JP5041323B2 - Powder material and paste material - Google Patents

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JP5041323B2
JP5041323B2 JP2006119783A JP2006119783A JP5041323B2 JP 5041323 B2 JP5041323 B2 JP 5041323B2 JP 2006119783 A JP2006119783 A JP 2006119783A JP 2006119783 A JP2006119783 A JP 2006119783A JP 5041323 B2 JP5041323 B2 JP 5041323B2
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glass
powder
powder material
sealing
material
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JP2006342044A (en
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武民 菊谷
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日本電気硝子株式会社
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/12Silica-free oxide glass compositions
    • C03C3/16Silica-free oxide glass compositions containing phosphorus
    • C03C3/21Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum

Description

  The present invention uses glass that can be used for sealing display devices such as a fluorescent display device (VFD), a field emission display (FED), a plasma display panel (PDP), and a cathode ray tube (CRT), and the like. It relates to powder materials. The present invention also relates to glass that can be used for sealing electronic components such as a package containing a semiconductor element, a crystal resonator, and the like, and a powder material using the glass.

For sealing display devices such as VFD, FED, PDP, and CRT, sealing glass having characteristics such as a sealing temperature of 430 to 500 ° C. and a thermal expansion coefficient of about 60 to 100 × 10 −7 / ° C. is used. ing. Further, for sealing electronic components such as packages containing semiconductor elements and crystal resonators, the sealing temperature is 320 to 500 ° C., and the thermal expansion coefficient is about 60 to 100 × 10 −7 / ° C. Sealing glass is used.

  For sealing the display device, first, a glass paste is applied to a sealed portion of an object to be sealed, dried, and then heated for debinding. Then, the main baking is performed in a state of being in close contact with the other object to be sealed, and the sealing is completed. Note that display devices such as VFD, FED, PDP, and CRT are subjected to heat treatment for evacuation after sealing. Therefore, it is necessary to select a glass which does not deteriorate the airtightness due to the heat treatment.

  In order to obtain a stronger bond, it is necessary to heat the glass powder to a temperature sufficient to wet the adhesion surface of the object to be sealed. On the other hand, there are cases where the process temperature has to be kept as low as possible, for example, when sealing an electronic component containing a device that is sensitive to high temperatures, and a material that can be sealed even at a low temperature is desired.

Under such circumstances, conventionally, a powder material composed of a PbO—B 2 O 3 glass powder that can be sealed at a low temperature and a refractory filler powder is mainly used for this type of sealing material.

However, recently, from the viewpoint of environmental problems, it is required to remove lead from glass. As a glass not containing lead, for example, a tin phosphate glass is proposed in Patent Document 1. However, this type of glass contains a large amount of P 2 O 5 as a main glass-forming oxide, so it has high hygroscopicity, causes deterioration during storage of the powder, and deteriorates the weather resistance of the powder fired body. There was a case. Therefore, predetermined characteristics cannot be obtained, and there are cases where it cannot be used for electronic parts used under high temperature and high humidity.

In addition, tin phosphate glass tends to cause surface devitrification due to oxidation of SnO to SnO 2 in a debinding step and a sealing step, and a firing atmosphere for sealing with a target material. It was necessary to control. In particular, when SnO is contained in a large amount, the tendency is remarkable. Therefore, in reality, tin phosphate glass does not reach the characteristics of PbO—B 2 O 3 glass that is widely used at present.

In addition, Bi 2 O 3 —B 2 O 3 —ZnO-based glass is proposed in Patent Document 2 as a low melting point sealing composition. However, Bi 2 O 3 —B 2 O 3 —ZnO glass has a higher softening point than that of PbO—B 2 O 3 glass, and sufficient flow can be obtained unless the sealing temperature is increased. There was no problem. For this reason, it could not be used for sealing display devices and electronic parts whose characteristics deteriorate at high temperatures.

Furthermore, Patent Document 3 proposes a V 2 O 5 —ZnO—BaO—TeO 2 glass. This V 2 O 5 —ZnO—BaO—TeO 2 glass is a low melting point lead-free glass that can be sealed at a low temperature, but has a problem of poor water resistance. Further, the thermal stability is not sufficient, and there is a problem that the glass is devitrified when used in a high temperature range.
JP-A-7-69672 Japanese Patent Laid-Open No. 10-139478 JP 2004-250276 A

The present inventor improves these problems by conducting various experiments and proposes the present invention. That is, as a result of diligent efforts, the present inventors have solved these problems by using vanadium phosphate glass containing V 2 O 5 , P 2 O 5 and Bi 2 O 3 as glass compositions. It is proposed as an invention.

