JP7375804B2 - Lead-free low-melting glass compositions, low-melting glass composites, glass pastes and applied products - Google Patents

Description

The present invention relates to lead-free low melting point glass compositions, low melting point glass composite materials and applied products.

In display panels such as vacuum insulated double-glazed glass panels, plasma display panels, organic EL display panels, and fluorescent display tubes that are applied to window glass, and electrical and electronic components such as crystal resonators, IC ceramic packages, and semiconductor sensors. Sealing, adhesion, etc. are performed using a low melting point glass composite material containing a low melting point glass composition and low thermal expansion filler particles. This low melting point glass composite material is often applied in the form of a low melting point glass paste. The low melting point glass paste is applied to a base material by a screen printing method, a dispenser method, etc., and is baked after drying to be applied for sealing, adhesion, etc. During sealing, adhesion, etc., the low melting point glass composition contained in the low melting point glass composite material or the low melting point glass paste softens and flows to bring it into close contact with the member to be sealed, the member to be bonded, etc.

In addition, in many electrical and electronic components such as solar cells, image display devices, multilayer capacitors, crystal resonators, LEDs (light emitting diodes), and multilayer circuit boards, low melting point glass composites containing a low melting point glass composition and metal particles are used. Electrodes and wiring are formed depending on the material. This low-melting point glass composite material is also used as a conductive joint for electrical continuity and a heat dissipating joint for heat conduction. When forming electrodes, wiring, heat-dissipating joints, etc., the low-melting point glass composition contained in the low-melting point glass composite material and low-melting point glass paste softens and flows, causing sintering of metal particles and the formation of substrates. Close contact.

As the low melting point glass composition contained in the above-mentioned low melting point glass composite materials and their low melting point glass pastes, PbO-B ₂ O ₃ based low melting point glass compositions containing a very large amount of lead oxide were once widely used. Ta. This PbO-B ₂ O _3- based low melting point glass composition has a low softening point of 350 to 400°C, exhibits good softening fluidity at 400 to 450°C, and has relatively high chemical stability. ing.

However, in recent years, the trend toward green procurement and green design has become stronger worldwide, and safer materials are now required. For example, in Europe, the European Union (EU) Directive (RoHS Directive) regarding the restriction of the use of specific hazardous substances in electronic and electrical equipment came into effect on July 1, 2006. Under the RoHS Directive, lead, mercury, cadmium, and hexavalent chromium are designated as prohibited substances. For this reason, the above-mentioned PbO-B ₂ O _3- based low melting point glass composition is practically difficult to use.

Therefore, development of new low-melting point glass compositions that do not contain lead is underway.

Patent Document 1 describes 100 parts by weight of a mixed powder consisting of V ₂ O ₅ : 52.5 to 57.5 weight %, TeO ₂ : 40 to 45 weight %, and Li ₂ O : 2.5 to 7.5 weight %. discloses a method for producing a moisture-sensitive glass having crystallinity from a starting material powder containing 8 to 12 parts by weight of Ag ₂ O. Patent Document 1 discloses that 5 parts by weight or less of K ₂ O may be blended into the above-mentioned starting material powder.

Patent Document 2 contains Ag ₂ O, V ₂ O ₅ and TeO ₂ as main components, the total content is 75% by mass or more, and the remainder is P ₂ O ₅ , BaO, K ₂ O, and WO. A lead-free glass composition containing one or more of ₃ , Fe ₂ O ₃ , MnO ₂ , Sb ₂ O ₃ , and ZnO is disclosed. From Patent Document 2, this lead-free glass composition has a softening point of 320° C. or lower as determined from the second endothermic peak temperature of differential thermal analysis (DTA), and samples that give desirable results as examples have a softening point of 320° C. or less. It can be read that the temperature is 268°C or higher. Further, Patent Document 2 discloses a glass frit, a sealing glass paste, a conductive glass paste, and an electrical/electronic component using these, including this lead-free glass composition.

Japanese Unexamined Patent Publication No. 61-242927 Patent No. 5726698

In the Ag ₂ O-V ₂ O ₅ -TeO ₂ -Li ₂ O-based lead-free glass composition disclosed in Patent Document 1, the glass obtained by heating and firing is crystallized.

The _Ag2O - _{V2O5- TeO2} -based lead-free glass composition disclosed in Patent Document ₂ has a lower softening point than the conventional PbO- _{B2O3 -} based low melting point glass composition. However, there is room for improvement in adhesiveness in order to improve yield. Furthermore, since a large amount of silver oxide (Ag ₂ O) is used to lower the temperature, the unit cost of raw materials becomes extremely high, which is a problem in product application.

The purpose of the present invention is to improve adhesion, improve the yield of applied products, reduce the amount of silver oxide used, and have a low softening point and soften and flow at low temperatures. An object of the present invention is to provide a glass composition.

The lead-free low melting point glass composition of the present invention contains vanadium oxide, tellurium oxide, silver oxide, and lithium oxide, and as additional components, at least one of K ₂ O and Na ₂ O, and BaO, WO ₃ , and ZnO. , Fe ₂ O ₃ , Al ₂ O ₃ , La ₂ O ₃ , MgO, CeO ₂ and one or more selected from the group consisting of ZrO ₂ , and the following relational expression (1) in terms of oxides. satisfy.

2[V ₂ O ₅ ]≧[Ag ₂ O]+[R ₂ O]…(1)
₍ In the formula _, [X] represents _the content of _component be.)

According to the present invention, the adhesion is improved, the yield of applied products can be improved, the amount of silver oxide used is reduced, and the lead-free, low melting point material has a low softening point and softens and flows at low temperatures. A glass composition can be provided.

It is a graph showing the results of typical differential thermal analysis (DTA) specific to glass. FIG. 1 is a schematic plan view showing a vacuum insulated double-glazed glass panel of an example. FIG. 2A is a sectional view taken along line AA in FIG. 2A. FIG. 2B is a schematic plan view showing a part of the manufacturing process of the vacuum insulated double glass panel of FIG. 2A. FIG. 3A is a sectional view taken along line AA in FIG. 3A. FIG. 2B is a schematic plan view showing a part of the manufacturing process of the vacuum insulated double glass panel of FIG. 2A. FIG. 4A is a sectional view taken along line AA in FIG. 4A. FIG. 2B is a schematic cross-sectional view showing a part of the manufacturing process of the vacuum insulated double-glazed glass panel of FIG. 2A. 6 is a sealing temperature profile in the manufacturing process of the vacuum insulated double glass panel shown in FIG. 5.

