WO2012029930A1 - Tin borate glass and sealing component - Google Patents

Abstract

Provided is a tin borate glass having a low melting point and capable of producing a sealing material that has a small difference in thermal characteristics from the material to be sealed and that is kept from causing cracks etc. at the time of sealing, even without blending an additive such as a filler. The tin borate glass is characterized by having a composition containing 62-73% by mass of SnO, 19-25% by mass of B₂O₃, 0.1-7% by mass of P₂O₅, 0-6% by mass of ZnO, 0-3% by mass of CaO, 0-7% by mass of SrO, and 0-4% by mass of Al₂O₃.

Description

Tin borate glass and sealing parts

The present invention relates to a tin borate glass, and more particularly to a tin borate glass and a sealing part that are suitably used as a sealing material for a sealing material such as alumina or soda lime glass.

As a sealing material for sealing various materials such as glass, ceramics, and metals, and electronic parts such as semiconductor elements, sealing materials mainly composed of glass are used.

In particular, when sealing electronic parts, it is required to lower the sealing temperature as much as possible in order to prevent damage to the sealing material due to heat. For this reason, what has a lower melting point is calculated | required as sealing material.
In addition, if there is a large difference in thermal characteristics between the sealing material and the sealing material, thermal stress may occur between the two due to temperature changes, which may cause cracks in the sealing material and the sealing material. There is. For this reason, the sealing material is required to have a thermal property that is similar to the sealing material.

As a glass having a low melting point, for example, Patent Document 1 discloses that “SnO, B ₂ O ₃ and P ₂ O ₅ are the main components, SnO 30 to 80% in terms of mol%, and B ₂ O ₃ 5 to 60%. , A tin borophosphate-based glass having a composition of 5 to 24% of P ₂ O ₅ is disclosed.
Patent Document 2 discloses SnO—P ₂ O ₅ glass used for a phosphor composite material. Comparative Example 10 includes SnO 73%, P ₂ O in terms of mol%. ₅ A glass having a composition of 19.4%, B ₂ O ₃ 10% is described.

Japanese Patent No. 3845853 Japanese Unexamined Patent Publication No. 2010-229002

However, the tin borophosphate-based glass described in Patent Document 1 (see Examples) has a thermal expansion coefficient of 94 × 10 ⁻⁷ to 103 × 10 ⁻⁷ / ° C., and is variously used as a sealing material. Compared with materials (for example, soda lime glass and alumina), the difference in thermal expansion coefficient is excessive.
In particular, soda lime glass substrates for plasma display panels (PDP) tend to be used with a low thermal expansion coefficient (for example, the thermal expansion coefficient of soda lime glass widely used for PDP is 85 × 10 ^{− 7 /} ° C.), Therefore, when the fixation was gradually cooled to sealing material, by thermal stress caused by the difference in thermal properties of both, there is a possibility that cracks occur in the sealing material or the like.
Further, in the glass described in Patent Document 2, for example, the glass of Example 10 (Comparative Example) is in the composition range disclosed in Patent Document 1, and the thermal expansion coefficient is 94 × 10 ⁻⁷ to 103 × 10 ⁻⁷ / It can be estimated that it is ° C. Furthermore, from the Example of patent document 1, it exists in the tendency for a thermal expansion coefficient to be high, so that SnO content increases. The SnO content described in Patent Document 2 has a SnO content of 72 mol% or more, and even if B ₂ O ₃ and ZnO, which have the effect of lowering the thermal expansion coefficient, are 5 mol% or less, the thermal expansion coefficient is It is considered that it greatly exceeds 103 × 10 ⁻⁷ / ° C. Therefore, compared with various materials (for example, soda lime glass, alumina), the thermal expansion coefficient difference is excessive compared to the case of Patent Document 1, and when the sealing material is slowly cooled and fixed, the thermal characteristics of the two are obtained. The risk of cracking in the sealing material and the like due to the thermal stress associated with the difference becomes more serious.

On the other hand, in order to reduce the difference in thermal characteristics between the sealing material and the sealing material, filler such as alumina powder is mixed with the glass powder to reduce the thermal expansion coefficient of the entire sealing material. ing.
However, when the blending ratio of the filler with respect to the glass powder is increased, the fluidity of the glass is lowered and sealing may be difficult. Also, in this case, the light entering the glass is scattered by the filler, which may impair the transparency as a sealing material, and is used for sealing light-emitting diodes that require transparency. It may become impossible.

The present invention has been made in order to solve the above-described problems, has a low melting point, and has a small difference in thermal characteristics from the sealing material, more specifically, a difference in thermal expansion coefficient, and A tin borate-based glass that has a glass transition temperature within a predetermined range and that can provide a sealing material in which generation of cracks and the like during sealing is suppressed without adding an additive such as a filler. The purpose is to provide wearing parts.

That is, the tin borate-based glass of the present invention has a SnO content of 62 to 73%, a B ₂ O ₃ content of 19 to 25%, a P ₂ O ₅ content of 0.1 to 7%, and a ZnO content in terms of oxide mass%. 0 to 6%, CaO 0 to 3%, SrO 0 to 7%, and Al ₂ O ₃ 0 to 4%.
Unless otherwise specified, “to” indicating the numerical range described above is used to mean that the numerical values described before and after it are used as a lower limit value and an upper limit value, and hereinafter “to” Used with meaning.