Specifically, the V 2 O 5 in the glass composition is in the range of 60 mol% or less, thereby improving the thermal stability and improving the devitrification problem. Furthermore, thermal stability was improved by containing P 2 O 5 as a constituent component of glass, and a decrease in water resistance was suppressed by containing Bi 2 O 3 as a water resistance improving component.

In order to achieve the above object, the powder material of the present invention is a powder material including a glass powder made of vanadium phosphate glass and a refractory filler powder, and the vanadium phosphate glass is converted into the following oxide equivalent: As a glass composition in terms of mol%, V 2 O 5 10 to 45 %, P 2 O 5 5 to 40%, Bi 2 O 3 1 to 30%, ZnO 0 to 40%, TeO 2 0 to 40%, R 2 O 0-20% (R is Li, Na, K, Cs), R′O 0-30% (R ′ is Mg, Ca, Sr, Ba), Sb 2 O 3 0-20% (however, Sb 2 O 3 is included except for the case of 0.5 wt% or more), and is substantially free of PbO.

In the present invention, “does not contain PbO” means that it contains substantially no PbO, and specifically refers to a case where the PbO content is 1000 ppm or less.

Powder powder material of the present invention is preferably used in Viewing device or sealing of electrical components.

Powder powder material of the present invention is preferably used for the insulating layer formed of Viewing device or electrical parts.

Powder powder material of the present invention is preferably used for forming barrier ribs of Viewing device or electrical parts.

The paste material of the present invention is characterized by containing the above powder material, a resin binder, and a solvent.

The reason why the composition range of the glass in the vanadium phosphate glass according to the present invention is limited as described above will be described below. In addition, the following% display points out mol% unless there is particular limitation.

V 2 O 5 is a glass-forming oxide and at the same time a component that lowers the melting point of glass. When V 2 O 5 is less than 10%, the viscosity of the glass increases and the firing temperature increases. Even if V 2 O 5 exceeds 45 %, the glass is vitrified, but the devitrification property of the glass becomes strong. Further, when V 2 O 5 component is great, since easily foaming during firing is preferably 60% or less. If it is 20% or more, it is more preferable because it is excellent in fluidity and high airtightness can be obtained. If 4 5% or less, further devitrification is suppressed, it increases the thermal stability of the glass. Therefore, more preferable range of V 2 O 5 is 20-4 5%.

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 lowering the melting point of the glass cannot be obtained. When P 2 O 5 is in the range of 10 to 40%, high thermal stability is obtained, but when it exceeds 40%, moisture resistance is deteriorated. Further, if the P 2 O 5 is more than 20%, a glass is further stabilized, it tends to be somewhat poor weatherability of the glass exceeds 30%. Therefore, a 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. By containing Bi 2 O 3 in the glass component in an amount of 1% or more, the weather resistance of the glass can be improved. Furthermore, the weather resistance becomes better when the content is preferably 3% or more. On the other hand, if it exceeds 30%, the softening temperature of the glass becomes high and the fluidity may be impaired. Therefore, considering the balance between weather resistance 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 desirable to contain ZnO because it has a great 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, when there is a heat treatment step for a long time (for example, 1 hour or more) after sealing, devitrification is likely to occur, so it is necessary to consider that the glass becomes more stable. In such a case, the ZnO content is preferably 25% or less. Therefore, the preferable range of ZnO is 0 to 25%. On the other hand, when the ZnO content is less than 3%, the glass stabilizing effect is poor. 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 temperature. However, if the content of TeO 2 exceeds 40%, the expansion becomes too high. Further, since TeO 2 is an expensive raw material, if a large amount of TeO 2 is contained in the glass composition, the sealing glass becomes expensive, which is not realistic. Considering these, TeO 2 is preferably 0 to 40%. In particular, if TeO 2 is in the range of 0 to 25%, stabilization is possible without inhibiting the effect of the low melting point.