Embodiments of the present invention will be described in detail below with reference to the drawings. However, the present invention is not limited to the embodiments discussed here, and can be combined and improved as appropriate without changing the gist.

(Glass composition)
In so-called low melting point glass compositions, in general, the lower the characteristic temperatures such as transition point, yield point, softening point, etc., the better the softening fluidity at low temperatures. On the other hand, if the characteristic temperature is lowered too much, the crystallization tendency increases and crystallization becomes easier during heating and firing. This crystallization becomes a factor that reduces softening fluidity at low temperatures. Further, the lower the characteristic temperature of the glass, the worse the chemical stability such as moisture resistance and acid resistance. Furthermore, the impact on the environmental load tends to increase. For example, in conventional PbO-B ₂ O _3- based low-melting glass compositions, the higher the harmful PbO content, the lower the characteristic temperature, but the greater the crystallization tendency, and the lower the chemical stability. The impact on the environmental load will also be greater.

The present inventor has developed a glass composition that is substantially lead-free, yet has better softening fluidity at lower temperatures than conventional PbO-B ₂ O _3- based low melting point glass compositions, and has excellent adhesive properties. We conducted extensive research on glass compositions that have good chemical stability. As a result, the present inventors discovered that the above requirements were simultaneously met in a new lead-free glass composition, and completed the present invention. In particular, a glass composition that softens and flows at a sufficiently lower temperature (less than 300° C.) compared to conventional PbO-B ₂ O _3- based low melting point glass compositions was obtained.

Specifically, the lead-free low melting point glass composition according to the present invention contains vanadium oxide, tellurium oxide, silver oxide, and lithium oxide as main components, and the content of these main components is as follows in terms of oxides. Relational expression (1) is satisfied.

2[V ₂ O ₅ ]≧[Ag ₂ O]+[R ₂ O]…(1)
Here, [R ₂ O]=[Li ₂ O]+[K ₂ O]+[Na ₂ O]. In addition, the content of oxide X is expressed as [X] (the same applies hereinafter). Moreover, the unit is "mol%" (the same applies hereinafter). "Mole%" is the content of each component contained in the glass composition calculated as a proportion of the total glass composition in terms of oxide. Note that 2[V ₂ O ₅ ] means 2×[V ₂ O ₅ ], that is, twice [V ₂ O ₅ ].

Furthermore, at least one of BaO, WO ₃ , ZnO, K ₂ O, Fe ₂ O ₃ , Al ₂ O ₃ , La ₂ O ₃ , MgO, CeO ₂ , ZrO ₂ and Na ₂ O is added as an additional component. include.

Here, "lead-free" in the present invention means that the lead (Pb) content is 1000 ppm or less, which is the allowable range under the RoHS Directive.

By adding additional components, the crystallization tendency can be reduced.

In other words, the lead-free low melting point glass composition according to the present invention contains oxides of silver (Ag), tellurium (Te), vanadium (V) and lithium (Li) as main components, and barium (Ba) as an additional component. , tungsten (W), zinc (Zn), potassium (K), iron (Fe), aluminum (Al), yttrium (Y), lanthanum (La), magnesium (Mg), cerium (Ce), zirconium (Zr) and an oxide of at least one of sodium (Na), erbium (Er), praseodymium (Pr), yttribium (Yb), gallium (Ga), indium (In), and molybdenum (Mo).

Further, it is desirable that the lead-free low melting point glass composition according to the present invention satisfies the above relational expression (1) and also satisfies the following relational expressions (2) and (3).

[TeO ₂ ]＞[V ₂ O ₅ ]＞[Ag ₂ O]…(2)
30≦[TeO ₂ ]≦50…(3)
By setting the composition within the above range, the softening point of the glass can be lowered to 300° C. or lower.

Furthermore, although the lead-free low melting point glass composition of the present invention has a low softening point, it has high chemical stability such as moisture resistance and acid resistance, and is compliant with the RoHS Directive.

As will be described in detail in the explanation of FIG. 1 below, the present inventor compared the results of differential thermal analysis (DTA) and the temperature based on the definition based on viscosity regarding the transition point, yield point, and softening point of glass. It was confirmed that the second endothermic peak temperature determined by DTA was approximately equal to the softening point measured as the temperature corresponding to the viscosity. Therefore, in this specification, the second endothermic peak temperature determined by DTA is defined as "softening point T _s ".

The functions of the main components V ₂ O ₅ , TeO ₂ , Ag ₂ O and Li ₂ O in the lead-free low melting point glass composition of the present invention will be explained below.

The glass structure of the V ₂ O ₅ -TeO ₂ -Ag ₂ O-Li ₂ O-based lead-free low melting point glass composition of the present invention has a layered structure consisting of V ₂ O ₅ and TeO ₂ , with Ag between the layers. ₂ O exists in the form of Ag ⁺ and Li ₂ O exists in the form of Li ⁺ . Ag ₂ O is mixed in order to lower characteristic temperatures such as transition point, yield point, and softening point, and to improve chemical stability. It is thought that the characteristic temperature is lowered because Ag ⁺ enters between the layers of the layered structure consisting of V ₂ O ₅ and TeO ₂ and the interlayer force is weakened. Furthermore, the improvement in chemical stability is thought to be due to the fact that Ag ⁺ enters between the layers, preventing water molecules from entering. Therefore, the more Ag ⁺ exists between the layers, the lower the characteristic temperature and the better the chemical stability.

However, if the content of Ag ₂ O is too large, there will be problems such as precipitation of metallic silver (Ag) during glass production and problems of increased crystallization tendency of the produced glass. In addition, Li ⁺ present between the layers together with Ag ⁺ has a great effect on suppressing and preventing crystallization, and further improving and improving adhesiveness and adhesion. Li ⁺ , which is a monovalent cation with a small ionic radius, moves easily between layers when heated, and diffuses into the material to be sealed or bonded during sealing or bonding, resulting in high adhesiveness and adhesion. It is thought that it is possible to obtain

However, if the Li ₂ O content is too large, chemical stability such as moisture resistance and acid resistance will deteriorate, so care must be taken with the content.

It is considered that Ag ⁺ and Li ⁺ present between the layers are bonded to V ₂ O ₅ forming a layered structure. For each pentavalent vanadium ion (V ⁵⁺ ), up to two Ag ⁺ or Li ⁺ can be inserted in the form of ions between the layers in the glass structure. If it exceeds this, a problem arises in which metallic silver (Ag) is precipitated during glass production.

