WO2005073142A1

WO2005073142A1 - Sealing composition

Info

Publication number: WO2005073142A1
Application number: PCT/JP2005/001110
Authority: WO
Inventors: Yoshitaka Mayumi; Tsuyoshi Fujimoto; Tomoyuki Taguchi; Yoshinori Tanigami
Original assignee: Nihon Yamamura Glass Co., Ltd.
Priority date: 2004-01-30
Filing date: 2005-01-27
Publication date: 2005-08-11
Also published as: JP2005213103A; KR101125169B1; JP4498765B2; CN1914129A; KR20070006711A

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 weight% of a glass powder and 2-20 weight% of an inorganic filler containing a zirconium phosphate compound. The glass powder contains 70-85 weight% of Bi2O3, 4.5-10 weight% of B2O3, 8.0-20 weight% of ZnO and 0.1-1 weight% of Al2O3 in terms of oxides.

Description

Specification

Sealing composition

Technical field

The present invention relates to a sealing composition, and more particularly, to a sealing composition substantially free of lead.

Background art

[0002] Conventionally, lead glass powder such as PbO-SiO-BO-based glass and PbTi

2 2 3

A composition comprising a ceramic filler having a low coefficient of thermal expansion such as o is known. Shi

Three

However, this conventional sealing composition contains lead in both the glass and the ceramic filler.

In recent years, products containing lead tend to be avoided from an environmental point of view. On the other hand, as a glass which can be used in sealing compositions not containing lead, for example,! ³ 〇

2 ZnO, P〇 Sn〇, and Bi O glasses are known, with chemical durability

5 2 5 2 3

In view of this, BiO-based glass is often used.

twenty three

As a sealing composition comprising Bi-based glass and an inorganic filler, the applicant has

twenty three

Open 2003—Providing 95697.

Patent Document 1: JP 2003-95697 A

Disclosure of the invention

Problems to be solved by the invention

[0003] While pressing, the sealing composition comprising the Bi 2 O-based glass and the inorganic filler has a low temperature.

twenty three

However, it was difficult to achieve both sealing at the same time and lowering the coefficient of thermal expansion. That is, if a large amount of filler is contained, the thermal expansion coefficient of the sealing composition can be reduced to a desirable value s, while the sealing temperature must be raised to an undesirably high temperature. . In addition, when the amount of the filler is reduced, the sealing temperature can be lowered, the coefficient of thermal expansion increases, and the type of the object to be sealed is limited. For example, in a conventional lead-free sealing composition comprising a BiO-based glass and an inorganic filler, the sealing temperature is 52

twenty three

0 ° C and below, it is impossible and the coefficient of thermal expansion ^{80 X 10- 7 (1 / K} ) or less. In addition, when the sealing temperature required for the sealing composition increases, the high temperature at the time of the sealing causes deterioration and other adverse effects on the object to be sealed and other materials used.

Therefore, the present invention solves the above-mentioned problems of the conventional sealing composition, and is a lead-free sealing composition that can be sealed at a lower temperature and has a coefficient of thermal expansion (coefficient of thermal expansion). ) Is to provide a smaller sealing composition. Specifically sealable temperature 520 ° C or less, and an object of the invention to provide a thermal expansion coefficient of ^{80 X 10- 7 (1 / K} ) or less of sealing composition, for further sealing temperature, 480 ° An object of the present invention is to provide a sealing composition having a temperature of not more than C or 450 ° C or less.

Means for solving the problem

[0005] The inventor of the present invention has conducted intensive studies to solve the above-mentioned problems, and as a result, using a zirconium phosphate compound having a small thermal expansion coefficient (including those exhibiting a negative value) as an inorganic filler, and a specific glass as a glass. Using Bi O -BO -ZnO-Al O based glass with composition, specify both

2 3 2 3 2 3

It has been found that by using a lead-free sealing composition blended at a ratio of 1%, it is possible to seal well at a low temperature and to reduce the coefficient of thermal expansion (coefficient of thermal expansion). It has been found that the coefficient of thermal expansion of the zirconium phosphate compound and the glass is much lower (smaller) than the calculated coefficient of thermal expansion that can be theoretically calculated according to the mixing ratio of the zirconium phosphate compound and the glass. Was completed.