The tin borate-based glass preferably has a mass ratio of P ₂ O ₅ / B ₂ O ₃ satisfying 0.10 to 0.35. In addition, the tin borate-based glass preferably has a P ₂ O ₅ / (B ₂ O ₃ + SnO) ratio of 0.01 to 0.10 as a mass ratio in terms of oxide. The tin borate glass preferably has a thermal expansion coefficient at 50 to 250 ° C. of less than 90 × 10 ⁻⁷ / ° C., preferably 50 × 10 ⁻⁷ / ° C. or more and 90 × 10 ^−7. More preferably, it is less than / ° C. The tin borate-based glass preferably has a glass transition temperature (Tg) of 370 ° C. or lower, more preferably 300 ° C. or higher and 370 ° C. or lower. The difference between the crystallization peak temperature (Tc) and the glass transition temperature (Tg) is preferably 150 ° C. or higher.

The tin borate-based glass of the present invention contains SnO and B ₂ O ₃ as main components, and contains 0.1 to 7% of P ₂ O ₅ in terms of mass% in terms of oxide, at 50 to 250 ° C. The thermal expansion coefficient is less than 90 × 10 ⁻⁷ / ° C. The thermal expansion coefficient at 50 to 250 ° C. is preferably 50 × 10 ⁻⁷ / ° C. or more and less than 90 × 10 ⁻⁷ / ° C.

The tin borate-based glass is Sn-O 62-72%, B ₂ O ₃ 19-25%, ZnO 0-6%, CaO 0-3% and SrO 0 It is preferable to have a composition of ˜7% and Al ₂ O ₃ of 0˜4%.

Further, the sealing part of the present invention is characterized in that the surface or joint portion of a sealing member made of soda lime glass or alumina is sealed with the tin borate glass.

According to the present invention, sealing at a low temperature is possible, and since the difference in thermal characteristics from the material to be sealed is small, cracks accompanying temperature changes can be obtained without adding additives such as fillers. A tin borate-based glass from which a sealing material with suppressed generation can be obtained, and a sealing part using the same can be provided.

Hereinafter, embodiments of the present invention will be described.
The tin borate glass according to one embodiment of the present invention is mainly composed of SnO and B ₂ O ₃ , SnO is 62 to 73% and B ₂ O ₃ is 19 to 25 in terms of oxide mass%. %, P ₂ O ₅ 0.1 to 7%, ZnO 0 to 6%, CaO 0 to 3%, SrO 0 to 7%, and Al ₂ O ₃ 0 to 4%.

According to such a tin borate glass, the coefficient of thermal expansion can be reduced as compared with the conventional glass used as a sealing material by setting the content of each component within a predetermined range. For this reason, it is possible to reduce the difference in thermal expansion coefficient with alumina, soda lime glass, etc., which are widely used as sealing materials, and with temperature changes at the time of sealing without adding fillers, etc. A sealing material in which generation of cracks and the like is suppressed can be obtained.

Each component of tin borate glass will be described. In addition, in this specification, content of each component is described with the mass% display of oxide conversion.

SnO is a component that is paired with B ₂ O ₃ and / or P ₂ O ₅ and becomes the main skeleton (network former) of glass, and is an essential component. The content of SnO in the tin borate glass is 62% by mass or more.
When SnO is less than 62% by mass, the glass transition temperature (Tg) becomes excessively high, and the sealing temperature becomes high. From the viewpoint of obtaining a sealing material that can be sealed at a lower temperature, the content of SnO in the tin borate glass is preferably 65% by mass or more, and more preferably 66.5% by mass or more. .

On the other hand, the content of SnO in the tin borate glass is 73% by mass or less.
When SnO exceeds 73 mass%, glass will become unstable and water resistance and a weather resistance will come to fall. Further, the coefficient of thermal expansion becomes excessively high, and the difference in coefficient of thermal expansion from the sealing member increases. From the viewpoint of more excellent stability and weather resistance, the content of SnO is preferably 70% by mass or less, and more preferably 68% by mass or less.

B ₂ O ₃ is a component that becomes a main skeleton (network former) of glass and is an essential component. The content of B ₂ O ₃ in the tin borate glass is 19% by mass or more. If the content of B ₂ O ₃ is less than 19% by mass, it is difficult to obtain a stable glass, and vitrification may be difficult. From the viewpoint of more excellent stability, the content of B ₂ O ₃ is preferably 20% by mass or more, and more preferably 21% by mass or more.

On the other hand, the content of B ₂ O ₃ in the tin borate glass is 25% by mass or less.
When the content of B ₂ O ₃ exceeds 25 mass%, the glass transition temperature (Tg) becomes higher, the sealing temperature increases. From the viewpoint of obtaining a sealing material that can be sealed at a lower temperature, the content of B ₂ O ₃ is preferably 24% by mass or less, and more preferably 23% by mass or less.

P ₂ O ₅ is a component that suppresses the crystallization of glass to improve stability and improves weather resistance, and is an essential component. The content of P ₂ O ₅ in the tin borate glass is 0.1% by mass or more. When the content of P ₂ O ₅ is less than 0.1 wt%, there is a possibility that water resistance, weather resistance decreases. In addition, the glass may be easily crystallized.
From the viewpoint of more excellent weather resistance, the content of P ₂ O ₅ is preferably 3% by mass or more, and more preferably 5% by mass or more.