Unless Ag ₂ O as a glass component is present in the Ag ⁺ state between layers in the glass structure, the desired effect of lowering the temperature cannot be obtained. Therefore, when increasing the number of Ag ⁺ and Li ⁺ introduced between the layers, in addition to increasing the content of Ag ₂ O and Li ₂ O, it is also necessary to appropriately increase the content of V ₂ O ₅ . There is.

In this way, when introducing Ag ⁺ or Li ⁺ into the glass structure, V ₂ O ₅ that forms the layered structure is a glass component that plays an important role.

TeO ₂ is a vitrification component for vitrification, and unless TeO ₂ is contained, glass cannot be formed. Moreover, when the content of TeO ₂ is small, it is difficult to reduce the crystallization tendency. On the other hand, if the content is large, the crystallization tendency can be reduced, but it is difficult to lower the characteristic temperature. Furthermore, when the TeO ₂ content increases, the glass structure is no longer a layered structure for introducing Ag ⁺ and Li ⁺ .

Considering both the reduction of crystallization tendency and the lowering of the characteristic temperature, it is preferable to contain from 1 to 2 V ⁵⁺ per 1 tetravalent tellurium ion (Te ⁴⁺ ). A specific TeO ₂ content of 30 mol% or more and 50 mol% or less is effective.

Furthermore, the content of Ag ₂ O is preferably 5 mol% or more and less than 30 mol%. That is, it is preferable that 5≦[Ag ₂ O]<30.

Further, the content of V ₂ O ₅ is preferably 10 mol % or more and less than 30 mol %. That is, it is preferable that 10≦[V ₂ O ₅ ]<30.

LiO ₂ easily diffuses into the materials to be joined during joining, and has the effect of improving adhesiveness. However, if too much is added, the water resistance may deteriorate, so the amount of Li is desirably 3 mol% or more and 20 mol% or less.

Other alkali metals and additional components are also useful to control Li diffusion. Other alkali metals added for diffusion control are preferably K and Na. When adding these, it is desirable to satisfy [Li ₂ O]>[K ₂ O]+[Na ₂ O]. Further, the total amount of alkali metals including Li [Li ₂ O]+[K ₂ O]+[Na ₂ O] is desirably 3 mol % or more and 20 mol % or less.

The content of the additional component is preferably 3.0 mol% or more and 16 mol% or less in terms of oxide. By setting the content of the additional component to 3.0 mol% or more, a sufficient effect of reducing crystallization tendency can be obtained. Further, by setting the content of the additional component to 16 mol % or less, rise in characteristic temperature and crystallization can be suppressed.

Further, the lead-free low melting point glass composition of the present invention has high chemical stability such as moisture resistance and acid resistance despite having a low softening point, and is compliant with the RoHS Directive.

A low melting point glass composite material containing a lead-free low melting point glass composition and any one or more of low thermal expansion filler particles, metal particles and resin, or a low melting point glass paste made by pasting the low melting point glass composite material. For application to sealing structures, electrical and electronic parts, painted parts, etc., it is preferable to use a glass composition that has a small tendency to crystallize and a lower softening point. That is, by using a glass composition with a small crystallization tendency and a lower softening point, the softening fluidity of the glass composite material or glass paste at low temperatures is improved. However, in conventional low melting point glass compositions, lowering the softening point is often accompanied by lowering the crystallization initiation temperature.

Note that, in this specification, products manufactured using low-melting point glass composite materials, such as sealing structures, electrical and electronic parts, and painted parts, are collectively referred to as "applied products."

(Measurement of density)
Each of the prepared lead-free low-melting glasses was coarsely ground using a stamp mill, and then ground to under 45 μm using a jet mill. Using the glass powder, the density of each lead-free low melting glass was measured by the pycnometer method in helium gas.

(Measurement of characteristic temperature)
The characteristic temperature of each lead-free low-melting glass was determined by performing differential thermal analysis (DTA) using the same glass powder used for density measurement at a heating rate of 5° C./min in the atmosphere. Here, in order to clearly detect the characteristic points of the DTA curve unique to glass, a macrocell type DTA device was used, and high purity alumina (α-Al ₂ O ₃ ) powder was used as the standard sample.

FIG. 1 is an example of a typical DTA curve specific to glass. The horizontal axis represents the temperature of the standard sample, and the vertical axis represents the temperature difference (potential difference) between the glass sample to be measured and the standard sample.

In this figure, when the glass is heated at the temperature increase rate described above, it starts absorbing heat from the transition point T _g and reaches the yield point M _g corresponding to the first endothermic peak temperature. Then, the temperature difference becomes small once, and then becomes large again, reaching the softening point _Ts corresponding to the second endothermic peak temperature.

When heated further, exotherm starts from the crystallization temperature T _cry and reaches an exothermic peak. This exothermic peak is due to crystallization, and the temperature at which the exotherm starts is called the crystallization temperature T _cry . Although not shown, the temperature corresponding to the exothermic peak is referred to as crystallization peak temperature T _cry-p . The transition point T _g is the starting temperature of the first endothermic peak, and the yield point M _g is the first endothermic peak temperature. Note that each characteristic temperature is usually determined by the tangential method.

Strictly speaking, the transition point T _g , the yield point M _g and the softening point T _s are defined by the viscosity of the glass. T _g is a temperature corresponding to 10 ^13.3 poise, M _g is 10 ^11.0 poise, and T _s is a temperature corresponding to 10 ^7.65 poise.

The crystallization tendency is determined from the difference (absolute value) between the softening point T _s and the crystallization temperature T _cry and the height of the exothermic peak due to crystallization, that is, the calorific value thereof.

First, if the difference (absolute value) between the softening point _Ts and the crystallization temperature _Tcry is large, even if the glass reaches a temperature exceeding the softening point _Ts , the glass is softened and flowed within a temperature range that does not reach _Tcry . This makes it easier. In addition, if the amount of heat generated during crystallization is small, it is unlikely that an uncontrollable temperature rise due to heat generation will occur when heating at a constant temperature increase rate and T _cry is reached. can be suppressed.

Therefore, it can be said that an increase in the temperature of T _cry , that is, an increase in T _cry -T _s , and a decrease in the amount of heat generated by crystallization indicate a glass that is difficult to crystallize. That is, if a glass determined to have a low crystallization tendency is used, it becomes easy to form a desired sealing part and the like.

When sealing and adhering various parts and forming electrodes/wirings and conductive/heat dissipating joints using conventional low melting point glass compositions, the firing temperature is determined by the temperature of the low thermal expansion filler particles and metal particles contained. Although it is influenced by the type, content, particle size, and firing conditions such as heating rate, atmosphere, and pressure, it is usually set to about 30 to 50°C higher than the softening point _Ts . At this firing temperature, the low melting point glass composition does not crystallize and has good softening fluidity.