[0006] That is, the sealing composition of the present invention that achieves the above object does not substantially contain Pb, and contains an inorganic filler containing glass powder 80 98% by weight and a zirconium phosphate compound. 70-85% by weight of Bi 2 O in terms of oxides

twenty three

%, B〇 4.5-10% by weight, Zn〇 8.0-20% by weight, A1〇 0.1-1% by weight

2 3 2 3

The first characteristic is that it has a composition.

Sealing composition of the present invention may also, in addition to the first feature, the glass powder is in terms of oxide, 80- 83 weight ^_0/0, BO to the Bi_〇: 4. 5 8 weight ⁰ / ₀ , Zn〇 8.00 12 weight

2 3 2 3

The second feature is that the composition contains 0.1 to 0.5% by weight of Al 2 O 3.

twenty three

Further, in the sealing composition of the present invention, in addition to the first or second feature, the dinoreconium phosphate compound contained in the inorganic filler may be 2% by weight or more based on the total amount of the sealing composition. The third characteristic is A fourth feature of the sealing composition of the present invention is that, in addition to any one of the features of the thirteenth feature, the zirconium phosphate compound further includes dinoreconium tungstate phosphate.

The fifth aspect of the sealing composition of the present invention is that, in addition to any one of the above-mentioned features, the total amount of the zirconium phosphate compound is zirconium tungstate phosphate.

The invention's effect

[0007] According to the sealing composition of claim 1, the glass powder is composed of 80 to 98% by weight of a glass powder and 2 to 20% by weight of an inorganic filler containing a zirconium phosphate compound. In terms of material, Bi〇 is 70-85 weight ⁰ /. , 8. 4. 5-10 weight ^_0/0, ZnO the B_〇 0-

2 3 2 3

With a composition containing 20% by weight and 0.1-1% by weight of Al 2 O,

twenty three

Sealing can be performed at a sufficiently low temperature and with a sufficiently small coefficient of thermal expansion (sufficiently low coefficient of thermal expansion).

Specifically, the sealing temperature can be below 520 ° C, and the thermal expansion coefficient becomes possible to 80 X 10 _ ⁷ below.

Further, since the sealing composition of the present invention does not contain lead, it is also preferable from an environmental point of view.In the sealing composition of the present invention, the above-mentioned Bi O -B O -ZnO-

2 3 2 3

The use of Al 2 O 3 glass can lower the melting temperature,

twenty three

The glass can be hardly crystallized.

[0008] Further, according to the sealing composition of claim 2, in addition to the effect of the configuration of claim 1, the composition of the glass powder is further limited, so that the glass powder is converted into oxide. in, Bi_〇 a 80- 83 weight ^_0/0, BO 4. 5-8 wt ^_0/0, 8.0 12 weight Zn_〇 ^_0/0, A1

2 3 2 3 2

By having a composition containing 0.1-0.5% by weight of O,

Three

The effect of further reducing the melting of the sealing composition and suppressing the crystallization of the glass during the sealing and firing can be satisfactorily achieved.

[0009] According to the sealing composition of claim 3, in addition to the effect of the configuration of claim 1 or 2, the dinoreconium phosphate compound contained in the inorganic filler is sealed. By making it 2% by weight or more based on the total amount of the composition,

The thermal expansion coefficient of the sealing composition can be ensured to 80 X 10- ⁷ or less.

[0010] Further, according to the sealing composition of claim 4, in addition to the effect of the configuration according to any one of claims 13 to 13, the composition further contains dinoreconium tungstate phosphate as the dinoreconium phosphate compound. By doing

The effect of the negative coefficient of thermal expansion of zirconium tungstate phosphate is given to the coefficient of thermal expansion of the sealing composition as a whole, so that a small amount of filler makes it possible to use a sealing composition having a low sealing temperature and a low coefficient of thermal expansion. It can be provided reliably.

