler, the sealing composition of low sealing temperature, low thermal coefficient of expansion just can be provided reliably with amount of filler still less by this.
In addition, according to invention 5 described sealing compositions, except by the described effect that constitutes generation of each of foregoing invention 1～3, full dose by the zirconium phosphate compound is a phosphoric acid wolframic acid zirconium, the negative thermal expansivity that reason phosphoric acid wolframic acid zirconium has and the effect that produces and surpass the above-mentioned theory calculated value and reduce the effect of thermal expansivity can be provided at the sealing composition of the low thermal coefficient of expansion under the low sealing temperature more reliably.
Embodiment
The pottery, soda-lime glass, Plasmia indicating panel that sealing composition of the present invention can be used in aluminum oxide etc. is with the metal of high Ni alloy of glass, Kovar alloy and 50 alloys etc. of glass substrate etc. etc., in addition the sealing-in of various materials.
Among the present invention so-called " being substantially free of lead " be meant do not use PbO etc. all with the raw material of lead as principal constituent, do not get rid of the situation that the lead of the trace in the impurity of the raw material that derives from each composition that constitutes glass and mineral filler is sneaked into.
Sealing composition of the present invention is made of the glass powder of 80～98 weight % and the mineral filler that contains the zirconium phosphate compound of 2～20 weight %, converts with oxide compound, and above-mentioned glass powder is the Bi that contains 70～85 weight % 2O 3, 4.5～10 weight % B 2O 3, the ZnO of 8.0～20 weight % and the Al of 0.1～1 weight % 2O 3Composition.
The Bi of its constituent of conduct in the above-mentioned glass powder 2O 3It is the necessary composition that is used to make the thawing of glass eutectic.
Bi in the glass powder 2O 3When being lower than 70 weight %, it is insufficient that the eutectic of glass melts, and in addition, when surpassing 85 weight %, when sealing-in was burnt till, the easy crystallization of glass was as seal, sealing materials sintering well.
Preferred Bi 2O 3Content in glass powder is 80～83 weight %.
In the glass powder as the B of its constituent 2O 3Forming the network of glass, is that sealing-in is used to suppress the necessary composition of glass crystallization when burning till.
B in the glass powder 2O 3When being lower than 4.5 weight %, do not suppress the effect of glass crystallization when sealing-in is burnt till, in addition, when surpassing 10 weight %, the glass instability does not suppress the effect of glass crystallization yet.
Preferred B 2O 3Content in glass powder is 4.5～8 weight %.
The ZnO of the constituent of glass powder is the necessary composition that is used to make the thawing of glass eutectic.When the ZnO in the glass powder was lower than 8.0 weight %, it is insufficient that the eutectic of glass melts, and when surpassing 20 weight % in addition, the easy crystallization of glass when sealing-in is burnt till is as seal, sealing materials sintering well.
The preferred content of ZnO in glass powder is 9.0～12 weight %.
The constituent Al of glass powder 2O 3Stability in the time of can improving glass melting is the necessary composition that sealing-in is used to suppress the glass crystallization when burning till simultaneously.
Al in the glass powder 2O 3When being lower than 0.1 weight %, the glass crystallization when stability during to glass melting and inhibition sealing-in are burnt till does not have effect, and in addition, when surpassing 1 weight %, the eutectic of glass melts insufficient.
Preferred Al 2O 3Content in glass powder is 0.1～0.5 weight %.
The constituent of glass powder is except mentioned component, and the crystallization of the glass when stability during with the raising glass melting or inhibition sealing-in are burnt till turns to purpose, can make BaO, SiO 2Total contains 5 weight % or below it.
Except that above-mentioned constituent, can also contain CaO, MgO, SrO, TiO 2, ZrO 2Deng.
The mineral filler that contains above-mentioned zirconium phosphate compound contains 2～20 weight %.Preferably contain 5～20 weight %.
For example can enumerate phosphoric acid wolframic acid zirconium (Zr as the zirconium phosphate compound that contains in the above-mentioned mineral filler 2(WO 4) (PO 4) 2), zirconium phosphate ((ZrO) 2P 2O 7), calcium zirconyl phosphate (Ca 0.5Zr 2(PO 4) 3).These compounds can separately or be combined and be contained.
