KR20060116171A - Vanadium-phosphate glass - Google Patents

Abstract

Provided is vanadium-phosphate glass, which shows improved thermal stability and water resistance, and is useful for sealing in display devices including VFDs, FEDs, PDPs and CRTs. The vanadium-phosphate glass comprises V2O5, P2O5 and Bi2O3. Particularly, the vanadium-phosphate glass comprises: 10-60 mole% of V2O5; 5-40 mole% of P2O5; 1-30 mole% of Bi2O3; 0-40 mole% of ZnO; 0-40 mole% of TeO2; 0-20 mole% of R2O (wherein R is Li, Na, K or Cs); and 0-30 mole of R'O (wherein R' is Mg, Ca, Sr or Ba). The vanadium-phosphate glass is free from PbO. The vanadium-phosphate glass powder may be used in combination with refractory filler powder.

Description

Vanadium-phosphate glass {VANADIUM-PHOSPHATE GLASS}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to glass that can be used for sealing display devices such as fluorescent display devices (VFDs), field emission displays (FEDs), plasma display panels (PDPs), cathode ray tubes (CRTs), and the like, and powder materials using the same. Further, the present invention relates to glass that can be used for sealing electronic components such as a package containing a semiconductor element, a crystal oscillator and the like, and a powder material using the same.

The sealing glass which has the characteristics of sealing temperature of 430-500 degreeC and a thermal expansion coefficient of about 60-100x10 <^-7> / degreeC is used for sealing of display apparatuses, such as VFD, FED, PDP, and CRT. Moreover, the sealing glass which has the characteristic of sealing temperature of 320-500 degreeC and a thermal expansion coefficient of about 60-100x10 <^-7> / degreeC is used for sealing of electronic components, such as a package which accommodated a semiconductor element, a crystal oscillator, etc.

The sealing of the display device is first coated with a glass paste on the sealed portion of the to-be-sealed object, dried, and then heated for a debonding binder. Then, this firing is carried out in a state of being in close contact with the other to-be-encapsulated object to complete the sealing. In addition, in display devices such as VFD, FED, PDP and CRT, they are provided for heat treatment for vacuum exhaust after sealing. Therefore, as these sealing materials, it is necessary to select the glass which does not deteriorate and airtightness is impaired by the said heat processing.

In addition, to obtain a stronger bond, the glass powder needs to be heated to a temperature sufficient to wet the adhesive surface of the encapsulated object. On the other hand, the process temperature may be kept as low as possible, such as in the case of sealing an electronic component containing a device or the like, which is weak at high temperatures, and a material capable of sealing even at low temperatures is desired.

Due to these circumstances, examples of this kind of sealing material from the prior art, a powder material made of a PbO-B ₂ O ₃ based glass powder and the refractory filler powder sealing is possible at a low temperature has been mainly used.

However, recently, in view of environmental problems, it has been required to remove lead from glass. As glass which does not contain lead, tin phosphate type glass is proposed as patent document 1, for example. However, this glass, since the large amount of P ₂ O ₅ as the main glass-forming oxides, there is a case where moisture is high, causing a deterioration at the time of storage of the powder, or the weather resistance of the powder sintered body decreases. For this reason, a predetermined characteristic cannot be obtained and it cannot be used for the electronic component etc. which are used under high temperature and high humidity.

In addition, tin phosphate-based glass is susceptible to surface devitrification due to oxidation of SnO ₂ to SnO ₂ in the debinding step and the sealing step, and control of the baking atmosphere is required for sealing with the target material. In particular, when it contains a large amount of SnO, such a tendency was remarkable. Therefore, tin phosphate-based glass is still far from the characteristics of PbO-B ₂ O ₃ -based glass which is widely used at present.

In addition, the outside of a low melting point rod wear compositions, a _{Bi 2 O 3 -B 2 O 3} -ZnO based glass in Patent Document 2 has been proposed. However, Bi ₂ O ₃ -B ₂ O ₃ -ZnO-based glass has a higher softening point than glass of PbO-B ₂ O ₃ -based glass, and there is a problem that sufficient fluidity cannot be obtained unless the sealing temperature is increased. For this reason, it cannot be used for sealing of a display apparatus, an electronic component, etc. which characteristic falls at high temperature.

Furthermore, V ₂ O ₅ —ZnO—BaO—TeO ₂ -based glass has been proposed in Patent Document 3. The V ₂ O ₅ —ZnO—BaO—TeO ₂ -based glass has a problem of low melting point lead-free glass that can be sealed at low temperature, but poor water resistance. Moreover, there was also a problem that the glass was devitrified when used at a high temperature range because of insufficient thermal stability.