On the other hand, the content of P ₂ O ₅ in the tin borate glass is 7% by mass or less.
If the content of P ₂ O ₅ exceeds 7% by mass, the glass tends to phase-separate and there is a possibility that a homogeneous glass cannot be obtained. Moreover, there exists a possibility that the thermal expansion coefficient of glass may become high too much.
The content of P ₂ O _{5 in} the tin borate-based glass is preferably 6.5% by mass or less, and more preferably 6.0% by mass or less from the viewpoint of obtaining a homogeneous glass that is more difficult to separate phases.

Al ₂ O ₃ is a component that increases the stability of the glass and improves the weather resistance. The content of Al ₂ O ₃ in the tin borate glass is 4% by mass or less.
When the content of Al ₂ O ₃ exceeds 4% by mass, the glass transition temperature (Tg) becomes excessively high and the sealing temperature may be increased. From the viewpoint of obtaining a sealing material that can be sealed at a lower temperature, the content of Al ₂ O ₃ is preferably 3% by mass or less, and more preferably 2% by mass or less.

ZnO is a component that increases the stability of glass to improve water resistance and weather resistance, and reduces the coefficient of thermal expansion. The content of ZnO in the tin borate glass is 6% by mass or less. When the content of ZnO exceeds 6% by mass, the glass transition temperature (Tg) becomes excessively high and the sealing temperature may be increased.
From the viewpoint of obtaining a sealing material that can be sealed at a lower temperature, the content of ZnO is preferably 5% by mass or less, and more preferably 4% by mass or less.

CaO suppresses the crystallization of the glass by suppressing the diffusion of Sn ions (Sn ²⁺ ) in the glass. The content of CaO in the tin borate glass is 3% by mass or less.
When the content of CaO exceeds 3% by mass, the glass transition temperature (Tg) becomes excessively high and the sealing temperature may be increased. From the viewpoint of obtaining a sealing material that can be sealed at a lower temperature, the content of CaO is preferably 2% by mass or less.

SrO suppresses the crystallization of the glass by suppressing the diffusion of Sn ions (Sn ²⁺ ) in the glass. The content of SrO in the tin borate glass is 7% by mass or less. If the content of SrO exceeds 7% by mass, the glass transition temperature (Tg) becomes excessively high and the sealing temperature may be increased. From the viewpoint of obtaining a sealing material that can be sealed at a lower temperature, the content of SrO is preferably 5% by mass or less, and more preferably 3% by mass or less.

The ratio P ₂ O ₅ / B ₂ O ₃ between the content of P ₂ O _{5 and} the content of B ₂ O ₃ contained in the tin borate glass is 0.10 to 0.35 by mass ratio. Is preferred.
When the mass ratio of P ₂ O ₅ / B ₂ O ₃ exceeds 0.35, the presence of P—O—P bonding sites becomes excessive, and the proportion of components in the melt increases (clustering). Glass tends to phase-separate and there is a possibility that a homogeneous glass cannot be obtained. The above clustering means a state in which a plurality of PO ₄ tetrahedron units are locally connected, and the same applies to the following. On the other hand, when P ₂ O ₅ / B ₂ O ₃ is less than 0.10, water resistance and weather resistance may be lowered.

The ratio of the content of P ₂ O _{5 and} the content of (B ₂ O ₃ + SnO) contained in the tin borate-based glass, that is, P ₂ O ₅ / (B ₂ O ₃ + SnO) is 0. It is preferably 01 to 0.10. When the mass ratio of P ₂ O ₅ / (B ₂ O ₃ + SnO) exceeds 0.10, the thermal expansion coefficient may be excessively increased. Further, the presence of P—O—P bonding sites becomes excessive, and the ratio of clustering of components in the melt increases, so that the glass tends to phase-separate and there is a possibility that a homogeneous glass cannot be obtained. In order to make it easy to obtain homogeneous glass, P ₂ O ₅ / (B ₂ O ₃ + SnO) is more preferably 0.08 or less.
On the other hand, when the mass ratio of P ₂ O ₅ / (B ₂ O ₃ + SnO) is less than 0.01, water resistance and weather resistance may be lowered. In order to further increase the water resistance, it is more preferable that P ₂ O ₅ / (B ₂ O ₃ + SnO) is 0.05 or more.

The glass powder of tin borate-based glass can usually be produced by producing glass having the above composition by a melting method and then pulverizing the glass. The pulverization method is not particularly limited, and may be dry pulverization or wet pulverization. In the case of wet pulverization, it is preferable to use water as a solvent. For pulverization, a pulverizer such as a roll mill, a ball mill, or a jet mill can be appropriately used. After pulverization, the glass may be dried and classified as necessary.

The thermal expansion coefficient of tin borate glass at 50 to 250 ° C. is preferably 50 × 10 ⁻⁷ / ° C. or more and less than 90 × 10 ⁻⁷ / ° C. When the thermal expansion coefficient at 50 to 250 ° C. is 90 × 10 ⁻⁷ / ° C. or more or smaller than 50 × 10 ⁻⁷ / ° C., alumina or soda lime glass generally used as a sealing material The difference in coefficient of thermal expansion from various materials such as (ie, the sealing material) becomes large, and thermal stress tends to occur between these sealing materials, so that cracks and the like are likely to occur. The soda lime glass described above is a so-called soda lime glass in a broad sense, and refers to soda lime silicate glass having a composition containing SiO ₂ , Na ₂ O and CaO as main components. Such soda-lime glass may contain Al ₂ O ₃ , K ₂ O, alkaline earth oxides, and other components that are appropriately added according to the purpose. Hereinafter, the soda lime glass in the present specification means the above-mentioned soda lime glass.
The upper limit of the thermal expansion coefficient of tin borate glass at 50 to 250 ° C. is more preferably 87 × 10 ⁻⁷ / ° C. or less, further preferably 85 × 10 ⁻⁷ / ° C. or less, and most preferably It is 82 × 10 ⁻⁷ / ° C. or lower. The lower limit of the coefficient of thermal expansion of tin borate glass at 50 to 250 ° C. is more preferably 60 × 10 ⁻⁷ / ° C. or more.

