JP4136346B2 - Sealing composition - Google Patents

Sealing composition Download PDF

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Publication number
JP4136346B2
JP4136346B2 JP2001283095A JP2001283095A JP4136346B2 JP 4136346 B2 JP4136346 B2 JP 4136346B2 JP 2001283095 A JP2001283095 A JP 2001283095A JP 2001283095 A JP2001283095 A JP 2001283095A JP 4136346 B2 JP4136346 B2 JP 4136346B2
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Prior art keywords
glass
bismuth
sealing composition
weight
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JP2003095697A (en
Inventor
浩三 前田
智之 田口
嘉規 谷上
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日本山村硝子株式会社
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Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24Fusion 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

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a sealing composition, and particularly relates to a sealing composition substantially free of lead.
[0002]
[Prior art]
Conventionally, a sealing composition is generally composed of a lead glass powder such as PbO—SiO 2 —B 2 O 3 and a ceramic filler such as PbTiO 3 . However, in recent years, glass containing lead has tended to be avoided from an environmental point of view. Under such circumstances, development of a composition that does not contain a lead component and can be sealed at a low temperature is urgently required.
As the low melting point glass not containing lead, phosphate glass, borosilicate glass, alkali silicate glass, etc. are known. Among them, firing at low temperature is possible, that is, low melting and chemical properties of glass. From the viewpoint of durability, bismuth-based glass has attracted attention.
However, most of the bismuth-based glasses that have been developed so far have a low melting point, but have problems such as a high coefficient of thermal expansion or poor stability. For example, Bi 2 O 3 based glass disclosed in Japanese Patent Application Laid-Open No. 9-278483 has a problem that the coefficient of thermal expansion is large because the amount of ZnO is small.
A glass containing a large amount of ZnO has also been developed (Japanese Patent Laid-Open No. 10-139478). However, since the amount of Bi 2 O 3 is large and Al 2 O 3 is not contained, there is a problem in the chemical durability of the glass. There is. Further, since the amount of Bi 2 O 3 is large, the stability of the glass is poor, and when heat treatment is performed with a filler contained, crystallization is promoted and sufficient sealing cannot be achieved.
Therefore, development of a bismuth-based glass having a low melting point, a low thermal expansion coefficient and a high stability, and a sealing composition comprising the glass and a refractory filler have been strongly desired.
[0003]
[Problems to be solved by the invention]
Therefore, the present invention eliminates the problems in the sealing composition using the conventional bismuth-based glass, and can be sealed at a low temperature even if a refractory filler is contained, and the thermal expansion coefficient is not so high. In addition, it is an object to provide a sealing composition with good stability.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have found that a sealing composition containing a bismuth-based glass powder having a load softening point of 500 ° C. or less solves the above problems. Based on this, the present invention has been completed.
That is, the sealing composition of the present invention is a sealing composition containing substantially no PbO and containing a bismuth-based glass powder having a load softening point (Td) of 500 ° C. or less. but, by weight percentages, Bi 2 O 3: 65~76% , ZnO: 13~20%, CaO, SrO and at least one of BaO: 0.5~10%, Al 2 O 3: 0. 5~1.5%, B 2 O 3: is a first feature in that it has 5-12% of the composition.
In addition to the first feature, the sealing composition of the present invention has a second feature that the bismuth-based glass powder contains 4% by weight or less of SiO 2 .
Further, in the sealing composition of the present invention, in addition to the first or second feature, the bismuth-based glass powder is CuO x (x = 0.5 or 1), FeO y (y = 1 or 1.5). ) And 5% by weight or less of at least one of WO 3 is a third feature.
The sealing composition of the present invention is, in addition to the characteristics described in any one of the first to third aspects described above, the fourth characteristic that the bismuth-based glass powder contains 10% by weight or less of P 2 O 5. It is said.
The sealing composition of the present invention is characterized in that, in addition to any of the first to fourth features, the bismuth-based glass powder contains SnO z (z = 1 or 2) at 10% by weight or less. 5 features.
Further, in the sealing composition of the present invention, in addition to any of the above first to fifth features, the bismuth-based glass powder contains 5% by weight of at least one of LiO 2 , Na 2 O and K 2 O. It is the 6th characteristic to contain% or less.
Further, in the sealing composition of the present invention, in addition to any of the above first to sixth characteristics, the bismuth-based glass powder contains REO q (RE = Y or a lanthanoid element, q = 1.5 or 2). The seventh feature is that the content is 3% by weight or less.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The reasons for limiting the composition and physical properties of the bismuth glass constituting the sealing composition of the present invention will be described below.
In the present invention, “substantially does not contain PbO” means that no raw material mainly composed of lead such as PbO is used, and is derived from impurities in the raw materials of the respective components constituting the glass. It does not exclude glass that contains trace amounts of lead.
In addition, the “load softening point” in the present invention is a temperature increase from room temperature to 10 K / min using a thermomechanical analyzer (TMA) with a 10 g weight applied to each of the glass rod and the quartz glass rod of the standard sample. The temperature when the maximum length of the TMA curve obtained in this way is reached.
[0006]
The load softening point of bismuth-based glass must be 500 ° C. or lower. When the load softening point exceeds 500 ° C., it becomes difficult to seal without impairing the physical properties of the material to be sealed.
[0007]
Bi 2 O 3 is an oxide that forms the network of the glass of the present invention . When B i 2 O 3 is less than 50% by weight, glass may be obtained, but the load softening point may be too high. Moreover, when it exceeds 85 weight%, there exists a possibility that a thermal expansion coefficient may become high too much. Content of Bi 2 O 3, load softening point, in consideration of thermal expansion coefficient and the like, it is good preferable is 65 to 76 wt%.
[0008]
ZnO lowers the thermal expansion coefficient, Ru component der to and lowering the load softening point. When ZnO is less than 10% by weight, the thermal expansion coefficient may be too high. On the other hand, if it exceeds 25% by weight, the stability of the glass deteriorates and the glass may not be obtained. The content of ZnO is load softening point, thermal expansion coefficient, considering the stability of the glass, it is favorable preferable is 13 to 20 wt%.
[0009]
CaO, SrO, BaO is a component to increase more the thermal expansion coefficient, further lowering the load softening point by coexistence with ZnO, Ru component der to and improving stability of the glass. When CaO, SrO, and BaO are less than 0.2% by weight in total, the effect of improving the stability of the glass is small. Moreover, when it exceeds 20 weight%, there exists a possibility that a thermal expansion coefficient may become high too much. CaO, SrO, BaO content, the thermal expansion coefficient, the load softening point, in consideration of the stability of the glass, it is better good is 0.5 to 10 wt% of one or more of them in total Yes.