[Patent Document 1] Japanese Patent Laid-Open No. H7-69672

[Patent Document 2] Japanese Patent Laid-Open No. H10-139478

[Patent Document 3] Japanese Patent Laid-Open No. 2004-250276

MEANS TO SOLVE THE PROBLEM This inventor improves such a problem through various experiments, and proposes as this invention. That is, the present inventors, cases efforts result, a vanadium containing _{V 2 O 5, P 2 O} 5 and Bi ₂ O ₃ as the glass composition - by using a phosphoric acid-based glass, to address these issues, the proposed as the present invention will be.

Specifically, by setting the V ₂ O ₅ in the glass composition to be 60 mol% or less, thermal stability was improved to improve the problem of devitrification. In addition, by improving the thermal stability, by containing the P ₂ O ₅ as a component of the glass and, containing Bi ₂ O ₃ as a water-resistance enhancing component it was suppress the reduction of water resistance.

In order to achieve the above object, the vanadium-phosphate-based glass of the present invention is characterized by containing V ₂ O ₅ , P ₂ O ₅ and Bi ₂ O ₃ as the glass composition.

Secondly, the vanadium-phosphate-based glass of the present invention is expressed in mol% in terms of the following oxides, and as a glass composition, V ₂ O ₅ 10 to 60%, P ₂ O _{5 5 to} 40%, Bi ₂ O ₃ 1-30%, ZnO 0-40%, TeO ₂ 0-40%, R ₂ O 0-20% (R is Li, Na, K, Cs), R'O 0-30% (R 'is Mg, Ca, Sr, and Ba).

Third, the vanadium-phosphate glass of the present invention is characterized by not containing PbO. In addition, in this invention, "it does not contain PbO" means that it does not contain PbO substantially, and it means the case where PbO content is 1000 ppm or less specifically ,.

Fourthly, the powder material of the present invention is characterized by containing 45 to 100% by volume of the vanadium-phosphate-based glass powder and 0 to 55% by volume of the refractory filler powder.

Fifthly, the conductive powder material of the present invention is characterized by containing 10 to 60% by weight of the vanadium-phosphate-based glass powder, 40 to 90% by weight of the metal powder, and 0 to 20% by weight of the refractory filler powder.

Sixthly, the sealing powder material of the present invention contains 45 to 100% by volume of the vanadium-phosphate-based glass powder and 0 to 55% by volume of the refractory filler powder, and is used for a display device or an electric component. .

Seventhly, the powder material for forming an insulating layer of the present invention contains 45 to 100% by volume of the vanadium-phosphate-based glass powder and 0 to 55% by volume of the refractory filler powder, and is used for a display device or an electric component. It is done.

Eighth, the partition material for forming a partition of the present invention contains 45 to 100% by volume of the vanadium-phosphate-based glass powder and 0 to 55% by volume of the refractory filler powder, and is used for a display device or an electronic component. do.

Ninth, the paste material of this invention contains said powder material, a resin binder, and a solvent, It is characterized by the above-mentioned.

In the vanadium-phosphate-based glass of the present invention, the reason for limiting the composition range of the glass as described above is described below. In addition, the following% display means mol% unless there exists a special limitation.

V ₂ O ₅ is a glass forming oxide and a component that lowers the glass. If V ₂ O ₅ is less than 10%, the viscosity of the glass becomes high and the firing temperature becomes high. V ₂ O ₅ be vitrified exceeds 60%, but becomes strong thread covered with the glass. In addition, V ₂ O ₅ component is therefore liable to be expanded at the time of large plastic, preferably not more than 60%. If it is 20% or more, since fluidity is excellent and high airtightness can be obtained, it is more preferable. If it is 49% or less, devitrification is further suppressed and since thermal stability of glass improves, it is more preferable. Therefore, the more preferable range of V ₂ O ₅ is 20 to 49%, and particularly preferably 20 to 45%.

P ₂ O ₅ is a glass forming oxide. In the region where P ₂ O ₅ is less than 5%, the stability of the glass is insufficient, and the effect of low melting point of the glass cannot be obtained. In the P ₂ O ₅ is 10 to 40% range, but to obtain a high thermal stability, when it is more than 40% deteriorates the moisture resistance. In addition, if the P ₂ O ₅ is more than 20%, but the glass is further stabilized, and if it exceeds 30% tends to deteriorate the weather resistance of the glass slightly. Therefore, the more preferable range of P ₂ O ₅ is 20 to 30%.

Bi ₂ O ₃ is an intermediate oxide and is an essential component in the present invention. The incorporation of the Bi ₂ O ₃ in the glass composition at least 1%, it is possible to improve the weather resistance of the glass. If the content is preferably 3% or more, the weather resistance is further improved. On the other hand, when it exceeds 30%, there exists a possibility that the softening temperature of glass may become high and fluidity may be impaired. Therefore, when considering the balance of weatherability and fluidity of the glass, the content of Bi ₂ O ₃ is preferably 1 to 30%, particularly 3 to 10%.