The thermal expansivity of zirconium phosphate compound is little or show negative value, has the effect of the thermal expansivity reduction that makes sealing composition.
The zirconium phosphate compound contains 2～20 weight % with respect to the sealing composition full dose.When being lower than 2 weight %, the reduction of the thermal expansivity of sealing composition is insufficient and not preferred.In addition, when surpassing 20 weight %, not preferred owing to the sintering that hinders sealing composition.
More preferably the content with respect to the zirconium phosphate compound of the full dose of sealing composition is 5～20 weight %.10～20 weight % especially preferably.
Preferably contain phosphoric acid wolframic acid zirconium as above-mentioned zirconium phosphate compound.
The thermal expansivity of phosphoric acid wolframic acid zirconium shows negative value, by containing in sealing composition, can reduce the thermal expansivity of sealing composition effectively.Particularly make phosphoric acid wolframic acid zirconium and Bi 2O 3-B 2O 3-ZnO-Al 2O 3It is the occasion that glass combination constitutes sealing composition, with cooperate the thermal expansivity of the sealing composition of ratio Theoretical Calculation by both and compare, one of the thermal expansivity of actual sealing composition can be to show littler effect, therefore, the sealing composition of more cryogenic sealing temperature, littler thermal expansivity just can be provided reliably with the amount of still less filler.
The full dose of above-mentioned zirconium phosphate compound can be taken as phosphoric acid wolframic acid zirconium.That is the full dose of the zirconium phosphate compound that, contains in the sealing composition can be made up of phosphoric acid wolframic acid zirconium.
According to like this, can reduce the thermal expansivity of sealing composition significantly with little amount of filler, and the cooperation ratio of glass powder increases, only this part just can obviously play the effect that sealing temperature reduces, thereby, as a result of, can provide sealing temperature the fully low and also abundant little sealing composition of thermal expansivity.
Phosphoric acid wolframic acid zirconium can be taken as 2～20 weight % with respect to the full dose of sealing composition.When being lower than 2 weight %, the reduction of the thermal expansivity of sealing composition is insufficient, and is when surpassing 20 weight %, not preferred owing to the sintering that hinders sealing composition.
Be 5 weight % or more than it more preferably with respect to the content (2～20 weight %) of the phosphoric acid wolframic acid zirconium of the full dose of sealing composition, if furtherly, 10 weight % especially preferably.
Except the zirconium phosphate compound, can also contain the mineral filler with low-thermal-expansion rate of beta-eucryptite etc. as above-mentioned mineral filler.
In addition, as mineral filler, except the zirconium phosphate compound, under the degree that does not hinder thermal expansivity to reduce, can also contain the ceramic packing and the silica glass filler of trichroite, aluminium titanates, zircon, mullite, β-triphane, aluminum oxide, celsian-felspar, willemite, silica (alpha-quartz, cristobalite, tridymite) etc.
In addition, glass, mineral filler while separated pulverizing with the regulation composition, preferably make glass powder become the glass powder of median size 2～7 μ m, preferably make mineral filler become the mineral filler of median size 10～20 μ m by for example sieve of mesh 44 μ m by for example sieve of mesh 106 μ m.
From the stability of thermal expansivity, the size-grade distribution of preferred mineral filler is few at 1 μ m or the micro mist below it, and from the uniformity aspect of sealing composition, preferred 44 μ m or its above coarse grain are also few.
Embodiment
Below enumerate embodiment and illustrate in greater detail the present invention, but the present invention is not subjected to any restriction because of these embodiment.
In addition, the raw material that uses in an embodiment is Bi 2O 3, H 3BO 3, ZnO, Al (OH) 3, Ba (NO 3) 2, SiO 2
In an embodiment, measure the median size of glass powder, the glass transition temperature Tg of glass powder, the sealing-in (flowability) of sealing composition, the thermal expansivity of sealing composition with following method.
(1) median size of glass powder
Obtain the value of the D50 of volume distributed median type with laser scattering type size-grade distribution meter.