In particular, the inventor has found that zirconium tungstate phosphate can be used as a Bi〇

When the sealing composition is composed in combination with a 23-series glass, it is compared with the thermal expansion coefficient of the sealing composition calculated as the theoretically calculated value of the mixing ratio force of dinoleconium tungstate phosphate and glass. Therefore, it has been found that the thermal expansion coefficient of the actual sealing composition is much smaller than that of the actual sealing composition, whereby the sealing composition having a lower sealing temperature and a lower thermal expansion coefficient can be obtained with a smaller amount of filler. Can be reliably provided.

[0011] Further, according to the sealing composition of claim 5, in addition to the effect of the configuration of claim 13, the total amount of the zirconium phosphate compound is reduced to the total amount of zirconium phosphate tungstate. By being

By the effect of the negative coefficient of thermal expansion of zirconium tungstate phosphate and the effect of lowering the coefficient of thermal expansion beyond the theoretically calculated value, the sealing composition having a lower coefficient of thermal expansion at a lower sealing temperature can be surely obtained. Can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

The sealing composition of the present invention includes ceramics such as alumina, soda lime glass, glass such as glass substrates for plasma display panels, metals such as Kovar and high Ni alloys such as 50 alloy, and other various materials. It can be used for sealing.

The term "substantially free of Pb" as used in the present invention means that no raw material containing lead as a main component such as PbO is used at all, and the raw materials of each component constituting the glass and the impurities of the inorganic filler are not used. It does not exclude the inclusion of trace amounts of lead from products.

[0013] The sealing composition of the present invention comprises 80-98% by weight of glass powder and zirconium phosphate compound. An inorganic filler 2-20 weight percent containing objects, in the glass powder in terms of oxide, Bi_〇 a 70-85wt ^_0/0, BO 4-5- 10 weight ^_0/0, the Zn_〇 8 . 0 20 weight ^_0/0, A1_rei

The composition contains 0.13 to 1% by weight of 2 3 2 3 2 3.

[0014] In the glass powder, Bi O, which is a component of the glass powder, lowers the melting temperature of glass.

twenty three

Indispensable component for.

If the content of Bi ガラス in the glass powder is less than 70% by weight, the low melting of the glass is insufficient.

twenty three

If it exceeds 85% by weight, the glass is crystallized at the time of baking for sealing and does not immediately sinter as a sealing material.

The content of Bi〇 in the glass powder is preferably 80-83% by weight.

twenty three

[0015] In the glass powder, the component B O forms a glass network and seals and fires.

twenty three

It is an essential component for suppressing crystallization of the glass at the time of formation.

If B O in glass powder is less than 4.5% by weight, suppression of crystallization of glass during sealing firing

twenty three

If the content exceeds 10% by weight, the glass becomes unstable and has no effect on suppressing crystallization of the glass.

The content of B O in the glass powder is preferably 4.5-8% by weight.

twenty three

[0016] ZnO, which is a constituent component of the glass powder, is an essential component for reducing the melting of glass. If the Zn content in the glass powder is less than 8.0% by weight, the low melting of the glass is insufficient, and if it exceeds 20% by weight, the glass crystallizes at the time of sealing and firing, so that it is preferably fired as a sealing material. Do not tie.

The content of Zn〇 in the glass powder is preferably 9.0 to 12% by weight.

[0017] Al O, which is a component of the glass powder, not only enhances the stability of the glass during melting, but also seals

twenty three

If Al O in glass powder is less than 0.1% by weight, stability during glass melting and firing during sealing

twenty three

It is not effective in suppressing the crystallization of the glass. If it exceeds 1% by weight, the low melting of the glass becomes insufficient.

The content of Al 2 O 3 in the glass powder is preferably 0.1 to 0.5% by weight.

twenty three

[0018] In addition to the above-mentioned components, the glass powder is composed of 5% by weight of BaO and SiO in total for the purpose of enhancing stability during melting of the glass and suppressing crystallization of the glass during sealing and firing. Less than Below can be included.

Furthermore, in addition to the above components, CaO, Mg〇, Sr〇, Ti〇, ZrO, etc.

twenty two

Can do.

[0019] The inorganic filter containing the dinoconium phosphate compound is contained at 220% by weight. Preferably, the content is 520% by weight.

[0020] Examples of the zirconium phosphate compound contained in the inorganic filler include zirconium phosphate (Zr (WO) (PO)) and zirconium phosphate ((ZrO) PO).