ZnO is an intermediate oxide. Although ZnO is not an essential component, it is preferable to contain ZnO because it has a large effect of stabilizing the glass. However, when ZnO exceeds 40%, the devitrification of the glass becomes strong. Therefore, the preferable range of ZnO is 0 to 40%. In addition, in the case where there is a heat treatment step of a long time (for example, 1 hour or more) after sealing and the like, devitrification easily occurs, it is necessary to consider further for stabilization of the glass. In this case, the content of ZnO is preferably 25% or less. Therefore, the range of preferable ZnO is 0 to 25%. Moreover, when content of ZnO is less than 3%, the stabilization effect of glass will run short. Therefore, the more preferable range of ZnO is 3 to 25%.

TeO ₂ is an intermediate oxide. TeO ₂ has the effect of lowering the glass. However, when TeO ₂ exceeds 40%, the expansion becomes too high. In addition, since TeO ₂ is an expensive raw material, when a large amount of TeO ₂ is contained in a glass composition, since sealing glass becomes expensive, it is unrealistic. In consideration of these, it is preferable that TeO ₂ is 0 to 40%. In particular, when TeO ₂ is in the range of 0 to 25%, stabilization is possible without inhibiting the effect of low melting point.

R ₂ O (R is Li, Na, K, Cs) is an essential component, but, of the R ₂ O component, at least one is added to the composition thereby becomes stronger the adhesive force between the pibong complexes. However, when total amount exceeds 20%, it will become easy to devitrify at the time of baking. In addition, in consideration of devitrification and fluidity, the total amount of R ₂ O is preferably 10% or less. In addition, the component of the R ₂ O, Li ₂ O, since the effect of improving the adhesive force between the substrate the high, it is preferred to use as possible. However, when not less than 5% Li ₂ O alone becomes liable to devitrification, it is better used in combination with other alkali components.

R'O (R 'is Mg, Ca, Sr, Ba) is a component that stabilizes the glass, and is a net wood oxide (網 目 修飾 酸化 物). R'O can be contained in 30% or less of the total amount. Moreover, the reason for limiting content of such a stabilizing component to 30% or less is because when it exceeds 30%, glass will become unstable and it will become easy to devitrify at the time of shaping | molding. In order to obtain more stable glass, it is preferable to make R'O 25% or less. In particular, BaO is most effective for stabilizing the glass. MgO also has the effect of stabilizing the glass.

In addition, the vanadium-phosphate-based glass of the present invention, in addition to the above components, B ₂ O ₃ 0-20%, Fe ₂ O ₃ 0-10%, Al ₂ O ₃ 0-10%, SiO ₂ 0- You may contain 10% of components. Below, the reason which limited each component to the said range is demonstrated.

B ₂ O ₃ is a glass forming oxide. B ₂ O ₃ is an essential component, but it is preferably contained because the effect of stabilizing the glass size, more than 2%. However, B ₂ O ₃ is much higher than the viscosity of the glass over 20%, the fluidity at the time of firing and falls significantly, this airtight sealing portion is impaired. The suitable range of B ₂ O ₃ is 0 to 20%, and more preferably 2 to 10%.

Fe ₂ O ₃ is a mesh oxide. Fe ₂ O ₃ is an essential component, but it is preferably contained because the effect of stabilizing the glass size, greater than or equal to 1%. However, Fe ₂ O ₃ is more than 10%, the higher the viscosity of the glass excessively, the fluidity at the time of firing and falls significantly. The suitable range of Fe ₂ O ₃ is 0 to 10%, and more preferably 1 to 5%.

Al ₂ O ₃ is a mesh tree oxide. Al ₂ O ₃ is not an essential component, but has an effect of stabilizing the glass. It also has the effect of lowering the coefficient of thermal expansion. When Al ₂ O ₃ exceeds 10%, the softening temperature is increased, which impairs fluidity during firing. Further, when considering the stability and the fluidity of the glass, the preferred range of Al ₂ O ₃ is 0-10%, more preferred range is 0 to 5%.

SiO ₂ is a glass forming oxide. SiO ₂ is an essential component, but, since an effect of suppressing devitrification and improving weathering resistance, it is desirable to contain as much as possible. Further, when SiO ₂ exceeds 10%, the softening temperature increases, the fluidity at the time of firing and falls significantly. In consideration of fluidity during firing and the like, the content of SiO ₂ is preferably 0 to 10%.