R 2 O (R is Li, Na, K, Cs) is not an essential component, but when at least one of the R 2 O components is added to the composition, the adhesive strength with the object to be sealed becomes strong. However, if the total amount exceeds 20%, devitrification tends to occur during firing. In consideration of devitrification and fluidity, the total R 2 O content is preferably 10% or less. Of the R 2 O components, Li 2 O has the highest effect of improving the adhesive strength with the substrate, so it is desirable to use it as much as possible. However, if Li 2 O is contained alone in an amount of 5% or more, it tends to devitrify, so it is preferable to use it in combination with other alkali components.

  R′O (R ′ is a component that stabilizes glass such as Mg, Ca, Sr, Ba) and is a network-modified oxide. R'O can be contained in a total amount of 30% or less. The reason why the content of these stabilizing components is limited to 30% or less is that if it exceeds 30%, the glass becomes unstable and easily devitrifies during molding. In order to obtain a more stable glass, R′O is preferably 25% or less. In particular, BaO is most effective for stabilizing the glass. MgO also has the effect of stabilizing the glass.

The vanadium phosphate glass according to 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 a 10% component. The reason why each component is limited to the above range will be described below.

B 2 O 3 is a glass forming oxide. Although B 2 O 3 is not an essential component, it is desirable to contain 2% or more because it has a great effect of stabilizing the glass. However, if the B 2 O 3 content is more than 20%, the viscosity of the glass becomes too high, the fluidity during firing becomes extremely poor, and the hermeticity of the sealing part is impaired. A preferred range of B 2 O 3 is 0-20%, more preferably 2-10%.

Fe 2 O 3 is a network-modified oxide. Fe 2 O 3 is not an essential component, but it is desirable to contain 1% or more because it has a great effect of stabilizing the glass. However, if Fe 2 O 3 is more than 10%, the viscosity of the glass becomes too high, and the fluidity during firing becomes extremely poor. A preferred range of Fe 2 O 3 is 0-10%, more preferably 1-5%.

Al 2 O 3 is a network-modified oxide. Al 2 O 3 is not an essential component but has an effect of stabilizing the glass. It also has the effect of reducing the thermal expansion coefficient. If Al 2 O 3 exceeds 10%, the softening temperature rises and the fluidity during firing is hindered. Incidentally, considering such stability and 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. Although SiO 2 is not an essential component, it has an effect of suppressing devitrification and improving weather resistance, so it is desirable to contain it as much as possible. If SiO 2 exceeds 10%, the softening temperature rises and the fluidity during firing becomes extremely poor. In consideration of fluidity during firing, the content of SiO 2 is preferably 0 to 10%.

In addition to the above components, the vanadium phosphate glass according to the present invention can further contain various 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 can be contained, and in order to improve weather resistance and moisture resistance In 2 O 3 or the like can also be contained.

  The content of the stabilizing component and the reason for limitation will be described below.

The contents of WO 3 and MoO 3 are both preferably 0 to 20%, particularly preferably 0 to 10%. If each of these components exceeds 20%, the viscosity of the glass tends to increase.

Although Sb 2 O 3 is not an essential component, it has an effect of improving water resistance, so it can be contained in a certain amount. Further, Sb 2 O 3 is too the softening temperature multi increases flow is inhibited. Therefore, the content of Sb 2 O 3 is 0 to 20% (except when Sb 2 O 3 is 0.5% by weight or more) .

The contents of Ta 2 O 5 , Nb 2 O 5 , TiO 2 and ZrO 2 are all preferably 0 to 15%, particularly preferably 0 to 10%. If these components exceed 15%, the tendency to devitrify the glass tends to increase.

  The content of CuO and MnO is preferably 0 to 10%, particularly 0 to 5%. If these components exceed 10%, the glass tends to be unstable.

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 realistic to include a large amount in the glass composition. On the other hand, if In 2 O 3 exceeds 10%, the fluidity during firing is lowered. Therefore, the content of In 2 O 3 is preferably 0 to 10%.

The powder material of the present invention is a material whose thermal expansion coefficient is not suitable, such as alumina (70 × 10 −7 / ° C.), high strain point glass (85 × 10 −7 / ° C.), soda plate glass (90 × 10 −7 / ° C.). ° C.) or the like in order to seal a refractory filler powder added to the powder of the vanadium phosphate glass, it shall be the complex (composite). It is important that the thermal expansion coefficient of the composite is designed to be about 10 to 30 × 10 −7 / ° C. lower than the material to be sealed. In general, since the sealing material is weaker than the object to be sealed, it is desirable that the distortion remaining in the sealing material portion constituting the adhesive layer is on the compression (compression) side. Thereby, destruction of the sealing material can be prevented.