The glass transition temperature (Tg) of the tin borate glass is preferably 300 to 370 ° C.
When the glass transition temperature (Tg) of the tin borate glass exceeds 370 ° C., the temperature required for sealing (that is, the sealing temperature) becomes excessively high. There is a risk of damaging certain electronic components. From the viewpoint of obtaining a sealing material that can be sealed at a lower temperature, the glass transition temperature (Tg) of the tin borate glass is preferably 360 ° C. or lower.
On the other hand, if the glass transition temperature (Tg) of the tin borate glass is less than 300 ° C., the glass becomes unstable and the weather resistance may be lowered. The glass transition temperature (Tg) of the tin borate glass is more preferably 320 ° C. or higher, and further preferably 340 ° C. or higher.

The difference between the crystallization peak temperature (Tc) and the glass transition temperature (Tg), which is measured by a differential thermal analyzer (DTA), is preferably 150 ° C. or higher.
If the difference between the crystallization peak temperature (Tc) and the glass transition temperature (Tg) is less than 150 ° C., the temperature range that can be sealed is too narrow, and efficient production may be difficult.
Since the difference between the crystallization peak temperature (Tc) and the glass transition temperature (Tg) is within the above range, the temperature range in which an amorphous state can be obtained is widened, and the sealing by heat treatment is stabilized in a wide temperature range. Can be performed.
The difference between the crystallization peak temperature (Tc) and the glass transition temperature (Tg) is more preferably 160 ° C. or higher, further preferably 165 ° C. or higher, and most preferably 170 ° C. or higher.

If the crystallization peak temperature (Tc) is not detected by measurement with a differential thermal analyzer (DTA), the temperature range in which the amorphous state can be obtained becomes wider, and the sealing by heat treatment is stable in a wider temperature range. Can be performed. If the crystallization peak temperature (Tc) is not detected, it can be interpreted that the temperature difference is infinite (∞). In this case, the crystallization peak temperature (Tc) and the glass transition temperature (Tg) ) There is no particular upper limit to the temperature difference.

The thus obtained tin borate-based glass has a predetermined mass ratio of fillers such as alumina powder and zirconia powder, and other components as required, as long as the fluidity and transparency of the glass are not impaired. It is also possible to use as a composition prepared by blending and mixing.

Hereinafter, another embodiment of the present invention will be described.
The tin borate glass according to the present embodiment contains SnO and B ₂ O ₃ as main components, and contains 0.1 to 7% of P ₂ O ₅ in terms of mass% in terms of oxides, and 50 to 250 The thermal expansion coefficient at 0 ° C. is less than 90 × 10 ⁻⁷ / ° C.

According to such a tin borate-based glass, the thermal expansion coefficient is within a predetermined range, so that the heat of the sealing material such as alumina and soda lime glass can be increased compared to the conventional glass used as the sealing material. The difference in characteristic characteristics can be reduced. For this reason, even if it does not add a filler, the sealing material by which generation | occurrence | production of the crack at the time of sealing various materials mentioned above was suppressed can be obtained.

Various materials such as alumina and soda lime glass that are generally used as sealing materials when the thermal expansion coefficient at 50 to 250 ° C. is 90 × 10 ⁻⁷ / ° C. or more (that is, sealing materials) The thermal characteristic difference between the two and the sealing material increases, and thermal stress is likely to occur between these materials to be sealed. The upper limit of the thermal expansion coefficient of tin borate glass at 50 to 250 ° C. is more preferably 87 × 10 ⁻⁷ / ° C. or less, further preferably 85 × 10 ⁻⁷ / ° C. or less, and most preferably It is 82 × 10 ⁻⁷ / ° C. or lower.

The thermal expansion coefficient of tin borate glass at 50 to 250 ° C. is preferably 50 × 10 ⁻⁷ / ° C. or higher. When the thermal expansion coefficient at 50 to 250 ° C. is less than 50 × 10 ⁻⁷ / ° C., heat with various materials (sealing materials) such as alumina and soda lime glass, which are generally used as sealing materials Since the difference in expansion coefficient becomes large and thermal stress is likely to occur between these materials to be sealed, cracks and the like may be easily generated.
The lower limit of the thermal expansion coefficient of tin borate glass at 50 to 250 ° C. is more preferably 60 × 10 ⁻⁷ / ° C. or more.

Hereinafter, each component of the tin borate glass according to the present embodiment will be described.

The ratio of the content of P ₂ O _{5 and} the content of (B ₂ O ₃ + SnO) contained in the tin borate-based glass, that is, P ₂ O ₅ / (B ₂ O ₃ + SnO) is 0. It is preferably 01 to 0.10. When the mass ratio of P ₂ O ₅ / (B ₂ O ₃ + SnO) exceeds 0.10, the thermal expansion coefficient may be excessively increased. Further, the presence of P—O—P bonding sites becomes excessive, and the ratio of clustering of components in the melt increases, so that the glass tends to phase-separate and there is a possibility that a homogeneous glass cannot be obtained. In order to make it easy to obtain homogeneous glass, P ₂ O ₅ / (B ₂ O ₃ + SnO) is more preferably 0.08 or less.
On the other hand, when the mass ratio of P ₂ O ₅ / (B ₂ O ₃ + SnO) is less than 0.01, water resistance and weather resistance may be lowered. In order to further increase the water resistance, it is more preferable that P ₂ O ₅ / (B ₂ O ₃ + SnO) is 0.05 or more.