2 4 4 2 2 2 7

And calcium zirconium phosphate (Ca Zr (PO 3)). Each of these

O. 5 2 4 3

The compounds can be contained alone or in combination together.

The dinoconium phosphate compound has a small or negative coefficient of thermal expansion and has a function of lowering the coefficient of thermal expansion of the sealing composition.

The dinorconium phosphate compound is contained in an amount of 2 to 20% by weight based on the total amount of the sealing composition. If the content is less than 2% by weight, the thermal expansion coefficient of the sealing composition is insufficiently reduced, which is not preferable. On the other hand, if it exceeds 20% by weight, sintering of the sealing composition is hindered, which is not preferred. The content of the zirconium phosphate compound relative to the total amount of the sealing composition is more preferably 5 to 20% by weight. More preferably, the content is 10 to 20% by weight.

[0021] The zirconium phosphate compound preferably contains zirconium tungstate phosphate.

Zirconium phosphate tungstate has a negative coefficient of thermal expansion and is contained in the sealing composition, whereby the thermal expansion coefficient of the sealing composition can be effectively reduced. In particular, zirconium phosphate tungstate is used for Bi〇_B O -ZnO-Al〇 glass.

2 3 2 3 2 3

When the sealing composition is composed in combination, the thermal expansion coefficient of the actual sealing composition is more than the thermal expansion coefficient of the sealing composition theoretically calculated from the mixing ratio of the two. The effect has been found to be considerably smaller, which makes it possible to reliably provide a lower sealing temperature, a lower coefficient of thermal expansion sealing composition with a lower amount of filler.

[0022] The whole amount of the zirconium phosphate compound can be zirconium tungstate phosphate. That is, the total amount of the zirconium phosphate compound contained in the sealing composition is reduced. It can be made of zirconium tungstate.

By doing so, the thermal expansion coefficient of the sealing composition can be greatly reduced with a small amount of filler, and the effect of lowering the sealing temperature is increased by increasing the mixing ratio of the glass powder. As a result, a sealing composition having a sufficiently low sealing temperature and a sufficiently low thermal expansion coefficient can be provided.

[0023] Zirconium tungstate phosphate is preferably used in an amount of 220% by weight based on the total amount of the sealing composition. If the amount is less than 2% by weight, the thermal expansion coefficient of the sealing composition will not be sufficiently reduced, and if it exceeds 20% by weight, sintering of the sealing composition will be impaired.

The content (220% by weight) of zirconium phosphate tungstate relative to the total amount of the sealing composition is preferably 5% by weight or more, more preferably 10% by weight.

[0024] As the inorganic filler, an inorganic filler having a low coefficient of thermal expansion such as j3-eucryptite can be contained in addition to the dinoleconium phosphate compound.

As an inorganic filler, in addition to the zirconium phosphate compound, cordierite, aluminum titanate, zircon, mullite, β-spodumene, anoremina, senorocyan, willemite, silica (α- A ceramic filler such as quartz, cristobalite, or tridymite) or a quartz glass filler can be contained.

[0025] Note that glass, and Kona碎respective ones inorganic FILLER one together predetermined composition, glass powder, for example, shake of mesh 106 mu m les, average particle size by passing it was 2-7 _beta m Preferably, the inorganic filter is made to have an average particle size of S10-20 μm by passing through a sieve having an opening of 44 μΐη, for example.

The particle size distribution of the inorganic filler is preferably low in fine powder of 1 βm or less from the viewpoint of stability of thermal expansion coefficient. preferable.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The raw materials used in the examples were Bi〇, HBO, Zn〇, Al (OH), Ba (NO

2 3 3 3 3

), Si〇. The average particle size of the glass powder, the glass transition point Tg of the glass powder, the sealing property (flow property) of the sealing composition, and the thermal expansion coefficient of the sealing composition are as follows. It was measured by the method.

(1) Average particle size of glass powder

Using a laser scattering particle size distribution meter, the value of D50 in the volume distribution mode was determined.