However, the lead-free low melting point glass composition according to the present invention has significantly lower characteristic temperatures of transition point T _g , yield point M _g , and softening point T _s than conventional low melting point glass compositions, and the difference in each temperature is small. . Therefore, the viscosity gradient in this temperature range is large. Therefore, even if the firing temperature is near the softening point _Ts , good softening fluidity can be obtained if the temperature is maintained. Furthermore, even if the holding time is short, sufficient softening fluidity will occur if the temperature is approximately 20 to 30° C. higher than T _s .

(Low melting point glass composite material and low melting point glass paste)
The low melting point glass composite material includes the lead-free low melting point glass composition according to the present invention and any one or more of low thermal expansion filler particles, metal particles, and resin.

Hereinafter, a low melting point glass composite material containing low thermal expansion filler particles, metal particles, or resin will be explained.

The low melting point glass composite material containing low thermal expansion filler particles preferably contains a lead-free low melting point glass composition of 35% by volume or more and less than 100% by volume, and contains low thermal expansion filler particles of more than 0% by volume and 65% by volume or less. By setting the lead-free low melting point glass composition to 35% by volume or more or the low thermal expansion filler particles to 65% by volume or less, good softening fluidity and good adhesion and adhesion to the sealed and bonded materials can be achieved. You can get sex.

Examples of low thermal expansion filler particles to be mixed in order to reduce thermal expansion of a low melting point glass composite material include zirconium phosphotungstate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ), β-eucryptite (Li ₂ O - Either _{of Al2O3.2SiO2} ), cordierite ( _{2MgO.2Al2O3.5SiO2} ), quartz glass ( _{SiO2 ) , niobium} oxide ( _Nb2O5 ), and silicon (Si ₎ . It is preferable that there be. Low thermal expansion filler particles that are particularly effective for reducing thermal expansion of low melting point glass composite materials include zirconium tungstate phosphate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ) or zirconium tungstate phosphate (Zr ₂ (WO ₄ )( _PO4 ) ₂ ), and its preferable content is 30% by volume or more and 60% by volume or less.

The low melting point glass composite material containing metal particles preferably contains a lead-free low melting point glass composition of 10% by volume or more and 80% by volume or less and metal particles of 20% by volume or more and 90% by volume or less. By setting the content of the lead-free low-melting glass composition to 10% by volume or more or the content of metal particles to 90% by volume or less, sintering between metal particles and adhesion and adhesion to the base material are improved.

From the viewpoint of improving conductivity and heat dissipation, metal particles include silver (Ag), silver alloy, copper (Cu), copper alloy, aluminum (Al), aluminum alloy, tin (Sn), and tin alloy. Either of these is preferred. Particularly effective metal particles for improving the conductivity and heat dissipation of the low melting point glass composite material of the present invention are silver (Ag) or aluminum (Al), and the preferred content thereof is 10 to 90% by volume. . This is because the lead-free low melting point glass composition of the present invention can promote sintering of silver (Ag) particles and can remove surface oxide films of aluminum (Al) particles.

The low melting point glass composite material containing a resin contains a lead-free low melting point glass composition of 5% by volume or more and less than 100% by volume, and contains a resin of more than 0% by volume and 95% by volume or less. By setting the lead-free low melting point glass composition of the present invention to 5% by volume or more, or by setting the resin to 95% by volume or less, the lead-free glass composition and the resin can be effectively combined.

The resin is preferably any one of epoxy resin, phenoxy resin, phenol resin, acrylic resin, urethane resin, and fluororesin. By using these resins, the resin of the lead-free low melting point glass composition has good softening fluidity.

The low melting point glass paste contains a low melting point glass composite material containing the lead-free low melting point glass composition according to the present invention, and a solvent. As the solvent, it is preferable to use dihydroterpineol, α-terpineol or carbitol acetate. This is because these solvents are solvents that are difficult to crystallize for the lead-free low melting point glass composition of the present invention. Further, the stability and applicability of the low melting point glass paste can be adjusted by adding a viscosity modifier, a wetting agent, etc. as necessary.

When sealing or adhering a sealing structure using a low melting point glass composite material containing low thermal expansion filler particles or its low melting point glass paste, it is necessary to It is preferable to arrange or apply the low melting point glass composite material or the low melting point glass paste, and to fire it at a temperature ranging from around the softening point T _s of the lead-free low melting point glass composition to about 20° C. higher than the softening point T _s of the lead-free low melting point glass composition.

The glass composite material and glass paste of the present invention use a lead-free low melting point glass composition with a reduced crystallization tendency and a lower softening point, so they improve softening fluidity at low temperatures and reduce the firing temperature. The temperature can be lowered. This makes it possible to reduce thermal damage to the sealing structure (improve functionality) and improve productivity (reduce takt time) while reducing the impact on the environment. Moreover, since the lead-free low melting point glass composition of the present invention has good adhesion, adhesion, and chemical stability, reliability of the sealed structure can also be ensured.

In addition, when forming electrodes/wirings or conductive/heat dissipating joints in electrical and electronic components using a low-melting point glass composite material containing metal particles or its low-melting point glass paste, it is necessary to It is preferable to arrange or apply a melting point glass composite material or a low melting point glass paste, and then sinter it in a temperature range from around the softening point T _s of the lead-free low melting point glass composition contained therein to about 20° C. higher than the softening point T _s . In addition, when the metal particles used are metals that are easily oxidized, it is desirable that the firing atmosphere be an inert gas or vacuum in order to prevent oxidation of the metal particles.

The low melting point glass composite material and low melting point glass paste of the present invention use a lead-free low melting point glass composition that has a reduced crystallization tendency and a lower softening point, so it has improved softening fluidity at low temperatures. , the firing temperature can be lowered. As a result, the formation temperature of the electrode/wiring and the conductive/heat dissipating joint, that is, the firing temperature can be lowered. This makes it possible to reduce thermal damage to electrical and electronic components (improve functionality) and improve productivity (reduce takt time) while reducing the impact on the environment. Moreover, since the lead-free low melting point glass composition of the present invention has good adhesion, adhesion, and chemical stability, it can also ensure the reliability of electrical and electronic components.