SnO is a component that is paired with B ₂ O ₃ and / or P ₂ O ₅ and becomes the main skeleton (network former) of glass, and is an essential component. The SnO content in the tin borate glass is preferably 62% by mass or more.
When SnO is less than 62% by mass, the glass transition temperature (Tg) becomes excessively high, and the sealing temperature becomes high. From the viewpoint of obtaining a sealing material that can be sealed at a lower temperature, the content of SnO in the tin borate glass is preferably 65% by mass or more, and more preferably 66.5% by mass or more. .

On the other hand, the SnO content in the tin borate-based glass is preferably 72% by mass or less.
When SnO exceeds 72 mass%, glass will become unstable and water resistance and weather resistance will fall. In addition, the coefficient of thermal expansion increases, and the difference in coefficient of thermal expansion from the sealing member increases. From the viewpoint of more excellent stability and weather resistance, the content of SnO is preferably 70% by mass or less, and more preferably 68% by mass or less.

B ₂ O ₃ is a component that becomes a main skeleton (network former) of glass and is an essential component. The content of B ₂ O ₃ in the tin borate glass is preferably 19% by mass or more. If the content of B ₂ O ₃ is less than 19% by mass, it is difficult to obtain a stable glass, and vitrification may be difficult. From the viewpoint of more excellent stability, the content of B ₂ O ₃ is preferably 20% by mass or more, and more preferably 21% by mass or more.

On the other hand, the content of B ₂ O ₃ in the tin borate glass is preferably 25% by mass or less.
When the content of B ₂ O ₃ exceeds 25 mass%, the glass transition temperature (Tg) becomes higher, the sealing temperature increases. From the viewpoint of obtaining a sealing material that can be sealed at a lower temperature, the content of B ₂ O ₃ is preferably 24% by mass or less, and more preferably 23% by mass or less.

P ₂ O ₅ is a component that suppresses the crystallization of glass to improve stability and improves weather resistance, and is an essential component. The content of P ₂ O ₅ in the tin borate glass is 0.1% by mass or more. When the content of P ₂ O ₅ is less than 0.1 wt%, there is a possibility that water resistance, weather resistance decreases. In addition, the glass may be easily crystallized.
From the viewpoint of more excellent weather resistance, the content of P ₂ O ₅ is preferably 3% by mass or more, and more preferably 5% by mass or more.

On the other hand, the content of P ₂ O ₅ in the tin borate glass is 7% by mass or less.
If the content of P ₂ O ₅ exceeds 7% by mass, the glass tends to phase-separate and there is a possibility that a homogeneous glass cannot be obtained. Moreover, there exists a possibility that the thermal expansion coefficient of glass may become high too much.
The content of P ₂ O _{5 in} the tin borate-based glass is preferably 6.5% by mass or less, and more preferably 6.0% by mass or less from the viewpoint of obtaining a homogeneous glass that is more difficult to separate phases.

Al ₂ O ₃ is a component that increases the stability of the glass and improves the weather resistance. The content of Al ₂ O ₃ in the tin borate glass is preferably 4% by mass or less.
When the content of Al ₂ O ₃ exceeds 4% by mass, the glass transition temperature (Tg) becomes excessively high and the sealing temperature may be increased. From the viewpoint of obtaining a sealing material that can be sealed at a lower temperature, the content of Al ₂ O ₃ is preferably 3% by mass or less, and more preferably 2% by mass or less.

ZnO is a component that increases the stability of glass to improve water resistance and weather resistance, and reduces the coefficient of thermal expansion. The content of ZnO in the tin borate glass is preferably 6% by mass or less. When the content of ZnO exceeds 6% by mass, the glass transition temperature (Tg) becomes excessively high and the sealing temperature may be increased.
From the viewpoint of obtaining a sealing material that can be sealed at a lower temperature, the content of ZnO is preferably 5% by mass or less, and more preferably 4% by mass or less.

CaO suppresses the crystallization of the glass by suppressing the diffusion of Sn ions (Sn ²⁺ ) in the glass. The content of CaO in the tin borate glass is preferably 3% by mass or less.
When the content of CaO exceeds 3% by mass, the glass transition temperature (Tg) becomes excessively high and the sealing temperature may be increased. From the viewpoint of obtaining a sealing material that can be sealed at a lower temperature, the content of CaO is preferably 2% by mass or less.

SrO suppresses the crystallization of the glass by suppressing the diffusion of Sn ions (Sn ²⁺ ) in the glass. The content of SrO in the tin borate glass is preferably 7% by mass or less. If the content of SrO exceeds 7% by mass, the glass transition temperature (Tg) becomes excessively high and the sealing temperature may be increased. From the viewpoint of obtaining a sealing material that can be sealed at a lower temperature, the content of SrO is preferably 5% by mass or less, and more preferably 3% by mass or less.