(2) glass transition temperature Tg of glass powder
Use differential thermal analysis determinator (DTA), obtain by the temperature (extrapolation point) that the initial heat absorption of the DTA curve that obtains when room temperature heats up with 20 ℃/min begins.
(3) sealing-in (flowability)
The powder of 10g sealing composition is made the round shape of diameter 20mm, is positioned in the top of soda-lime glass, under the sealing temperature shown in the table 1,2, burn till, measure the sintered compact that obtains profile maximum value and obtain.This flow diameter (maximum value of profile) is lower than the occasion of 22mm, can not use as seal, sealing materials.
(4) thermal expansivity
To be cut into 3mm * about 3mm * about 10mm by the sintered body that (3) obtain, use thermo-mechanical analysis determinator (TMA), as standard test specimen, obtain thermal expansivity under 50～250 ℃ with silica glass by the TMA curve that when room temperature heats up with 10 ℃/min, obtains.
Embodiment 1～6, comparative example 1～5
(making of glass powder)
According to the chemical constitution shown in the table 1,2 allotment raw material and mix, should allocate raw material and put into platinum crucible at 1000 ℃ of following fusions chilling and make glass after 1 hour.The glass that obtains is put into ball mill carry out after dry type pulverizes, the sieve by mesh 106 μ m obtains glass powder.The median size of the glass powder that obtains is 3～6 μ m.The glass transition temperature Tg of glass powder is shown in table 1,2.
(making of sealing composition)
Glass powder and mineral filler (upright altogether マ テ リ ア Le Co., Ltd. system, phosphoric acid wolframic acid zirconium (ZWP), zirconium phosphate (ZP)) are mixed with the proportioning shown in the table 1,2, make sealing composition.The sealing-in of the sealing composition that mensuration obtains (flowability), thermal expansivity.The results are shown in table 1,2.In addition, the occasion that is lower than 22mm owing to flow diameter when measuring flowability is not just used as seal, sealing materials, so also just no longer implement the mensuration of thermal expansivity.
[table 1]
Figure A20058000347500101
[table 2]
Comparative example
1 2 3 4 5
Glass forms ︵ % by weight ︶ Bi 2O 3 70.6 82.2 85.4 85.0 82.2
B 2O 3 8.4 4.8 5.0 4.3 8.4
ZnO 17.8 10.9 9.2 10.0 7.3
Al 2O 3 0.8 0.4 0.4 0.4 0.4
BaO 0.4 0.3 0.3 0.3
SiO 2 2.0 1.4 1.4
Add up to 100 100 100 100 100
Glass transition temperature Tg (℃) 401 365 346 343 377
Filler Kind ZWP βSPJ ZWP ZWP ZWP
Use level (%) 21 5 10 10 10
Sealing temperature (℃) 520 450 450 450 450
Flow diameter (mm) 17.5 22.0 21.5 19.5 19.0
The thermal expansivity of seal, sealing materials * 10 -7(1/K) - 90 - - -
β SPJ: β-triphane
As table 1,2 shows, as can be known, among the embodiment 1～5 of sealing composition of the present invention, all can be in sealing-in under 520 ℃ or the low temperature below it, and can make thermal expansivity little to 80 * 10 -7Or below it.
1 use level that changes mineral filler of embodiment 1 and comparative example.Use level as the ZWP of mineral filler is the sealing composition of 21 weight %, and flow diameter becomes 17.5mm, its sealing-in generation problem.
2 of embodiment 3 and comparative examples have changed as the mineral filler of using filler.Because mineral filler changes β SPJ into by ZWP, thermal expansivity increases.
Comparative example 1 surpasses 20 weight % as the amount of the phosphoric acid wolframic acid zirconium of mineral filler, and is mobile poor, is difficult 520 ℃ or sealing-in below it in fact.
Comparative example 2 uses β-triphane (β SPJ) as mineral filler, though at low temperatures can sealing-in, poor on this aspect greatly at thermal expansivity.
The a certain item that comparative example 3～5 is formed owing to glass goes beyond the scope, the easy crystallization of glass when burning till, thereby mobile poor, sealing-in difficulty at low temperatures.