Further, when forming a coating film on a painted part using a low melting point glass composite material or a low melting point glass paste containing resin, metal, ceramics, or glass is effective as the base material. A low melting point glass composite material or a low melting point glass paste is placed or applied on a predetermined location of the base material, and the temperature ranges from around the softening point _Ts of the lead-free low melting point glass composition contained therein to about 20°C higher than the softening _{point Ts} . Fire at a temperature range.

The low melting point glass composite material and the low melting point glass paste of the present invention have improved softening fluidity at low temperatures by using a lead-free low melting point glass composition that has a reduced crystallization tendency and a lower softening point. The firing temperature can be lowered. This makes it possible to reduce the impact on the environment and improve the reliability of the paint film adhesion, heat resistance, chemical stability, etc. of the painted parts.

(Sealing structure)
The low melting point glass composite material and the low melting point glass paste according to the present invention can be used in display panels such as vacuum insulated double glass panels, plasma display panels, organic EL display panels, and fluorescent display tubes, which are applied to window glass, etc., and crystal display panels. It is suitably used for sealing package devices such as vibrators, IC packages, and MEMS.

The sealing structure according to the present invention uses a glass plate, a circuit board, etc., and a low melting point glass composite material or a low melting point glass paste.

The sealing structure may have an internal space separated from the outside. In this case, the boundary between the internal space and the outside may be formed by a sealing part containing a low-melting glass composite material. The content of the lead-free low melting point glass composition contained in the low melting point glass composite material forming the sealing portion is preferably 40 volume % or more and less than 100 volume %. It is also effective to mix low thermal expansion filler particles into the low melting point glass composite material. Further, instead of the low thermal expansion filler particles, soft metal particles may be mixed to alleviate residual stress in the sealing portion.

(Electrical and electronic parts)
The low melting point glass composite material and the low melting point glass paste according to the present invention can be used for electrical and electronic components such as solar cells, image display devices, multilayer capacitors, inductors, crystal resonators, light emitting diodes (LEDs), multilayer circuit boards, and semiconductor modules. It is suitably used for forming electrodes, wiring, conductive joints, and heat dissipating joints. In this case, the content of metal particles contained in the low melting point glass composite material is preferably 50% by volume or more.

(Painted parts)
The low melting point glass composite material and low melting point glass paste according to the present invention can also be used as a paint.

The painted component according to the present invention includes a member and a coating film formed by applying a paint to the surface of the member. The members are metals, ceramics, glass, etc. The coating comprises a low melting point glass composite material according to the invention.

A resin may be mixed with the low melting point glass composite material that forms the coating film. It is effective that the content of the resin is 50% by volume or more. Suitable examples of painted parts include electric wires, car bodies, airframes, washing machine tubs, toilet bowls, bathtub tiles, and the like.

Hereinafter, the present invention will be described in detail based on specific examples. However, the present invention is not limited to the embodiments discussed here, but includes variations thereof.

[Example 1]
In this example, a V ₂ O ₅ -TeO ₂ -Ag ₂ O-Li ₂ O-based lead-free glass composition was prepared, and the influence of the glass composition on the glass properties was investigated. As for the glass properties, the vitrification state, characteristic temperature, thermal expansion properties, adhesiveness, salt water resistance, and softening fluidity of the prepared lead-free glass composition were evaluated.

(Preparation of lead-free glass composition)
Tables 1 and 2 show the compositions of lead-free glass compositions S-01 to S-17 of Examples and lead-free glass compositions C1 to C2 of Comparative Examples, and the characteristics of each lead-free glass composition. . Lead-free glass compositions S-01 to S-17 of Examples are lead-free glass compositions containing V ₂ O ₅ , TeO ₂ , Ag ₂ O, and Li ₂ O as main and essential components.

The main starting materials were V ₂ O ₅ and TeO ₂ manufactured by Shinko Kagaku Kogyo Co., Ltd., Ag ₂ O manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., and Li ₂ CO manufactured by Kojundo Kagaku Kenkyusho Co., Ltd. _{No. 3} powder was used.

In addition, starting materials for additional components _include BaCO ₃ , WO ₃ , ZnO, K ₂ CO ₃ , Fe ₂ O ₃ , Al _{2 O 3 , La 2 O 3} , MgO, CeO ₂ , ZrO ₂ and Na ₂ CO ₃ powder was used. All of these are manufactured by Kojundo Kagaku Kenkyusho Co., Ltd.

Each starting material powder was weighed, blended, mixed, and placed in a quartz glass crucible so that the total amount was about 200 g. The quartz glass crucible charged with the raw material mixed powder is placed in a glass melting furnace and heated to 700-750°C at a temperature increase rate of approximately 10°C/min, in order to uniformize the composition of the melt in the quartz glass crucible. The mixture was maintained for 1 hour while stirring with an alumina rod. Thereafter, the quartz glass crucible was taken out from the glass melting furnace, and the melt was poured into a stainless steel mold to produce Examples S-01 to S-17 and Comparative Examples C1 to C2, respectively. Next, the produced lead-free glass composition was ground to under 45 μm.

(Evaluation of vitrification state)
The vitrification state of the produced lead-free glass compositions S-01 to S-17 and C1 to C2 was evaluated by determining whether crystals were precipitated by X-ray diffraction using the glass powder. In both comparative examples, no crystal precipitation was observed, and the vitrification state was good.

(Evaluation of characteristic temperature)
The characteristic temperatures of the produced lead-free glass compositions S-01 to S-17 and C1 to C2 were evaluated by DTA using the glass powder. Macro cell type was used for DTA. Approximately 500 mg of glass powder was placed in a macrocell and heated from room temperature to 320°C at a heating rate of 5°C/min in the atmosphere to obtain a DTA curve as shown in FIG. The transition point T _g , yield point M _g , softening point T _s , crystallization temperature T _cry and crystallization peak temperature T _cry-p were measured from the obtained DTA curve. The calorific value (μV) of the crystallization peak was also measured. From the measurement results, the temperature difference between T _cry and T _s (hereinafter also referred to as "T _cry - _{T s} ") was calculated. Note that the calorific value of the crystallization peak is also referred to as "T _cry-p calorific value."

(Measurement of thermal expansion coefficient)
The produced lead-free glass compositions S-01 to S-17 and C1 to C2 were heated in the temperature range of transition point T _g to yield point M _g by DTA, and then slowly cooled to remove residual thermal strain, and It was processed into a 4 x 20 mm square column. Using this, the thermal expansion curve of each lead-free glass composition was measured using a thermal dilatometer at a heating rate of 5° C./min in the atmosphere. Note that a cylindrical quartz glass with a diameter of 5 mm and 20 mm was used as a standard sample.

The thermal expansion coefficient at 150°C was used as the thermal expansion property.