Moreover, in the case of sealing of VFD, FED, PDP, and CRT, it adjusts so that a thermal expansion coefficient may be set to about 60-90 * 10 < -7 > / degreeC. In addition to the adjustment of the thermal expansion coefficient, for example, a refractory filler powder can be added to improve the mechanical strength.

When mixing a refractory filler powder, the mixing amount is preferably 45 to 100% by volume of glass powder and 0 to 55% by volume of filler powder. This is because if the amount of the refractory filler powder is more than 55% by volume, the ratio of the glass powder becomes relatively low and it becomes difficult to obtain the required fluidity. In addition, the particle size of the glass powder and the refractory filler powder is preferably 1.0 to 15.0 μm in terms of an average particle size (D 50 ) in a laser diffraction particle size distribution analyzer (SALD-2000J manufactured by Shimadzu Corporation). When the average particle size is less than 1.0 μm, it is difficult to obtain the effect of reducing the expansion of the refractory filler. When the average particle size exceeds 15 μm, the fluidity of the sealing material is hindered or the electronic component package is sealed. In such a case, it becomes difficult to obtain airtight reliability.

  Various materials can be used as the refractory filler, such as zircon (zirconium silicate), zirconium oxide, tin oxide, niobium oxide, zirconium phosphate, willemite, mullite, cordierite, and alumina.

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

Among these refractory fillers, the glass of the present invention includes zircon, 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 fits well. In particular, Na 0.5 Nb 0.5 Zr 1.5 (PO 4 ) 3 , KZr 2 (PO 4 ) 3 , and Ca 0.25 Nb 0.5 Zr 1.5 (PO 4 ) 3 have a particularly strong effect of lowering the expansion than when other fillers are used. However, the expansion can be lowered with a small content. If necessary, a refractory white pigment (for example, TiO 2 ) and a refractory black pigment (for example, Fe—Mn, Fe—Co—Cr, and Fe—Mn—Al pigments) may be added.

Next, an example use when using the powder material using the vanadium phosphate glass according to the present invention VFD, FED, PDP, as the sealing material of the display device such as a CRT.

  First, a sealing material is applied to the sealing surface of an object to be sealed and dried. The sealing material may be applied by making the sealing material into a paste and using a dispenser or the like. If necessary, heating for debinding is performed, and then baking is performed while contacting with the other object to be sealed. In this case, the objects to be sealed can be sealed together by baking under conditions sufficient for the glass to wet the adhesion surface of the objects to be sealed. In VFD, FED, PDP, and CRT, the sealing temperature is generally 430 to 500 ° C. The holding time at the maximum temperature for sealing is usually about 20 to 30 minutes for CRT, FED and PDP, and about 10 minutes for VFD.

In addition, when pasting the powder material using the vanadium phosphate glass according to the present invention , a resin binder such as ethyl cellulose, nitrocellulose, acrylic resin, butyral resin, terpineol, isoamyl acetate, ethyl cellosolve, dibutyl cellosolve, butyl A mixture of solvents such as carbitol, butyl carbitol acetate, and ethylene glycol monophenyl ether may be used as the vehicle. If necessary, plasticizers, thickeners and surfactants can be added to the vehicle. The kneading of the powder material using the vehicle and the vanadium phosphate glass can be performed by a three-roll mill or the like.

When using a powdered material using the vanadium phosphate glass according to the present invention as a conductive powder, 10 to 60 wt% powder of vanadium phosphate glass and metal powder 40 to 90 wt% and the refractory filler powder 0 A powder material containing 20% by weight is preferred. This is because if the amount of the metal powder is more than 90% by weight, the ratio of the glass powder becomes relatively low and it becomes difficult to obtain the required fluidity, and if it is less than 40% by weight, the conductivity cannot be ensured. Moreover, when there are more refractory filler powders than 20 weight%, the ratio of a glass powder will become comparatively too low, and it will become difficult to obtain required fluidity | liquidity. Here, examples of the metal powder include powders of Ag, Pd, Al, Ni, Cu, Au, or a mixture thereof. Moreover, as a refractory filler powder, the same powder material for sealing can be used. A fire-resistant white pigment (for example, TiO 2 ) and a fire-resistant black pigment (for example, Fe—Mn, Fe—Co—Cr, and Fe—Mn—Al pigments) can be added as necessary.