[0010]
Al 2 O 3 lowers the thermal expansion coefficient, Ru component der to and improving stability of the glass. If Al 2 O 3 is less than 0.1% by weight, the thermal expansion coefficient may be too high, and the stability of the glass will not be improved. If it exceeds 5% by weight, the raw material may remain as an unmelted product. The content of Al 2 O 3, the thermal expansion coefficient, stability of the glass, taking into account the melting properties and the like, it is good preferable from 0.5 to 1.5 wt%.
[0011]
B 2 O 3 is lower thermal expansion coefficient, Ru component der to improve the stability of the glass. When B 2 O 3 is less than 2% by weight, the stability of the glass is not improved. If it exceeds 20% by weight, the softening point may be too high. The content of B 2 O 3, the thermal expansion coefficient, stability of the glass, taking into account the load softening point or the like, it is good preferable 5 to 12 wt%.
[0012]
In addition to the above components, SiO 2 can be contained in an amount of 4% by weight or less as required. By containing SiO 2 in the above range, the thermal expansion coefficient is lowered and the stability of the glass is improved. When the content exceeds 4% by weight, the softening point may be rapidly increased as compared with B 2 O 3 .
[0013]
In addition to the above components, if necessary, one or more of CuO x (x = 0.5 or 1), FeO y (y = 1 or 1.5) and WO 3 may be 5% by weight or less in total. It can be included. By containing CuO x (x = 0.5 or 1) in the above range, the load softening point can be lowered. Further, by containing FeO y (y = 1 or 1.5) and WO 3 in the above range, the thermal expansion coefficient can be lowered without increasing the load softening point so much.
[0014]
In addition to the above components, 10% by weight or less of P 2 O 5 can be contained as necessary. By containing P 2 O 5 in the above range, the stability of the glass is improved.
[0015]
In addition to the above components, SnO z (z = 1 or 2) can be contained in an amount of 10% by weight or less as required. By including SnO z (z = 1 or 2) within the above range, the load softening point can be lowered.
[0016]
In addition to the above components, if necessary, one or more of Li 2 O, Na 2 O and K 2 O can be contained in a total of 5% by weight or less. By containing Li 2 O, Na 2 O, and K 2 O in the above range, the stability of the glass can be improved and the load softening point can be lowered.
[0017]
In addition to the above components, 3% by weight or less of REO q (RE = Y or a lanthanoid element, q = 1.5 or 2) can be contained as necessary. By adding REO q (RE = Y or a lanthanoid element, q = 1.5 or 2) within the above range, the stability of the glass is improved.
The raw material for obtaining the bismuth-based glass is not particularly limited as long as it is a compound that can be an oxide of the glass.
[0018]
In the sealing composition of the present invention, the amount of the bismuth-based glass powder is in the range of 60 to 95% by weight with respect to the total amount of the bismuth-based glass and the refractory filler, and the amount of the refractory filler is based on the total amount. It is essential to be in the range of 5-40% by weight. If the refractory filler is less than 5% by weight, the coefficient of thermal expansion of the bismuth-based glass is so large that the difference in coefficient of thermal expansion from the material to be sealed becomes too large, resulting in insufficient sealing and desired performance. There is a risk of disappearing. Moreover, when a refractory filler exceeds 40 weight%, there exists a possibility that sealing may become difficult.
[0019]
The refractory filler can be at least one of a ceramic filler and a quartz glass filler.
Examples of the ceramic filler include cordierite, β-eucryptite, aluminum titanate, zircon, mullite, β-spodumene, alumina, celsian, willemite, zirconium phosphate, silica (α-quartz, cristobalite, tridymite). It is preferable to use at least one of them. By using these fillers, sufficient sealing can be performed on various substrates.
[0020]
【Example】
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
The raw materials used in the examples are Bi 2 O 3 , ZnO, Ca (OH) 2 , SrCO 3 , BaCO 3 , Al (OH) 3 , H 3 BO 3 , SiO 2 , CuO, Fe 2 O 3 , WO 3 , NH 4 H 2 PO 4 , SnO 2 , Li 2 CO 3 , NaCO 3 , KNO 3 , Y 2 O 3 , La 2 O 3 , CeO 2 .
[0021]
In Examples, the load softening point (Td) of glass, the flow temperature and the thermal expansion coefficient (α) of a mixture of glass and refractory filler were measured by the following methods.
(1) Load softening point (Td)
Glass is processed into a rod shape with a diameter of about 5 mm and a length of 15 to 20 mm. Using a thermomechanical analyzer (TMA), quartz glass is used as a standard sample, the load is 10 g each, and the temperature is increased from room temperature to 10 K / min. From the TMA curve obtained as described above, the temperature when the maximum length was obtained was defined as the load softening point (Td).
(2) Flow temperature Glass powder and refractory filler are mixed at a predetermined ratio, and the mixed powder is press-molded so as to be a rod having a diameter of about 10 mm and a length of 12 to 15 mm. This rod is placed on an alumina plate and raised to a predetermined temperature. The temperature when the rod was deformed and bent at a predetermined temperature and fell on the alumina plate was defined as the flow temperature.
(3) Thermal expansion coefficient (α)
The sintered body obtained by the flow shown above is processed into a rod shape, and an average value line of 50 to 350 ° C. is obtained from a thermal expansion curve obtained using a thermomechanical analyzer (TMA) in the same manner as (1). The thermal expansion coefficient was determined.
[0022]
Samples 7, 17, 19, 23, 29, and 30 among the samples 1 to 31 are examples that fall within the composition range of the sealing composition of the present invention . Other samples 1-6, 8-16, 18, 20-22, 24-28, 31 are reference examples.
About each sample 1-31 shown to Tables 1-4 , each component raw material is prepared so that it may become a glass composition shown by weight% display to a table | surface, respectively . This was put into a platinum crucible raised to 1000 ° C. in an electric furnace, melted for 2 hours, rapidly cooled by a twin roll method to obtain glass flakes, and poured into a preheated iron plate to produce a block. . After that, the block was put into an electric furnace set to a temperature about 50 ° C. higher than the expected glass transition point, slowly cooled, cut out, polished, and used as a sample for measuring the load softening point. The glass flakes were pulverized into powder. The load softening point of this glass was measured according to the above method .
Moreover, about each sample 1-31, the refractory filler was selected, respectively, and it was made to mix and flow so that it might become the weight% shown to a table | surface, respectively.
[0023]
Tables 1 to 4 show the results of the load softening point (Td), the flow temperature (° C.), and the thermal expansion coefficient (α) for each of the samples 1 to 31.
[0024]
[Table 1]
[0025]
[Table 2]
[0026]
[Table 3]
[0027]
[Table 4]
[0028]
As is clear from the above examples, it can be seen that the sealing composition of the present invention can be sealed at a low temperature.
[0029]
【The invention's effect】
The present invention has the above-described configuration and action. According to the sealing composition of the present invention, it does not contain substances that may cause environmental pollution such as lead, and can be sealed at a low temperature, with a coefficient of thermal expansion. Is not so high and stability is also good.