(2) Glass transition point Tg of glass powder

Using a differential thermal analyzer (DTA), the temperature was determined from the temperature at the first endothermic end (outer 揷 point) of the DTA curve obtained when the temperature was raised from room temperature at 20 ° C./min.

(3) Sealability (flowability)

10 g of the powder of the sealing composition was formed into a cylindrical shape with a diameter of 20 mm, placed on soda lime glass, and fired at the sealing temperatures shown in Tables 1 and 2, and the maximum value of the outer shape of the obtained sintered body was measured. I got it. If this flow diameter (maximum outer shape) is less than 22 mm, it cannot be used as a sealing material.

(4) Thermal expansion coefficient

The fired body obtained in (3) was cut into a piece of about 3 mm X about 3 mm X about 1 Omm, and the temperature was raised from room temperature to 10 ° C / min using a quartz glass as a standard sample using a thermomechanical analyzer (TMA). The thermal expansion coefficient at 50-250 ° C was determined from the TMA curve obtained in this case.

Example 1-6, Comparative Example 1-5

(Preparation of glass powder)

Raw materials were prepared and mixed so as to have the chemical compositions shown in Tables 1 and 2, and the prepared raw materials were put into a platinum crucible, melted at 1000 ° C. for 1 hour, and quenched to produce glass. The obtained glass was put into a ball mill and pulverized by a dry method, and then passed through a sieve having openings of 106 μm to obtain glass powder. The average particle size of the obtained glass powder was 3-6 x m. Tables 1 and 2 show the glass transition point Tg of the glass powder.

(Preparation of sealing composition)

Glass powder and an inorganic filler (manufactured by Kyoritsu Materials Co., Ltd., zirconium phosphate tungstate (ZWP), dinorecone phosphate (ZP)) were mixed at the compounding ratios shown in Tables 1 and 2 to prepare a sealing composition. Measure the sealing properties (flow properties) and thermal expansion coefficient of the obtained sealing composition did. The results are shown in Tables 1 and 2. In the measurement of the flow property, when the flow diameter is less than 22 mm, it cannot be used as a sealing material, so the measurement of the thermal expansion coefficient was not performed.

[table 1]

[Table 2] Comparative example

1 2 3 4 5

B ^! 2 ° 3 70.6 82.2 85.4 85.0 82.2

8.4 4.8 5.0 4.3 8.4 LA ^B 2 ° 3

S

Z n O 17.8 10.9 9.2 10.0 7.3 pairs

A ¹ 2 ° 3 0.8 0.4 0.4 0.4 0.4

B a O 0.4 0.3 0.3 0.3 ri

% sio ₂ 2.0 1.4 1.4

≡ ±

Mouth PT 100 100 100 100 100 Glass transition temperature T g (° C) 401 365 346 343 377

Z ZWP S P J ZWP ZWP ZWP ラ

I Content (%) 21 5 10 10 10 Sealing temperature (° c) 520 450 450 450 450 Flow diameter (■) 17.5 22.0 21.5 19.5 19.0 Thermal expansion coefficient of sealing material

― 90 ― ― ―

X 1 0— ⁷ (1 ZK) β SPJ: β-spodumene

As is clear from Tables 1 and 2, in Examples 115 of the sealing composition according to the present invention, all can be sealed at a low temperature of 520 ° C. or less, and the thermal expansion coefficient is 80 × 10 It can be seen that it can be reduced to -7 or less.

Example 1 and Comparative Example 1 are different from each other in the amount of the inorganic filler. When the content of ZWP as an inorganic filler is 21% by weight, the flow diameter becomes 17.5 mm and the sealing property is improved. Problems arise.

Example 3 and Comparative Example 2 are different from the inorganic filler used as the filler. When the inorganic filler changes from ZWP to β SPJ, the coefficient of thermal expansion increases.

In Comparative Example 1, the amount of zirconium tungstate phosphate as an inorganic filler exceeds 20% by weight, and the actual sealing at 520 ° C. or lower is difficult because of poor flowability.

In Comparative Example 2, β-spodumene (j3 SPJ) was used as the inorganic filler, and although sealing could be performed at a low temperature, it was inferior in that the coefficient of thermal expansion was large.