  In order to form a conductor pattern using this conductive powder, it is preferable to add the above-mentioned vehicle as appropriate to the conductive powder material to obtain a paste material. The conductive paste thus obtained can form a conductive pattern by heating and baking at 400 to 900 ° C. for about 5 minutes to 1 hour.

And Turkey use the powder material using the vanadium phosphate glass and refractory filler powder according to the present invention as a powder material for forming the insulating layer is preferable. Examples of use as an insulating layer forming powder material (insulating coating powder material) such as VFD and PDP are shown below.

First, a powder material for forming an insulating layer is prepared by adding a refractory filler powder to a glass powder as necessary so that the thermal expansion coefficient is suitable for a substrate on which an insulating layer is to be formed (coated). Since soda plate glass (about 90 × 10 −7 / ° C.) is mainly used for VFD and high strain point glass (about 85 × 10 −7 / ° C.) is mainly used for PDP, the thermal expansion coefficient is 60 to 80 × 10 −7. The temperature may be adjusted to about / ° C.

  Next, the insulating layer-forming powder material is applied to the surface of the substrate on which electrical wiring or the like has been applied by screen printing. For application, the powder material may be used in the form of a paste, similar to the sealing material.

  Thereafter, the insulating layer can be formed by baking under conditions sufficient for the glass to wet the surface of the object to be sealed. The heat treatment condition of the insulating layer forming powder material is generally processed at a temperature higher than that of the sealing material, and is about 500 ° C. to 580 ° C.

It can be used in the display device and the partition wall formed of an electronic component powder material using the vanadium phosphate glass and refractory filler powder according to the present invention. Moreover, as a low expansion | extension fireproof filler powder, the thing similar to the powder material for sealing can be used. A white pigment (for example, TiO 2 ) and a black pigment (for example, Fe—Mn, Fe—Co—Cr, and Fe—Mn—Al pigments) may be added as necessary.

  The use of the powder material using vanadium phosphate glass is not limited to the above description, and can be used, for example, for sealing and covering IC packages, lamps, and optical fiber-connected components.

(Embodiment of the Invention)
Hereinafter, the present invention will be described in detail based on examples.

Tables 1 to 5 show glass powder samples (samples a to w) according to the present invention , respectively.

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

  Moreover, 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 normal phosphoric acid (orthophosphoric acid) as a liquid raw material was not used as much as possible, and a phosphate raw material was used.

  The reason is as follows. When the liquid raw material is directly melted, a problem such as spilling of the melt from the melting crucible occurs. In order to avoid this, the glass batch must be dried at a high temperature to volatilize the water contained in the orthophosphoric acid. On the other hand, when a solid raw material is used, there is no inconvenience such as spilled melt or drying of a glass batch, and conventional production equipment and melting conditions can be employed. Therefore, only when the phosphoric acid component could not be introduced with only the phosphate raw material, the insufficient phosphoric acid component was supplemented with normal phosphoric acid.

  Next, the molten glass is passed through a water-cooled roller, formed into a thin plate shape, pulverized by a ball mill, and then passed through a sieve having a mesh size of 105 μm. ) To obtain a vanadium phosphate glass powder having an average particle size of about 10 μm.

About the obtained glass powder sample, the devitrification state, the glass transition point, the thermal expansion coefficient, and the weather resistance of the fired body were evaluated. As a result, all the samples a to w are in a vitrified state, no devitrification occurs in the fired body, the glass transition point is 297 to 345 ° C., and the thermal expansion coefficient is 96 to 118 × 10 −7 / ° C. there were. Moreover, the weather resistance of the samples a to w as examples was maintained in a glossy state or in a state in which the glass component did not bleed out, and there was no problem in actual use.

  The evaluation methods for the above items are described below.

  The evaluation of the vitrification state was performed by visually judging whether the glass was glossy and homogeneous using a glass film formed into a thin plate by passing molten glass between water-cooled rollers and an annealed glass bulk. If it was good, it was marked as ◯, and if it was devitrified or phase-separated, it was marked as x.