(calculated value of thermal expansivity and measured value different)
Below represented especially be engaged in the used Bi of the present invention as filler with phosphoric acid wolframic acid zirconium (ZWP) 2O 3-B 2O 3-ZnO-Al 2O 3In the glass of system and in the sealing composition that forms, by two materials thermal expansivity and the proportioning theoretical thermal expansivity that can calculate and the thermal expansivity of practical measurement separately.
(1) sealing composition shown in the embodiment 1 (glass powder 82 weight %, ZWP18 weight %)
Theoretical Calculation thermal expansivity: 60 * 10 -7(1/K)
Actual measurement thermal expansivity: 40 * 10 -7(1/K)
(2) in the glass powder of the embodiment 3 of 90 weight %, cooperate the sealing composition of 10 weight %ZWP
Theoretical Calculation thermal expansivity: 78 * 10 -7(1/K)
Actual measurement thermal expansivity: 64 * 10 -7(1/K)
(3) in the glass powder of the embodiment 3 of 90 weight %, cooperate the sealing composition of 10 weight %ZP
Theoretical Calculation thermal expansivity: 82 * 10 -7(1/K)
Actual measurement thermal expansivity: 79 * 10 -7(1/K)
(4) in the glass powder of the embodiment 3 of 90 weight %, cooperate the sealing composition of 10 weight % β SPJ
Theoretical Calculation thermal expansivity: 91 * 10 -7(1/K)
Actual measurement thermal expansivity: 90 * 10 -7(1/K)
(5) in the glass powder of the embodiment 3 of 90 weight %, cooperate 10 weight %Al 2O 3Sealing composition
Theoretical Calculation thermal expansivity: 95 * 10 -7(1/K)
Actual measurement thermal expansivity: 96 * 10 -7(1/K)
As show by Theoretical Calculation thermal expansivity shown in above-mentioned and actual measurement thermal expansivity like that, as the occasion that filler cooperates, can obtain having the sealing composition of the thermal expansivity of the thermal expansivity of considering than theory more obvious low (little) with phosphoric acid wolframic acid zirconium (ZWP).
In addition, even in the occasion that cooperates as filler with zirconium phosphate (ZP), the thermal expansivity of sealing composition also has the tendency than the thermal expansivity low (little) of Theoretical Calculation.
In addition as can be seen, cooperate β SPJ and Al as filler 2O 3Occasion, almost can't see the tendency that the thermal expansivity of sealing composition improves.
Industrial applicibility
In the integrated circuit of Plasmia indicating panel manufacturing and other was made, the present invention can be used in the sealing-in of material of pottery, glass, metal etc. Be adapted to environment as not containing plumbous glass for sealing, can using in the purposes widely.

Claims (5)

1. a sealing composition is characterized in that,
Be substantially free of lead, and constitute by the glass powder of 80～98 weight % and the mineral filler that contains the zirconium phosphate compound of 2～20 weight %,
Convert with oxide compound, above-mentioned glass powder is to contain
Bi 2O 3: 70～85 weight %
B 2O 3: 4.5～10 weight %
ZnO:8.0～20 weight %
Al 2O 3: the composition of 0.1～1 weight %.
2. sealing composition according to claim 1 is characterized in that, converts with oxide compound, and glass powder is to contain
Bi 2O 3: 80～83 weight %
B 2O 3: 4.5～8 weight %
ZnO:8.0～12 weight %
Al 2O 3: the composition of 0.1～0.5 weight %.
3. sealing composition according to claim 1 and 2 is characterized in that, the zirconium phosphate compound that contains in mineral filler is 2 weight % or more than it with respect to the full dose of sealing composition.
4. according to each described sealing composition of claim 1～3, it is characterized in that,, contain phosphoric acid wolframic acid zirconium as the zirconium phosphate compound.
5. according to each described sealing composition of claim 1～3, it is characterized in that the full dose of zirconium phosphate compound is a phosphoric acid wolframic acid zirconium.
CNA2005800034755A 2004-01-30 2005-01-27 Sealing composition Pending CN1914129A (en)

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JP2004022735A JP4498765B2 (en) 2004-01-30 2004-01-30 Sealing composition
JP022735/2004 2004-01-30

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WO2005073142A1 (en) 2005-08-11

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