In Comparative Examples 3-5, the composition of the glass was out of the range in any case, and the glass was easily crystallized at the time of firing, so that the flowability was poor and it was difficult to seal at low temperatures.

(Difference between theoretically calculated and actual measured values of thermal expansion coefficient)

In particular, both materials in a sealing composition obtained by blending dinorcone tungstate phosphate (ZWP) as a filler with the Bi-BO-ZnO-AI-based glass used in the present invention.

2 3 2 3 2 3

The following shows the theoretical thermal expansion coefficient that can be calculated from the individual thermal expansion coefficients and the compounding ratios, and the actually measured thermal expansion coefficient.

(1) The sealing composition shown in Example 1 (glass powder 82% by weight, ZWP 18% by weight)

Theoretical thermal expansion ^{coefficient: 60 X 10- 7 (1 /} K)

Found thermal expansion ^{coefficient: 40 X 10- 7 (1 /} K)

(2) sealing composition theoretically calculated thermal expansion coefficient was blended sigma \ 10 wt% in the glass powder 90 wt% of Example ^{3:? 78 X 10- 7 (} 1 / K)

Found coefficient of thermal ^{expansion: 64 X 10- 7 (1 /} K)

(3) Sealing composition containing 90% by weight of the glass powder of Example 3 and 10% by weight

Theoretical calculation coefficient of thermal expansion: 82 X 10— ⁷ (1 / Κ)

Found coefficient of thermal expansion: 79 X 10- ⁷ (1ZK)

(4) Example Glass powder 90% by weight beta 3 of _3> blending 10 wt% was sealing composition theoretically calculated thermal expansion ^{coefficient:? 91 X 10- 7 (1} / Κ)

Found coefficient of thermal expansion: 90 X 10- ⁷ (1ΖΚ)

(5) A sealing composition in which 90% by weight of the glass powder of Example 3 and 10% by weight of Al were blended.

twenty three

Theoretical calculation coefficient of thermal expansion: 95 X 10 " ⁷ (1 / Κ) Found coefficient of thermal ^{expansion: 96 X 10- 7 (1 /} K)

[0033] As is clear from the theoretically calculated thermal expansion coefficient and the measured thermal expansion coefficient shown in the above paragraph 0032, when dinoreconium tungstate phosphate (ZWP) is blended as a filler, the theoretically considered thermal expansion coefficient is considered. Sealing compositions having a coefficient of thermal expansion significantly lower (smaller) than the coefficient of expansion can be obtained.

Also, when zirconium phosphate (ZP) is blended as a filler, the thermal expansion coefficient of the sealing composition tends to be lower (smaller) than the theoretically calculated thermal expansion coefficient. When SPJ or Al O is blended as a filler, the thermal expansion of the sealing composition

twenty three

It can be seen that there is little tendency for improvement in the coefficient.

Industrial applicability

In the manufacture of plasma display panels and other integrated circuits, it can be used for sealing materials such as ceramics, glass, and metals. As a lead-free sealing glass, it can be used in a wide range of applications, adapting to the environment.

Claims

The scope of the claims

Substantially contains no Pb, and a glass powder 80 98 wt ^_0/0, an inorganic filler 2-20 weight percent containing phosphate Jinorekoniumu of compounds,

The glass powder, in terms of oxide,

Bi O: 70-85% by weight

twenty three

B〇: 4.5-10% by weight

twenty three

ZnO: 8.0-20% by weight

A1〇: 0.1-1% by weight

twenty three

A composition for sealing, which is a composition containing:

Glass powder is converted to oxide,

Bi O: 80-83% by weight

twenty three

B〇: 4.5-8% by weight

twenty three

ZnO: 8.0-12% by weight

A1_rei:. 0. 1-0 5 weight ^_0/0

twenty three

2. The sealing composition according to claim 1, wherein the composition comprises:

3. The sealing composition according to claim 1, wherein the zirconium phosphate compound contained in the inorganic filler is at least 2% by weight based on the total amount of the sealing composition. 14. The sealing composition according to claim 13, wherein the composition comprises zirconium tungstate phosphate as the dinoreconium phosphate compound.

14. The sealing composition according to claim 13, wherein the total amount of the zirconium phosphate compound is zirconium tungstate phosphate.