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

  Glass powder having a weight corresponding to the true specific gravity of powder glass was dry-pressed with a mold having an outer diameter of 20 mm to obtain a button-shaped glass powder molded body. Thereafter, this molded body was fired under conditions of 480 ° C. for 10 minutes. The devitrification was evaluated by observing the surface state of the obtained button-like fired body with an optical microscope. The case where the crystal | crystallization did not precipitate on the surface of a baking body was set as (circle), and the case where the crystal | crystallization precipitated was set as x.

  The glass transition point was determined by differential thermal analysis (DTA), and the thermal expansion coefficient (30 to 250 ° C.) was determined by a push rod type thermal expansion measuring device (TMA).

  The weather resistance was evaluated as follows. The button-shaped fired body of the powder described above was placed in a constant temperature and humidity chamber at 70 ° C. and 90% for 480 hours, and it was confirmed whether or not the surface state was changed. When the same gloss is maintained as before being placed in a thermo-hygrostat, ◎, when there is no gloss but there is no leaching of glass components such as phosphoric acid components, ○ from the fired body of glass components such as phosphoric acid components What exuded was made x.

  Table 6 shows glass powders (samples A to E) of comparative examples.

Each glass powder of the comparative example was prepared in the same manner as in the example, and the obtained glass powder sample was evaluated for the devitrification state, glass transition point, thermal expansion coefficient, and weather resistance of the powder glass fired body in the same manner as in the example. . Moreover, evaluation of the vitrification state was also evaluated in the same manner as in the above-described Examples. As a result, samples A to E had a glass transition point of 258 to 327 ° C. and a thermal expansion coefficient of 84 to 100 × 10 −7 / ° C.

  Sample C was non-homogeneous because of glass phase separation. Sample A was in a vitrified state, but had a crystal on the surface of the sintered body of powdered glass and was devitrified, and did not function as a sealing glass. Samples B, D, and E had good vitrification, and the surface of the sintered body of powdered glass was glossy and good, but in the weather resistance test, the glass component exuded from the glass surface and sealed. It was not at the level of weather resistance that could be used as glass.

Next, the glass powder samples of the examples were mixed with the filler powder at the ratios shown in Tables 7 to 9 to obtain powder samples. Sample No. 1-3 are VFD sealing materials, which are materials for sealing two soda glass plates (coefficient of thermal expansion 90 × 10 −7 / ° C.). Sample No. 4 to 15 are sealing materials for PDP, which are materials for sealing two high strain point glass plates (coefficient of thermal expansion 85 × 10 −7 / ° C.).

The filler powder includes zircon, niobium oxide, tin dioxide, Na 0.5 Nb 0.5 Zr 1.5 (PO 4 ) 3 (NaNbZP in the table), KZr 2 (PO 4 ) 3 (KZP in the table), Ca 0.25 Nb. 0.5 Zr 1.5 (PO 4 ) 3 (CaNbZP in the table) was used.

  The sample thus prepared was subjected to various evaluations. The evaluation results are shown in Tables 7-9.

As is apparent from Tables 7 to 9, No. 1 as an example of the present invention. Each of the samples 1 to 3 had a thermal expansion coefficient of 74 to 76 × 10 −7 / ° C. at 30 to 250 ° C., and was suitable for sealing VFD. In addition, No. which is an embodiment of the present invention. Each sample of 4 to 15 had a thermal expansion coefficient of 69 to 71 × 10 −7 / ° C. at 30 to 250 ° C., and was suitable for sealing PDP. Furthermore, no. Each of the samples 1 to 15 showed a flow diameter of 20 to 22 mm under the firing conditions shown in the table, and had good fluidity. All the samples had good weather resistance with no problem such as oozing out of glass components.

  The flow diameter was evaluated by performing the following flow button test. First, a powder having a weight corresponding to the true 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 molded body. Next, the molded body was placed on a window glass, heated to 480 ° C. at a rate of 10 ° C./min and held for 10 minutes, and then the diameter of the obtained button was measured. When used as a sealing material, generally, the diameter of the flow button is preferably 20 mm or more.

  In addition, even if it is a case where a flow diameter is less than 20 mm in this evaluation, when glass substrates are bonded together, if pressure jigs, such as a clip, are used, the sealing between substrates will be attained.

  Evaluation of the weather resistance of the fired body was performed on the sample after the flow button test in the same manner as in the case of glass.