(Adhesiveness evaluation)
Two soda lime glass plates were used as the materials to be joined. The glass plate size is 20×50×t2.7 mm. Using each of the produced lead-free glass compositions S-01 to S-17 and C1 to C2, the center portions of glass plates were adhered in a cross pattern, and then a load was applied to one side of the glass to peel the glass plates. The load relative to the adhesive area when the two glass plates were peeled off was measured. The firing conditions during bonding were: 230°C for 30 minutes, 300°C for 30 minutes, temperature increase at 6°C/min, and temperature decrease at 2°C/min. The bonding strength was evaluated using the average value of 10 N samples.

The bonding strengths of the lead-free glass compositions S-01 to S-17 and C1 to C2 used this time were 0.25 to 0.45 MPa. The bonding strength calculated from the load value that does not cause any problems in bonding was 0.3 MPa or more, and the bonding strength in this range was rated as "○" in adhesiveness. When the bonding strength was 0.25 to 0.3 MPa, the adhesiveness was evaluated as "Δ", and when the bonding strength was less than 0.25 MPa, the adhesiveness was evaluated as "x".

Although all the components satisfied the performance as adhesive glass, higher adhesiveness was confirmed in the examples than in the comparative examples. Therefore, in the glass of the example, the adhesiveness is higher than that of the comparative example, and the yield during use is higher.

(Salt water resistance evaluation (salt water spray test and salt water impregnation test))
In a salt water spray test (based on Japanese Industrial Standards JIS Z 2371:2015) in which salt water is sprayed onto glass, no particular change was observed in the glasses of any composition, and no difference occurred between each example. .

As an accelerated test, each test piece was immersed in 10% salt water at 40° C. for 120 hours to conduct a salt water impregnation test.

Regarding the presence or absence of precipitates in the glass, those in which precipitation was observed throughout are marked as "x", those in which several precipitated areas were found are marked as "△", and those in which no precipitates were found are marked as "○". evaluated.

It was confirmed that lead-free glass compositions S-16 and S-17 had no precipitation at all and had high salt water resistance. Therefore, it was found that high salt water resistance was exhibited when Ce, Fe, and Al were used as additional components.

(Evaluation of softening fluidity)
The softening fluidity of the produced lead-free glass compositions S-01 to S-17 and C1 to C2 was evaluated by a button flow test of a compact formed using the glass powder.

The powder compact was molded into a cylindrical shape with a diameter of 12 mm and a height of about 3 mm using a mold and a hand press under conditions of 500 kg/cm ² . Then, the compacted powder compact is placed on a soda lime glass substrate, introduced into an electric furnace, and heated from room temperature to 20 to 30°C above the softening point _Ts at a heating rate of 10°C/min in the atmosphere. Heat to high temperature and hold for 30 minutes. Thereafter, it was cooled in a furnace and evaluated for softening fluidity and crystallization state.

Regarding softening fluidity, the sample of the compacted compact was judged as "passing" if it was clear that it not only deformed but also became liquid and flowed, and then solidified in a glossy state. . On the other hand, if there was devitrification (surface crystallization) even after softening and flow, or if the softening and flow was insufficient due to crystallization, it was judged as "fail".

Note that _the conventional leaded low melting point _{glass composition} (84PbO-13B ₂ O ₃ -2SiO ₂ -1Al ₂ O ₃ % by mass) was subjected to a similar button flow test at 430°C, the softening fluidity was "passed". However, cracks were observed to occur due to the large difference in thermal expansion with the soda lime glass substrate. The occurrence of cracks can be countered by mixing low thermal expansion filler particles into the powder of the leaded low melting point glass composition.

(Evaluation of water resistance)
Water resistance was determined by HAST (High Accelerated Stress Test) under the conditions of 120° C., 100% humidity, and 2 atm for 48 hours, and the presence or absence of elution from the button sample. "○" means no elution at all. "Δ" indicates a case where very slight elution is observed on the back side. "x" indicates a case where elution is observed.

From the above, an effective glass composition contains Ag ₂ O, TeO ₂ , V ₂ O ₅ and Li ₂ O as main components. Furthermore, additional components include _Ba2O , _Y2O3 , _{La2O3 , CeO2 , Er2O3 , Yb2O3 , Al2O3 , Ga2O3 , In2O3 , Fe2O. 3} , WO ₃ and MoO ₃ in small amounts. In particular, the content of the main components is mol%, Ag ₂ O > TeO ₂ ≧V ₂ O ₅ , 2V ₂ O ₅ ≧Ag ₂ O + R ₂ O, the content of TeO ₂ is 30 mol % or more and 50 mol % or less is preferred.

More preferably, the content of Ag ₂ O is 10 mol % or more and less than 25 mol %, and the content of V ₂ O ₅ is 18 mol % or more and less than 28 mol %. Further, the content of the additional component is 3.0 mol % or more and 16.0 mol % or less in terms of the above-mentioned oxide.

Note that it has been confirmed that a lead-free glass composition using ZrO ₂ instead of CeO ₂ has the same characteristics as a case containing CeO ₂ . Furthermore, it has been confirmed that a lead-free glass composition using Na ₂ O instead of K ₂ O has properties similar to those containing K ₂ O.

In the following examples, the above-mentioned glass composite materials and glass pastes containing the lead-free glass compositions of the present invention, as well as sealing structures, electrical and electronic parts, and painted parts to which these glass composite materials and glass pastes are applied, will be described. I will explain in detail.

[Example 2: Paste]
Hereinafter, a method of using the lead-free glass composition will be specifically explained.

Example 2 is an example in which a glass composite material containing a lead-free glass composition and metal particles is used, and metal substrates of the same type and different types are bonded to each other. As the metal particles, silver (Ag), copper (Cu), aluminum (Al), tin (Sn), etc. can be used. Furthermore, aluminum (Al), copper (Cu), nickel (Ni), iron (Fe), etc. can be used as the metal base material. A glass paste containing particles of a lead-free glass composition, metal particles, and a solvent is prepared, and it is applied to a metal substrate such as aluminum (Al), dried, and after calcining, the same or different metal substrates are combined, Can be joined by resistance welding.

Solder is often used to form conductive joints and heat-dissipating joints between metal substrates, but considering its differentiation from solder, it is important to use solder as metal particles contained in glass composite materials and their glass pastes. Ag particles and Al particles are effective. In addition, with solder, it is difficult to achieve good conductive and heat dissipation bonding to metal substrates with a natural oxide film formed on the surface, such as Al, but with the glass composite material of the present invention and its glass paste. Due to the action of the lead-free glass composition of the present invention contained therein, conductive bonding and heat dissipating bonding are possible even with such metal substrates.