Claims (7)

  1. A sealing composition containing substantially no PbO and a bismuth-based glass powder having a load softening point (Td) of 500 ° C. or less, wherein the bismuth-based glass powder is expressed in terms of wt%,
    Bi 2 O 3: 65~76%
    ZnO: 13-20%
    At least one of CaO, SrO and BaO: 0.5 to 10%
    Al 2 O 3 : 0.5 to 1.5%
    B 2 O 3: 5~12%
    A sealing composition having the following composition:
  2. Bismuth glass powder, sealing composition according to claim 1, characterized in that it contains SiO 2 4% by weight.
  3. The bismuth-based glass powder contains 5% by weight or less of at least one of CuO x (x = 0.5 or 1), FeO y (y = 1 or 1.5) and WO 3. The sealing composition according to claim 1 or 2.
  4. Bismuth glass powder, sealing composition according to any one of claims 1 to 3, characterized in that it contains P 2 O 5 10 wt% or less.
  5. The sealing composition according to claim 1, wherein the bismuth-based glass powder contains SnO z (z = 1 or 2) in an amount of 10% by weight or less.
  6. Bismuth glass powder, LiO 2, Na 2 sealing composition according to any one of claims 1 to 5 O and at least one of K 2 O, characterized in that it contains 5 wt% or less.
  7. The sealing composition according to claim 1, wherein the bismuth-based glass powder contains 3% by weight or less of REO q (RE = Y or a lanthanoid element, q = 1.5 or 2). object.
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