The glass powder of tin borate-based glass can usually be produced by producing glass having the above composition by a melting method and then pulverizing the glass. The pulverization method is not particularly limited, and may be dry pulverization or wet pulverization. In the case of wet pulverization, it is preferable to use water as a solvent. For pulverization, a pulverizer such as a roll mill, a ball mill, or a jet mill can be appropriately used. After pulverization, the glass may be dried and classified as necessary.

The glass transition temperature (Tg) of the tin borate glass is preferably 300 to 370 ° C. When the glass transition temperature (Tg) of the tin borate glass exceeds 370 ° C., the temperature required for sealing (that is, the sealing temperature) becomes excessively high. There is a risk of damaging certain electronic components. From the viewpoint of obtaining a sealing material that can be sealed at a lower temperature, the glass transition temperature (Tg) of the tin borate glass is preferably 360 ° C. or lower.
On the other hand, if the glass transition temperature (Tg) of the tin borate glass is less than 300 ° C., the glass becomes unstable and the weather resistance may be lowered. The glass transition temperature (Tg) of the tin borate glass is more preferably 320 ° C. or higher, and further preferably 340 ° C. or higher.

The difference between the crystallization peak temperature (Tc) and the glass transition temperature (Tg), which is measured by a differential thermal analyzer (DTA), is preferably 150 ° C. or higher.
If the difference between the crystallization peak temperature (Tc) and the glass transition temperature (Tg) is less than 150 ° C., the temperature range that can be sealed is too narrow, and efficient production may be difficult.
Since the difference between the crystallization peak temperature (Tc) and the glass transition temperature (Tg) is within the above range, the temperature range in which an amorphous state can be obtained is widened, and the sealing by heat treatment is stabilized in a wide temperature range. Can be performed.
The difference between the crystallization peak temperature (Tc) and the glass transition temperature (Tg) is more preferably 160 ° C. or higher, further preferably 165 ° C. or higher, and most preferably 170 ° C. or higher.
As described above, when the crystallization peak temperature (Tc) is not detected by measurement with a differential thermal analyzer (DTA), the temperature range in which the amorphous state can be obtained becomes wider, and the sealing by heat treatment is performed in a wider temperature range. It is possible to perform wearing stably. If the crystallization peak temperature (Tc) is not detected, it can be interpreted that the temperature difference is infinite (∞). In this case, the crystallization peak temperature (Tc) and the glass transition temperature (Tg) ) There is no particular upper limit to the temperature difference.

The thus obtained tin borate-based glass has a predetermined mass ratio of fillers such as alumina powder and zirconia powder, and other components as required, as long as the fluidity and transparency of the glass are not impaired. It is also possible to use as a composition prepared by blending and mixing.

The tin borate glass of the present invention thus obtained is used for sealing electronic parts such as light emitting diode elements (LEDs) in addition to sealing general substrate materials such as soda lime glass and alumina. It is also possible to use it as a sealing material that is sealed using laser light. Furthermore, it can also be used as a binder for solar cell electrodes.

The sealing part of the present invention is formed by sealing the surface or bonding portion of the above-mentioned sealed member made of soda lime glass or alumina with the tin borate glass of the present invention.
According to the sealing component of the present invention, the use of tin borate-based glass having a small difference in thermal characteristics from the sealing material as a sealing material results in less defects such as cracks and warpage, and the sealing material It can be sealed with high airtightness.

Examples 1 to 20 and Comparative Examples 1 to 4
Formulated raw materials such as stannous oxide, tin pyrophosphate, zinc metaphosphate, calcium metaphosphate, aluminum metaphosphate, anhydrous boric acid and strontium carbonate so that the glass after mixing has the glass composition shown in Tables 1-3. Mixed. The mixed raw material was put into a quartz crucible and heated and melted at 1100 ° C. for 40 minutes, and then the molten glass was poured into a carbon mold and cooled.
The operations from preparation and mixing of the raw material compounds to cooling after heating and melting were all performed in a glove box (dew point temperature: −60 to −100 ° C.) in a dry nitrogen atmosphere.

About the obtained glass of each Example and Comparative Example, by the method shown below, measurement of glass transition temperature (Tg), crystallization peak temperature (Tc), yield point (Tf), thermal expansion coefficient (α), and The weather resistance and the presence or absence of devitrification were evaluated.
In addition, after measuring the glass transition temperature (Tg), with respect to the glass of each Example and Comparative Example that are subjected to processing operations by measuring the yield point (Tf) and the average thermal expansion coefficient (α) and evaluating the weather resistance, Annealing treatment was performed at a temperature 15 to 25 ° C. higher than the glass transition temperature (Tg) for about 1 hour. The results are shown in Tables 1 to 3.
In Table 3, “/” indicates that the glass transition point (Tg) or the like is not measurable (the column indicated as “/” in Comparative Examples 1 to 3) or not measured.