In addition, the vanadium-phosphate-based glass of the present invention can further add various components in addition to the above components. For example, WO ₃ , MoO ₃ , Sb ₂ O ₃ , Ta ₂ O ₅ , Nb ₂ O ₅ , TiO ₂ , ZrO ₂ , CuO, MnO, and the like may be contained, and In ₂ may be used to increase weather resistance and moisture resistance. O ₃ may be contained.

Below, content of a stabilizing component and the reason for limitation are demonstrated.

The content of WO ₃ and MoO ₃ is preferably both a 0 - 20%, in particular 0-10%. When each of these components exceeds 20%, the viscosity of glass will become high easily.

Sb ₂ O ₃ is an essential component, but, since the effect of improving the water resistance, and may contain a certain amount. Furthermore, Sb ₂ O _3, the fluidity is inhibited increases the softening temperature when it is more than 20%. Therefore, the content of Sb ₂ O ₃ is preferably 0 to 20%.

_{Ta 2 O 5, Nb 2 O} 5, the content of TiO ₂ and ZrO ₂ are preferably both a 0 - 15%, in particular 0-10%. If these components exceed 15%, the devitrification tendency of glass will become large easily.

As for content of CuO and MnO, all are 0 to 10%, especially 0 to 5% are preferable. When these components exceed 10%, glass will become unstable easily.

In ₂ O ₃ can be used for the purpose of improving weather resistance and moisture resistance. However, since In ₂ O ₃ is an expensive raw material, it is not practical to include a lot in the glass composition. In addition, if the In ₂ O ₃ exceeds 10%, the fluidity at the time of firing is reduced. Therefore, the content of In ₂ O ₃ is preferably from 0-10%.

The vanadium-phosphate-based glass of the present invention having such characteristics can be used alone as a sealing material for a material having a suitable thermal expansion coefficient.

On the other hand, materials having an unsuitable thermal expansion coefficient such as alumina (70 × 10 ^-7 / ° C), high distortion glass (85 × 10 ^-7 / ° C), soda plate glass (90 × 10 ^-7 / ° C), etc. In the case of sealing, it is preferable to add a refractory filler powder to the vanadium-phosphate-based glass powder to form a composite (composite), and the coefficient of thermal expansion of the composite is 10 to 30 x 10 ^-7 / ° C based on the adherend. In general, the encapsulating material is weaker than the encapsulated material, so that the distortion remaining in the encapsulating material portion constituting the adhesive layer is preferably on the compression (compression) side. can do.

Moreover, when sealing VFD, FED, PDP, and CRT, it adjusts so that a thermal expansion coefficient may be about 60-90x10 <^-7> / degreeC. In addition to adjusting the coefficient of thermal expansion, for example, a refractory filler powder may be added to improve mechanical strength.

When mixing a refractory filler powder, it is preferable that the mixing amount is 45-100 volume% of glass powder, and 0-55 volume% of filler powder. It is because when the refractory filler powder is more than 50% by volume, the proportion of the glass powder is relatively low, so that it is difficult to obtain the required fluidity. The particle size of the glass powder and the refractory filler powder is preferably 1.0 to 15.0 µm as an average particle diameter (D ₅₀ ) in a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, SALD-2000J). When the average particle diameter is smaller than 1.0 μm, it is difficult to obtain a low expansion effect of the fire resistant filler, and when the average particle diameter is larger than 15 μm, it is difficult to obtain the reliability of the airtightness when impairing the fluidity of the sealing material or when sealing a package of an electronic component. Lose.

Various materials can be used as a refractory filler, For example, a zircon (zirconium silicate), a zirconium oxide, a tin dioxide, niobium oxide, a zirconium phosphate, a willemite, a mullite, cordierite, an alumina, etc. can be used.

In addition, a fire resistant filler having a basic structure of [AB ₂ (MO ₄ ) ₃ ] can be used. Here, A is preferably an element such as Li, Na, K, Mg, Ca, Sr, Ba, Zn, Cu, Ni, Mn, or the like. B is suitable for elements such as Zr, Ti, Sn, Nb, Al, Sc, and Y. M is suitable for elements such as P, Si, W, and Mo.

Of these fire-resistant filler, with the glass of the present invention, zirconium, tin dioxide, niobium _{oxide, Na 0.5 Nb 0.5 Zr 1.5 (} PO 4) 3, KZr 2 (PO 4) 3, Ca 0 .25 Nb 0 .5 Zr 1 _{.5 (PO 4) 3, NbZr} (PO 4), KZr 2 (PO 4) 3, Na 0.5 Nb 0.5 Zr 1.5 (PO 4) 3, K 0 .5 Nb 0 .5 Zr 1 .5 (PO 4) _{3, Ca 0 .25 Nb 0 .5} Zr 1 .5 (PO 4) 3 are well suited. In _{particular, Na 0.5 Nb 0.5 Zr 1.5 (} PO 4) 3, KZr 2 (PO 4) 3, Ca 0 .25 Nb 0 .5 Zr 1 .5 (PO 4) ₃ of the effect that paengchanghwa is particularly strong, the other filler The expansion can be reduced with a smaller amount of content than when used. If necessary, refractory white pigments (for example, TiO ₂ ) and refractory black pigments (for example, Fe-Mn-based, Fe-Co-Cr-based and Fe-Mn-Al-based pigments) may be added. have.