Furthermore, glass composite materials and glass pastes containing metal particles can also be used as glass composite materials and glass pastes, if electrical conductivity is permitted in joints and sealing parts. In this case, low-temperature bonding or low-temperature sealing can be performed by relaxing stress depending on the size and amount of metal particles contained.

[Example 3: Electrode wiring]
In this example, an example will be described in which electrodes/wirings are formed on various substrates using a glass composite material containing the lead-free glass composition of the present invention and metal particles. As the metal particles, silver (Ag), copper (Cu), aluminum (Al), tin (Sn), etc. can be used. Furthermore, an alumina (Al ₂ O ₃ ) substrate, a borosilicate glass substrate, a silicon (Si) substrate, a ferrite substrate, a polyimide substrate, or the like can be used as the substrate. Electrodes/wirings can be formed by preparing a glass paste containing particles of a lead-free glass composition, metal particles, and a solvent, applying it to various substrates, drying it, and calcining it.

Various known methods can be applied to form electrodes and wiring in a desired wiring pattern. For example, a pattern is applied onto a substrate by screen printing using a conductive glass paste, dried, and then heated. By doing so, substrate wiring and electrodes can be formed.

[Example 4: Sealing structure]
In this example, a double-glazed glass panel for vacuum insulation is produced as a typical example of the sealing structure according to the present invention using two soda lime glass substrates and the glass composite material of the present invention. Explain an example.

FIG. 2A is a schematic plan view of the produced vacuum insulation double-glazed glass panel. Further, FIG. 2B is an enlarged view of the AA cross section near the sealing portion.

As shown in FIG. 2A, a double-glazed glass panel for vacuum insulation consists of a glass substrate 15 made of soda lime glass, etc., and another glass substrate (reference numeral 16 in FIG. 2B) stacked on top of this with a gap. It has a sealing part 14 on the peripheral edge. A plurality of spacers 18 are two-dimensionally arranged at equal intervals between these substrates (15, 16). An exhaust hole 20 is formed in the glass substrate (16), and the gap between the two substrates (15, 16) is evacuated through this exhaust hole 20 using a vacuum pump (not shown). ing. A cap 21 is attached to the exhaust hole 20.

As shown in FIG. 2B, there is a space 17 (the above-mentioned gap) between the pair of glass substrates 15 and 16 having a sealing part 14 on the outer periphery (periphery), and the space 17 is in a vacuum state. It is in. The glass composite material of the present invention is used for the sealing part 14. This vacuum insulation double-glazed glass panel can be applied to building window glass, vehicle window glass, commercial refrigerator and freezer doors, and the like.

In addition to containing the lead-free glass composition of the present invention, the glass composite material of the present invention used for the sealing portion 14 is made of a low thermal expansion material with a small thermal expansion coefficient in order to match the thermal expansion coefficients of the glass substrates 15 and 16. Filler particles are mixed. Since the glass substrates 15 and 16 have a heat resistance of approximately 500° C., it is necessary to form the sealing portion 14 at a temperature below that temperature. In addition, since the glass substrates 15 and 16 are easily damaged by rapid heating or cooling, it is necessary to gradually heat and cool the glass substrates during sealing. , sealing at low temperatures is required. Further, the glass substrates 15 and 16 are often subjected to wind cooling reinforcement for crime prevention and safety. This air-cooling strengthening forms a compressive strengthening layer on the surfaces of the glass substrates 15 and 16, and this strengthening layer gradually decreases when heated to 300° C. or higher, and disappears when heated to 400° C. or higher. For this reason as well, there is a strong demand for sealing at lower temperatures.

A plurality of spacers 18 are installed in the space 17 between the glass substrates 15 and 16 to ensure a space 17 in a vacuum state. Furthermore, in order to obtain the space portion 17 with an appropriate thickness, it is effective to introduce spherical beads 19 or the like with a uniform particle size into the spacer 18 or the sealing portion 14. Furthermore, the glass composite material of the present invention can be used to fix the spacer 18 in the same way as the sealing part 14. In order to obtain the space 17 having a vacuum state, an exhaust hole 20 is formed in the glass substrate 16 in advance, and the space 17 is evacuated through the exhaust hole 20 using a vacuum pump. After evacuation, the cap 21 is attached to maintain the degree of vacuum in the space 17. When applied as a building material window glass or a vehicle window glass, the heat ray reflective film 22 may be formed in advance on the inner surface of the glass substrate 15 by a vapor deposition method or the like.

(Production of vacuum insulated double glass panel)
A method for manufacturing the vacuum insulating double glass panel of this example will be explained using FIGS. 3A to 5.

FIG. 3A shows a state in which a sealing portion 14 and a spacer 18 are formed on an air-cooled tempered soda lime glass substrate 16 that constitutes the vacuum insulated double-glazed glass panel shown in FIGS. 2A and 2B.

As shown in FIG. 3A, the above glass paste was prepared and applied to the outer periphery (sealing part 14) and the inside (spacer 18) of the air-cooled strengthened soda lime glass substrate 16 by a dispenser method, and heated at 150° C. in the atmosphere. dry. This is heated to 220° C. at a heating rate of 5° C./min in the atmosphere and held for 30 minutes to attach the sealing portion 14 and spacer 18 to the air-cooled strengthened soda lime glass substrate 16.

FIG. 3B shows a cross section taken along line AA in FIG. 3A.

As shown in FIG. 3B, the sealing portion 14 and the spacer 18 include spherical beads 19.

FIG. 4A shows an air-cooled tempered soda lime glass substrate 15 that constitutes the vacuum insulated double-glazed glass panel shown in FIG. 2B.

FIG. 4B is a sectional view taken along line AA in FIG. 4A.

As shown in FIGS. 4A and 4B, a heat ray reflective film 22 is formed on one side of the air-cooled strengthened soda lime glass substrate 15.

FIG. 5 shows the final step of the method for making the vacuum insulated double glazing panel shown in FIGS. 2A and 2B.

In FIG. 5, two air-cooled tempered soda lime glass substrates 15 and 16 are opposed, aligned, and fixed with a plurality of heat-resistant clips. This is heat treated while being evacuated and sealed.

FIG. 6 shows the sealing temperature profile in the heat treatment shown in FIG.