(1) Glass transition temperature (Tg)
The glass transition temperature was measured by the method shown below.
That is, the glass of each Example and Comparative Example was pulverized with an alumina mortar to obtain glass powder. 100 mg of each glass powder obtained was filled in an alumina pan, and the glass transition temperature was raised by a differential thermal analyzer (trade name “EXSTAR6000TG / DTA” manufactured by Seiko Instruments Inc.) at a rate of 10 ° C./min. (Tg) (unit: ° C.) was measured.
(2) Crystallization peak temperature (Tc)
The crystallization peak temperature (Tc) was measured by the method shown below.
That is, the glass powders obtained by pulverizing the glass of each Example and Comparative Example were each subjected to a rate of 10 ° C./min using the same differential thermal analyzer as that used for measuring the glass transition temperature (Tg). The temperature of the crystallization exothermic peak (unit: ° C.) was measured.
(3) Bending point (Tf)
The yield point (Tf) was measured by the following method.
That is, the glass of each example and comparative example was processed into a cylindrical shape having a diameter of 5 mm and a length of 20 mm, respectively, and a horizontal differential detection type thermal dilatometer (Bruker AXS, trade name: TD5010) was used. Then, the temperature was raised at a rate of 10 ° C./min, and the yield point (Tf) (unit: ° C.) was measured.
(4) Average thermal expansion coefficient (α)
The average thermal expansion coefficient (α) was measured by the following method.
That is, with respect to each of the glass of each example and comparative example, the amount of elongation was measured with the above-mentioned horizontal differential detection type thermal dilatometer at a temperature rising rate of 10 ° C./min, and the average thermal expansion from 50 to 250 ° C. The coefficient (unit: / ° C.) was calculated.
(5) Weather resistance Weather resistance was evaluated by the following method.
That is, the glass of each example and comparative example was made into a glass block having a size of about 20 mm × 20 mm and a thickness of 2 mm, and both surfaces were mirror-polished, and the constant temperature and constant temperature set at 80 ° C. and relative humidity of 80%. Holding in a damp bath and taking out as appropriate, the spectral transmittance at 460 nm was measured using a spectrophotometer (manufactured by Perkin Elmer, product name “Lambda 950”), and the elapsed time with respect to the initial value T0 of the spectral transmittance The ratio of the subsequent spectral transmittance T1 was calculated based on the formula [(T1 / T0) × 100 (%)]. The time when the calculated value is 90% or less is shown in Tables 1 to 3 as “weather resistance [time]”.
(6) Presence or absence of devitrification Presence or absence of devitrification after glass production was evaluated by the following method.
That is, stannous oxide, tin pyrophosphate, zinc metaphosphate, calcium metaphosphate, aluminum metaphosphate, anhydrous boric acid and strontium carbonate were mixed and mixed so that the glass after mixing had the glass composition shown in Tables 1 to 3. .
The mixed raw material compound was put in a quartz crucible and heated and melted at 1100 ° C. for 40 minutes, and then the molten glass was poured out into a carbon mold, and the presence or absence of crystals was visually confirmed before being cooled and solidified. Tables 1 to 3 are shown as “◯” when no crystal precipitation was confirmed, and “X” when white turbidity (phase separation) due to crystal precipitation was confirmed partially or entirely.

As is apparent from Tables 1 to 3, the tin borate glasses having the specific compositions of Examples 1 to 20 exhibit a thermal expansion coefficient of less than 90 × 10 ⁻⁷ / ° C., and are the sealing materials. The difference in thermal expansion coefficient from the soda-lime glass (83 × 10 ⁻⁷ / ° C. to 85 × 10 ⁻⁷ / ° C.) and alumina (73 × 10 ⁻⁷ / ° C. to 81 × 10 ⁻⁷ / ° C.) It can be seen that cracks are less likely to occur when these materials are sealed. Further, since the glass powders of Examples 1 to 20 have a low yield point of 400 ° C. or lower, they can be sealed at a low temperature.

On the other hand, the tin borate glasses of Comparative Examples 1 to 3 containing P ₂ O ₅ in excess of 7% by mass caused phase separation when vitrified and could not obtain a stable glass state. .
The tin borate glass of Comparative Example 4 containing 22% by mass of P ₂ O ₅ has a thermal expansion coefficient of 103 × 10 ⁻⁷ / ° C., and the difference in thermal expansion coefficient from the soda lime glass or alumina described above. It can be seen that cracks are likely to occur when these materials are sealed.

(Example 21)
It has a composition of the glass powder described in Example 6, MnO 42% by mass, CuO 26% by mass, Fe ₂ O ₃ 15% by mass, Al ₂ O ₃ 8% by mass, SiO ₂ 5% by mass, and an average particle diameter Was prepared with a 1.2 μm laser absorber.

A sealing material was prepared by mixing 95% by mass of the glass powder and 5% by mass of the laser absorbing material.

Next, two glass substrates (dimensions: 100 mm × 100 mm × 0.55 mm thickness) made of soda lime glass (thermal expansion coefficient: 87 × 10 ⁻⁷ / ° C.) are prepared and sealed on one glass substrate. The material was dispersed and applied, and the other glass substrate was laminated.

Next, the soda-lime glass substrate formed by laminating the coating layer of the sealing material was placed on the sample holder of the laser irradiation apparatus.
A circular laser beam having a wavelength of 808 nm, an output density of 0.56 kW / cm ² , and a beam shape of 1.5 mm is applied to the sealing material coating layer at a position where the sealing material is applied at a scanning speed of 3 mm / second. Irradiation formed a sealing material layer.

When the state of the obtained sealing material layer was confirmed by SEM, it was confirmed that the entire sealing material layer was vitrified well and the two glass substrates were adhered together.