Next, the usage example when the powder material using the vanadium phosphate type glass of this invention is used as sealing material of display apparatuses, such as VFD, FED, PDP, and CRT, is shown.

First, a sealing material is applied to the sealing surface of the to-be-sealed object, and it dries. Application | coating of a sealing material may make a sealing material into paste form, and may apply | coat using a dispenser etc. If necessary, heating is performed for the debinder and then fired while being brought into contact with the other to-be-encapsulated object. In this case, the glass can be sealed under conditions sufficient to wet the adhesive surface of the to-be-sealed object. In VFD, FED, PDP and CRT, in general, the sealing temperature is 430 to 500 ° C. In addition, as for the holding time at the highest temperature to seal, about 20-30 minutes are suitable for CRT, FED, and PDP normally, and about 10 minutes are suitable for VFD.

In the case of pasting the powder material using the vanadium-phosphate-based glass of the present invention, a resin binder such as ethyl cellulose, nitrocellulose, acrylic resin, butyral resin, terpineol, isoamyl acetate, ethyl cell, etc. A mixture of solvents such as sorb, dibutyl cellosolve, butyl carbitol, butyl carbitol acetate, and ethylene glycol monophenyl ether may be used as the vehicle. If desired, it is also possible to add plasticizers, thickeners and surfactants to the vehicle. A three-stage roll mill or the like can be used for the mixed dough of the powder material using the vehicle and the vanadium-phosphate-based glass.

When the powder material using the vanadium-phosphate-based glass of the present invention is used as the conductive powder, it contains 10 to 60% by weight of the vanadium-phosphate-based glass powder, 40 to 90% by weight of the metal powder and 0 to 20% by weight of the refractory filler powder. It is preferable to set it as powder material. This is because when the metal powder is more than 90% by weight, the proportion of the glass powder is relatively low, so that it is difficult to obtain the required fluidity. When the metal powder is less than 40% by weight, the conductivity cannot be secured. In addition, when the refractory filler powder is more than 20% by weight, the proportion of the glass powder is relatively low, which makes it difficult to obtain the required fluidity. Here, powders, such as Ag, Pd, Al, Ni, Cu, Au, or a mixture thereof, are mentioned as a metal powder. As the fire resistant filler powder, the same ones as the sealing powder material can be used. If necessary, refractory white pigments (e.g. TiO ₂ ) and refractory black pigments (e.g. Fe-Mn-based, Fe-Co-Cr-based and Fe-Mn-Al-based pigments) may be added. have.

In order to form a conductor pattern using the said electroconductive powder, it is preferable to add the above-mentioned vehicle suitably to electroconductive powder material, and to make it as a paste material. The electrically conductive paste obtained in this way can form an electroconductive pattern by heat-firing for 5 minutes-about 1 hour at 400-900 degreeC.

When the powder material using the vanadium-phosphate-based glass of the present invention is used as the powder material for forming the insulating layer, the powder material contains 45 to 100% by volume of the vanadium-phosphate-based glass powder and 0 to 55% by volume of the refractory filler powder. It is preferable. Below, the usage example as powder material for insulating layer formation (insulation coating powder material), such as VFD and PDP, is shown.

First, a powder material for forming an insulating layer in which a refractory filler powder is added to a glass powder, if necessary, is prepared so that the thermal expansion coefficient is suitable for the substrate on which the insulating layer is to be formed (coated). For a VFD is soda glass (about 90 × 10 ^-7 / ℃) is, in the case of the PDP is high, because the distortion point of glass (about 85 × 10 ^-7 / ℃) is often used, the thermal expansion coefficient of 60~80 × 10 ^{- What} is necessary is just to adjust so that it may become about ⁷ / degreeC.

Next, by the screen printing, the powder material for forming the insulating layer is applied to the surface of the substrate on which the electrical wiring is made. In coating, like a sealing material, powder material may be used as paste shape.

Thereafter, the glass may be fired under conditions sufficient to wet the surface of the adherend, thereby forming an insulating layer. The heat treatment conditions of the powder material for forming the insulating layer are generally treated at a temperature higher than that of the sealing material, and is about 500 ° C to 580 ° C.