As shown in FIG. 6, after heating the lead-free glass composition S-12 at a heating rate of 5°C/min to a temperature 10 to 20°C higher than the yield point M _g (221°C) of lead-free glass composition S-12 and holding it for 30 minutes, the panel While evacuating the inside from the exhaust hole 20 with a vacuum pump, heat at a heating rate of 5°C/min to a temperature 10 to 20°C higher than the softening point T _s (267°C) of lead-free glass composition S-12 for 30 minutes. Hold and seal.

As shown in FIG. 5, during the heat treatment, the sealing portion 14 and the spacer 18 are crushed by atmospheric pressure and are brought into close contact with the two air-cooled strengthened soda lime glass substrates 15 and 16. Thereafter, a cap 21 is attached to the exhaust hole 20, and a vacuum insulating double glass panel is produced.

In a vacuum insulated double-glazed glass panel to which the glass composite material of the present invention or its glass paste is applied, a sealing portion with high adhesiveness and high reliability can be obtained. Furthermore, by using the glass composite material of the present invention or its glass composite material, the sealing temperature can be lowered, improving the productivity of vacuum insulated double-glazed glass panels, and applying soda lime glass substrates with air cooling reinforcement. It can also make a major contribution.

In addition, similar to the above-mentioned vacuum insulating double-glazed glass panel, it can also be effectively applied to sealing structures other than vacuum-insulated double-glazed glass panels, such as electrical and electronic components such as display panels and solar cells.

From the above, by applying the glass composite material containing the lead-free glass composition and metal particles or low thermal expansion filler particles of the present invention or its glass paste to the conductive joint or sealing part, the impact on the environmental load can be taken into consideration. It was found that a highly reliable crystal resonator package could be obtained. In this example, an example of application to a crystal resonator package was explained as one of the representative examples of the electric/electronic component and the sealing structure according to the present invention, but the glass composite material and its glass paste according to the present invention The present invention can be effectively applied not only to crystal resonator packages but also to many electrical and electronic components and sealing structures having conductive joints, sealing parts, and even heat dissipating joints.

In the examples, a vacuum insulated double-glazed glass panel was explained as a typical example of the sealing structure and electrical/electronic components according to the present invention, but the present invention is not limited thereto, and can be applied to various displays such as OLED displays. Package devices such as panels, solar cells, crystal resonator packages, image display devices, multilayer capacitors, inductors, light emitting diodes, multilayer circuit boards, semiconductor modules, semiconductor sensors, semiconductor sensors, and many other sealed structures and electrical and electronic devices. It is obvious that this method can be applied to parts.

14: sealing part, 15, 16: soda lime glass substrate, 17: space part, 18: spacer, 19: spherical beads, 20: exhaust hole, 21: cap, 22: heat ray reflective film.

Claims (17)

Contains vanadium oxide, tellurium oxide, silver oxide and lithium oxide, and
As an additional component, at least one of K ₂ O and Na ₂ O, and from the group consisting of BaO, WO ₃ , ZnO, Fe ₂ O ₃ , Al ₂ O ₃ , La ₂ O ₃ , MgO, CeO ₂ and ZrO ₂ including one or more selected types;
A lead-free low melting point glass composition that satisfies the following relational expressions (1) , (1-α), (4) and (5) in terms of oxides.
2[V ₂ O ₅ ]≧[Ag ₂ O]+[R ₂ O]…(1)
₍ In the _formula , [X] represents the content of _{component 2} O].)
[Li ₂ O]＞[K ₂ O]+[Na ₂ O]…(1−α)
5≦[Ag2O _] ＜30…(4)
10≦[V ₂ O ₅ ]＜30…(5) The lead-free low melting point glass composition according to claim 1 , which satisfies the following relational expression.
3≦[Li ₂ O]+[K ₂ O]+[Na ₂ O]≦20 The lead-free low melting point glass composition according to claim 1 or 2 , which satisfies the following relational expressions (2) and (3).
[TeO ₂ ]＞[V ₂ O ₅ ]＞[Ag ₂ O]…(2)
30≦[TeO ₂ ]≦50…(3) The lead-free low melting point glass composition according to any one of claims 1 to 3 , wherein the content of the additional component is 3.0 mol% or more and 16 mol% or less in terms of oxide. 5. The lead-free low melting point glass composition according to claim 4 , wherein the content of each metal element in the additional component is 6.0 mol% or less in terms of oxide. The lead-free low melting point glass composition according to any one of claims 1 to 5 , wherein the additional component includes one or more selected from the group consisting of _{Fe2O3 , Al2O3 ,} and _CeO2 . The lead-free low melting point glass composition according to any one of claims 1 to 6 ,
A low melting point glass composite material comprising any one of low thermal expansion filler particles, metal particles, and resin. comprising the low thermal expansion filler particles,
The low thermal expansion filler particles include zirconium phosphotungstate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ), quartz glass (SiO ₂ ), zirconium silicate (ZrSiO ₄ ), alumina (Al ₂ O ₃ ), and mullite. _The low melting point glass composite material according to _claim 7 , comprising _any one of ( _3Al2O3.2SiO2 ) and niobium oxide ( _Nb2O5 ). The content of the lead-free low melting point glass composition is 40 volume% or more and less than 100 volume%,
The low melting point glass composite material according to claim 8 , wherein the content of the low thermal expansion filler particles is more than 0% by volume and not more than 60% by volume. The low thermal expansion filler particles include zirconium phosphotungstate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ) ,
The low melting point glass composite material according to claim 8 , wherein the content of the low thermal expansion filler particles is 30% by volume or more and 60% by volume or less. comprising the metal particles,
The low melting point glass composite material according to claim 7 , wherein the metal particles include any one of Au, Ag, Cu, Al, and Sn. The content of the lead-free low melting point glass composition is 10% by volume or more and 80% by volume or less,
The low melting point glass composite material according to claim 11 , wherein the content of the metal particles is 20% by volume or more and 90% by volume or less. The metal particles contain Ag or Al,
The low melting point glass composite material according to claim 11 , wherein the content of the metal particles is 20% by volume or more and 90% by volume or less. comprising the resin;
8. The low melting point glass composite material according to claim 7 , wherein the resin includes any one of epoxy resin, phenoxy resin, phenol resin, acrylic resin, urethane resin, and fluororesin. The content of the lead-free low melting point glass composition is 5% by volume or more and less than 100% by volume,
The low melting point glass composite material according to claim 14 , wherein the content of the resin is more than 0% by volume and not more than 95% by volume. A glass paste comprising the low melting point glass composite material according to any one of claims 7 to 15 and a solvent. An applied product manufactured using the low melting point glass composite material according to any one of claims 7 to 15 .

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