(Reference Examples 1-2)
Laser irradiation was performed in the same manner as in Example 21 except that the output density was changed to 0.85 kW / cm ² . (Reference Example 1)
Also, output density 0.56kW ^/ cm ^2, while changing the order of ^{1.13kW / cm 2, 1.70kW / cm} 2, 2.26kW / cm 2, wavelength 808 nm, beam shape with a diameter of 1.5mm circular A fixed point was irradiated to the position where the sealing material was applied. The laser beam was irradiated for 10 seconds for each output density. (Reference Example 2)

When the state of each obtained sealing material layer was confirmed by SEM, the sealing material layer of Reference Example 1 obtained by irradiation at an output density of 0.85 kW / cm ² was generally well vitrified, Although the two glass substrates were bonded together, it was confirmed that they were partially crystallized.
In addition, the sealing material layer of Reference Example 2 obtained by irradiation while changing the power density from 0.56 kW / cm ² to 2.26 kW / cm ² is crystallized in the entire laser irradiation region, and the substrate is It could not be adhered.

In Example 21 and Reference Examples 1 and 2 described above, only the example in which sealing by laser irradiation (laser sealing) was performed was described. However, in the tin borate glass of the present invention, such laser irradiation is performed. The sealing is not limited to the above, and the sealing can be performed by optimizing the temperature condition using, for example, a general electric furnace.

According to the present invention, the filler has a low melting point, has a small difference in thermal expansion coefficient from the material to be sealed, and has a glass transition temperature within a predetermined range suitable for sealing with the material to be sealed. Even without the addition of additives such as, it is possible to obtain a tin borate glass for sealing materials in which the occurrence of cracks during sealing is suppressed, and the periphery of a soda-lime glass substrate for a plasma display panel It is useful for sealing of electronic parts such as light-emitting diode elements or other soda-lime glass substrates or alumina substrates.
The specification, claims and abstract of Japanese Patent Application 2010-198255 filed on September 3, 2010 and Japanese Patent Application 2010-198256 filed on September 3, 2010 The entire contents are hereby incorporated by reference into the present disclosure.

Claims (18)

1. SnO 62-73%, B ₂ O ₃ 19-25%, P ₂ O ₅ 0.1-7%, ZnO 0-6%, CaO 0-3% A tin borate-based glass having a composition of 0 to 7% of SrO and 0 to 4% of Al ₂ O ₃ .
2. The tin borate-based glass according to claim 1, wherein P ₂ O ₅ / B ₂ O ₃ satisfies 0.10 to 0.35 in terms of mass ratio in terms of oxide.
3. _{3. The} tin borate-based glass according to claim 1, wherein P ₂ O ₅ / (B ₂ O ₃ + SnO) satisfies 0.01 to 0.10 in terms of an oxide-converted mass ratio.
4. The tin borate-based glass according to any one of claims 1 to 3, wherein the thermal expansion coefficient at 50 to 250 ° C is less than 90 × 10 ^-7 / ° C.
5. The boric acid according to any one of claims 1 to 4, wherein the thermal expansion coefficient at 50 to 250 ° C is 50 x 10 ^-7 / ° C or more and less than 90 x 10 ^-7 / ° C. Tin-based glass.
6. The glass transition temperature (Tg) is 370 ° C. or lower, the tin borate-based glass according to any one of claims 1 to 5.
7. The glass transition temperature (Tg) is 300 ° C. or higher and 370 ° C. or lower, and the tin borate-based glass according to any one of claims 1 to 6.
8. The tin borate glass according to any one of claims 1 to 7, wherein a difference between a crystallization peak temperature (Tc) and a glass transition temperature (Tg) is 150 ° C or more.
9. It contains SnO and B ₂ O ₃ as main components, contains 0.1 to 7% of P ₂ O ₅ in terms of mass% in terms of oxide, and has a thermal expansion coefficient of 90 × 10 ⁻⁷ / 50 at 50 to 250 ° C. A tin borate-based glass characterized by a temperature of less than ° C.
10. 10. The tin borate glass according to claim 9, wherein the thermal expansion coefficient at 50 to 250 ° C. is 50 × 10 ⁻⁷ / ° C. or more and less than 90 × 10 ⁻⁷ / ° C.
11. The glass transition temperature (Tg) is 370 ° C or lower, the tin borate glass according to claim 9 or 10.
12. 12. The tin borate glass according to claim 9, wherein the glass transition temperature (Tg) is 300 ° C. or more and 370 ° C. or less.
13. The tin borate glass according to any one of claims 9 to 12, wherein a difference between a crystallization peak temperature (Tc) and a glass transition temperature (Tg) is 150 ° C or higher.
14. The tin borate according to any one of claims 9 to 13, wherein P ₂ O ₅ / (B ₂ O ₃ + SnO) satisfies 0.01 to 0.10 in terms of an oxide-converted mass ratio. Glass.
15. The tin borate according to any one of claims 9 to 14, wherein P ₂ O ₅ / (B ₂ O ₃ + SnO) satisfies 0.05 to 0.08 in terms of an oxide-converted mass ratio. Glass.
16. SnO 62-72%, B ₂ O ₃ 19-25%, ZnO 0-6%, CaO 0-3%, SrO 0-7%, Al ₂ O ₃ The tin borate-based glass according to any one of claims 9 to 15, which has a composition of 0 to 4%.
17. SnO is 65 to 70%, B ₂ O ₃ is 20 to 24%, P ₂ O ₅ is 3 to 6.5%, ZnO is 0 to 5%, and CaO is 0 to 3% in terms of mass% in terms of oxide. The tin borate-based glass according to any one of claims 9 to 16, which has a composition of 0 to 5% of SrO and 0 to ₂ % of Al ₂ O ₃ .
18. A sealed part formed by sealing the surface or bonded portion of a sealed member made of soda lime glass or alumina with the tin borate-based glass according to any one of claims 1 to 17. .