When the powder material using the vanadium-phosphate-based glass of the present invention is used to form partitions of display devices and electronic parts, the powder material contains 45 to 100% by volume of the vanadium-phosphate-based glass powder and 0 to 55% by volume of the refractory filler powder. It is preferable to set it as. As the low-expansion ceramic filler powder, one similar to the sealing powder material can be used. If necessary, white pigments (for example, TiO ₂ ) and black pigments (for example, Fe-Mn-based, Fe-Co-Cr-based and Fe-Mn-Al-based pigments) may be added.

In addition, the use of the powder material using vanadium phosphate-type glass is not limited to what was mentioned above, For example, it can also be used for sealing and coating | covering of IC package, a lamp, and an optical fiber connection component.

 Embodiment of the Invention

Hereinafter, the present invention will be described in detail based on examples.

Tables 1-5 show the glass powder samples (samples aw) of this invention, respectively.

Each glass powder was prepared as follows. First, the batch raw materials were combined to have a composition as shown in the table, and melted in air at a temperature of 900 ° C. for 2 hours.

In addition, the phosphate raw material was used for the batch raw material used. Specifically, zinc metaphosphate, magnesium phosphate, calcium phosphate, and aluminum phosphate were used, and phosphate raw material was used without using phosphoric acid (orthophosphoric acid) as a liquid raw material as much as possible.

The reason for this is as follows. Direct melting of the liquid raw material causes the melt to boil over from the melting crucible. To avoid this, the glass batch must be dried at high temperature to volatilize the moisture contained in the phosphorous acid. On the other hand, when using a solid raw material, there are no problems, such as boiling of a melt and drying of a glass batch, and conventional manufacturing facilities and melting conditions can be employ | adopted. Therefore, only when the phosphoric acid component cannot be introduced with only the phosphate raw material, the insufficient phosphoric acid component was supplemented with regular phosphoric acid.

Then, the molten glass is passed between the water-cooling rollers, formed into a thin plate shape, pulverized by a ball mill, and then passed through a sieve having a sieve hole of 105 µm, and a laser diffraction particle size distribution measuring device (manufactured by Shimadzu Corporation, SALD-2000J), a vanadium-phosphate glass powder having an average particle diameter of about 10 μm was obtained.

About the obtained glass powder sample, the devitrification state, glass transition point, thermal expansion coefficient, and weather resistance of a fired body were evaluated, respectively. As a result, all the samples a-w had favorable vitrification state, and no devitrification occurred in the fired body, the glass transition point was 297-345 degreeC, and the thermal expansion coefficient was 96-118x10 <^-7> / degreeC. In addition, the weather resistance of the samples a-w which is an Example maintained the state which was glossful, or the glass component did not bleed out, and was a state which does not have a problem in actual use.

Below, the evaluation method of said item is demonstrated.

Evaluation of the vitrification state was performed by visually judging whether the molten glass was in a glossy and homogeneous state by using a glass film annealed through a water-cooled roller and formed into a thin plate and annealing. In the case of good condition, (circle) and devitrification or powder separation were made into x.

Evaluation of the devitrification of the fired body was performed as follows.

A glass powder of a weight corresponding to the specific gravity of the powder glass was dry-pressed in a mold having an outer diameter of 20 mm to obtain a button-shaped glass powder molded body. Thereafter, the molded body was fired at 480 ° C. for 10 minutes. Permeability was evaluated by observing the surface state of the obtained button-shaped fired body with an optical microscope. (Circle) and the case where crystal precipitated were made into the case where crystal did not precipitate on the surface of a sintered compact.

The glass transition point was determined by differential thermal analysis (DTA), and the coefficient of thermal expansion (30-250 ° C.) was determined by a pressure-type thermal expansion measurement device (TMA).

Weather resistance was evaluated as follows. The button-like fired body of the above-described powder was put in a constant temperature and humidity chamber at 70 ° C. and 90% for 480 hours, and it was confirmed that there was no change in surface state. (Circle) and the case where the glass component, such as a phosphate component, bleed out from the baking body, were made into (circle) and the case where glass components, such as a phosphate component, did not bleed out, but had the same luster as before putting into a constant temperature and humidity chamber.

Table 6 has shown the glass powder (samples A-E) of a comparative example, respectively.

Each glass powder of the comparative example was prepared in the same manner as in Example, and the devitrification state, glass transition point, thermal expansion coefficient, and weather resistance of the powder glass fired body were evaluated in the same manner as in the Example with respect to the obtained glass powder sample. In addition, evaluation of the vitrification state was also evaluated similarly to the Example mentioned above. As a result, the glass transition points of the samples A-E were 258-327 degreeC, and the thermal expansion coefficient was 84-100x10 <^-7> / degreeC.

In addition, as for the sample C, glass became powdery and it was heterogeneous. Sample A had a good vitrification state, but crystals were devitrified on the surface of the powder glass fired body, so that it did not exhibit a function as a sealing glass. Samples B, D, and E had good vitrification, and the surface of the powder glass fired body was also gloss good, but the glass component oozed from the glass surface in the weather resistance test, and was not a weather resistance level that could be used as a sealing glass.

Next, the glass powder sample of the Example was mixed with the filler powder in the ratio shown to Tables 7-9, and it was set as the powder sample. In addition, sample No. 1-3 are for sealing VFD, and are materials for sealing two soda glass plates (coefficient of thermal expansion 90 × 10 ⁻⁷ / ° C.). Sample No. 4-15 is for sealing a PDP, and is a material for sealing two glass plates (coefficient of thermal expansion coefficient 85x10 <^-7> / degreeC) high with two sheets of distortion.

Further, the filler powder, zirconium, niobium oxide, tin _{dioxide, Na 0.5 Nb 0 .5 Zr 1} .5 (PO 4) 3 ( Table _{of, NaNbZP), KZr 2 (PO} 4) 3 (, KZP of the table), the _{Ca 0 .25 Nb 0 .5 Zr 1} .5 (PO 4) 3 (, CaNbZP of the table) was used.

The samples thus prepared were used for various evaluations. Evaluation results are shown in Tables 7-9.

As can be seen from Tables 7 to 9, each of the samples of Nos. 1 to 3, which is an example of the present invention, had a thermal expansion coefficient of 74 to 76 x 10 ^-7 / deg. C at 30 to 250 deg. C, and was suitable for sealing of VFD. . In addition, the samples of Nos. 4 to 15, which are examples of the present invention, had a coefficient of thermal expansion of 69 to 71 x 10 ^-7 / deg. C at 30 to 250 deg. Moreover, each of the samples Nos. 1 to 15 exhibited a flow diameter of 20 to 22 mm under the firing conditions shown in the table, and had good fluidity. And each sample had favorable weather resistance, without the problem that a glass component soaked out.

In addition, the flow diameter was evaluated through the following flow button test. First, a powder of a weight corresponding to the specific gravity of the powder sample was dry pressed using a mold having an outer diameter of 20 mm to obtain a button-shaped powder compact. Then, the molded body was placed on the window pane, and the temperature was raised to 10 ° C./min in air and held at 10 ° C./min for 10 minutes, and then the diameter of the obtained button was measured. When used as a sealing material, in general, the diameter of the flow button is preferably 20 mm or more.

In this evaluation, even when the flow diameter is less than 20 mm, when the glass substrates are bonded to each other, the use of a press jig such as a clip enables sealing between the substrates.

The weather resistance evaluation of the fired body was performed similarly to the case of glass about the sample after a flow button test.

Next, the manufacturing method of a filler powder is demonstrated.

The niobium oxide (Nb ₂ O ₅ ) filler and the tin dioxide (SnO ₂ ) filler were produced by the same method. First, 3 wt% of zinc oxide was added to the raw material powder as a sintering aid and mixed, and then calcined at 1400 ° C. for 16 hours in an alumina crucible. Subsequently, the sintered mass was taken out, pulverized in an alumina ball mill, and passed through a metal body of 325 mesh to obtain a filler of niobium oxide (Nb ₂ O ₅ ) and tin dioxide (SnO ₂ ) having an average particle diameter of 12 μm.

_{Na 0 .5 Nb 0 .5 Zr 1} .5 (PO 4) 3 filler was produced as follows. As a raw material, 0.5 mol equivalent of sodium phosphate (NaPO ₃ ), 0.5 mol equivalent of niobium phosphate (NbPO ₅ ), 0.5 mol equivalent of zirconium oxide (ZrO ₂ ), and 1 mol equivalent of zirconium phosphate (ZrP ₂ O ₇ ) are mixed, Magnesium oxide as a crystallization aid was added in an amount equivalent to 3 wt% of the total amount and mixed in an alumina ball mill for 1 hour. Then, in the mixed powder of alumina crucible, and fired for 16 hours to _{1450 ℃, Na 0 .5 Nb 0} .5 ethylamine _{Zr 1 .5 (PO 4) 3} . After cooling, the crucible _{Na 0.5 Nb 0.5 Zr 1.5 (PO} 4) ₃ was taken out of the sinter, ground, classified in an alumina ball mill, and then passed through a metal sieve of 325 mesh, the average particle diameter of 10μm Na _{0 .5 Nb 0 .5 Zr 1 .5 (PO} 4) ₃ to give the filler powder. KZr ₂ (PO _{4) 3} and _{Ca 0 .25 Nb 0 .5 Zr 1} .5 (PO 4) about _{3, Na 0 .5 Nb 0 .5} Zr 1 .5 (PO 4) ₃ as in the respective chemical The raw material equivalent to an equivalent was prepared, and the fire resistant filler was produced on the same baking conditions.

Hereinafter, the Example which applied the powder material using the vanadium phosphate type-glass of this invention to conductor patterns, an insulating layer, and partitions, such as PDP and VFD, is demonstrated.

When used for conductor patterns such as PDP and VFD, the glass powder d and the Al metal powder in Table 1 are mixed in a weight ratio of 40:60, and then mixed and kneaded with a vehicle made of terpineol in which ethyl cellulose is dissolved. And paste. The paste was screen printed in a predetermined pattern, dried, and then fired at a firing temperature of 480 ° C. to form a conductor pattern. As a result, the sinterability was good, and the coefficient of thermal expansion was 141 × 10 ⁻⁷ / ° C.

In the case of use for forming insulating layers such as PDP and VFD, glass powder c and alumina powder of Table 1 are mixed in a volume ratio of 70:30, and then mixed with a vehicle made of terpineol in which ethyl cellulose is dissolved. To paste. The paste was screen printed, dried, and then fired at a firing temperature of 480 ° C. As a result, the sinterability was good, and the coefficient of thermal expansion was 78 × 10 ⁻⁷ / ° C.

When used for bulkheads such as PDP and VFD, glass powder i and alumina powder of Table 2 are mixed in a volume ratio of 70:30, and then mixed and kneaded with a vehicle made of terpineol in which ethyl cellulose is dissolved. It was done. The paste was screen printed, dried, and patterned by sand blast. Moreover, you may mix photosensitive resin in a paste, screen-print, dry, expose, and then pattern-form by etching. The partition of predetermined shape was formed by baking at the baking temperature of 500 degreeC. As a result, the sinterability was good, and the coefficient of thermal expansion was 79 × 10 ⁻⁷ / ° C. In addition, the evaluation of sintering property observed the cross section of the fired body after baking at 1000 times with an electron microscope, and it is good that sinterability is good that void ratio (ratio of empty hole) is less than 20%, and that sinterability is bad is 20% or more. It was assumed that.

As described above, the vanadium-phosphate-based glass of the present invention exhibits good fluidity at 500 ° C or lower. Moreover, there are no weather resistance problems peculiar to phosphate glass. Therefore, the sealing material which has the performance equivalent to the conventional lead boric acid type glass can be manufactured. Therefore, the powder material using the vanadium-phosphate-based glass of the present invention can be sealed at a low temperature, such as a fluorescent display tube (VFD), a field emission display (FED), a plasma display panel (PDP), a cathode ray tube (CRT), and the like. It is suitable as a sealing material used for a display device.

Moreover, it can also be used as an insulating layer formation material of a board | substrate with electric wiring, such as FED and PDP, a partition formation material of PDP, an IC package, a sealing material of a lamp, etc. In addition to the above, the powder material using the vanadium-phosphate-based glass of the present invention is applicable as a substitute for a material containing lead-containing glass used in various electronic components.

Claims (9)

A vanadium-phosphate-based glass comprising V ₂ O ₅ , P ₂ O ₅ and Bi ₂ O ₃ as a glass composition. The molar% display in terms of the following oxides according to claim 1, wherein as a glass composition, V ₂ O ₅ 10 to 60%, P ₂ O _{5 5 to} 40%, Bi ₂ O ₃ 1 to 30%, ZnO 0 to 40%, TeO ₂ 0-40%, R ₂ O 0-20% (R is Li, Na, K, Cs), R'O 0-30% (R 'is Mg, Ca, Sr, Ba) Vanadium-phosphate-based glass, characterized in that. The vanadium-phosphate-based glass according to claim 1 or 2, which does not contain PbO. A powder material comprising 45 to 100% by volume of the vanadium-phosphate-based glass powder of claim 1 or 2 and 0 to 55% by volume of the refractory filler powder. 10 to 60% by weight of the vanadium-phosphate-based glass powder of claim 1 or 2, 40 to 90% by weight of the metal powder, and 0 to 20% by weight of the refractory filler powder. A sealing powder material containing 45 to 100% by volume of the vanadium-phosphate-based glass powder of claim 1 or 2 and 0 to 55% by volume of the refractory filler powder, which is used for a display device or an electronic component. A powder material for forming an insulating layer, comprising 45 to 100% by volume of the vanadium-phosphate-based glass powder of claim 1 or 2 and 0 to 55% by volume of a refractory filler powder, and used for a display device or an electronic component. A bulk material for forming partition walls, comprising 45 to 100% by volume of the vanadium-phosphate-based glass powder and 0 to 55% by volume of the refractory filler powder. A paste material comprising the powder material of claim 4, a resin binder, and a solvent.