  Next, a method for producing filler powder will be described.

A niobium oxide (Nb 2 O 5 ) filler and a 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, followed by firing at 1400 ° C. for 16 hours in an alumina crucible. Subsequently, the sintered ingot was taken out and pulverized with an alumina ball mill, and then passed through a metal 325 mesh sieve to obtain a niobium oxide (Nb 2 O 5 ) and tin dioxide (SnO 2 ) filler having an average particle diameter of 12 μm. It was.

The production of Na 0.5 Nb 0.5 Zr 1.5 (PO 4 ) 3 filler was performed as follows. As raw materials, sodium phosphate: NaPO 3 equivalent to 0.5 mol, niobium phosphate: NbPO 5 equivalent to 0.5 mol, zirconium oxide: ZrO 2 equivalent to 0.5 mol, zirconium phosphate: ZrP 2 O 7 equivalent equivalent to 1 mol Then, magnesium oxide as a crystallization aid was added in an amount corresponding to 3 wt% of the total amount, and mixed with an alumina ball mill for 1 hour. Next, this mixed powder was fired at 1450 ° C. for 16 hours in an alumina crucible to synthesize Na 0.5 Nb 0.5 Zr 1.5 (PO 4 ) 3 . After cooling, the sintered product of Na 0.5 Nb 0.5 Zr 1.5 (PO 4 ) 3 is taken out from the crucible, pulverized and classified with an alumina ball mill, passed through a metal 325 mesh sieve, and Na 0.5 Nb with an average particle size of 10 μm. 0.5 Zr 1.5 (PO 4 ) 3 filler powder was obtained. For KZr 2 (PO 4 ) 3 and Ca 0.25 Nb 0.5 Zr 1.5 (PO 4 ) 3 , raw materials corresponding to the respective chemical equivalents were prepared in the same manner as Na 0.5 Nb 0.5 Zr 1.5 (PO 4 ) 3, and the same firing was performed. A refractory filler was produced under the conditions.

Below, the Example which applied the powder material using the vanadium phosphate glass which concerns on this invention to conductor patterns, insulation layers, and partition walls, such as PDP and VFD, is shown.

When used for a conductor pattern such as PDP, VFD, etc., the glass powder d in Table 1 and an Al metal powder are mixed in a weight ratio of 40:60, and then kneaded with a vehicle made of terpineol in which ethylcellulose is dissolved. Turned into. 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 thermal expansion coefficient was 141 × 10 −7 / ° C.

When used for forming an insulating layer such as PDP, VFD, etc., glass powder c and alumina powder in Table 1 are mixed at a volume ratio of 70:30, and then kneaded with a vehicle made of terpineol in which ethylcellulose is dissolved. And pasted. The paste was screen printed, dried, and fired at a firing temperature of 480 ° C. As a result, the sinterability was good and the thermal expansion coefficient was 78 × 10 −7 / ° C.

When used for partition walls such as PDP and VFD, the glass powder i and the alumina powder in Table 2 are mixed at a volume ratio of 70:30, and then kneaded with a vehicle made of terpineol in which ethylcellulose is dissolved to form a paste. did. The paste was screen printed, dried and then patterned by sandblasting. Note that a photosensitive resin may be mixed in the paste, screen-printed, dried, exposed, and patterned by etching. The partition having a predetermined shape was formed by firing at a firing temperature of 500 ° C. As a result, the sinterability was good and the thermal expansion coefficient was 79 × 10 −7 / ° C. The evaluation of the sinterability was performed by observing the cross section of the fired body after firing at 1000 times with an electron microscope, and having a void ratio (void ratio) of less than 20% was considered to have good sinterability and 20% or more. The product was regarded as having poor sinterability.

(Effect of the invention)
As described above, vanadium phosphate glass according to the present invention show good flowability at 500 ° C. or less. Furthermore, there is no problem of weather resistance peculiar to phosphate glass. Therefore, it is possible to produce a sealing material having performance equivalent to that of conventional lead borate glass. Thus, the powder material using the vanadium phosphate glass according to the present invention is capable of low-temperature sealing, vacuum fluorescent display (VFD), field emission display (FED), plasma display panel (PDP), a cathode ray tube It is suitable as a sealing material used for display devices such as (CRT).

Further, it can also be used as a material for forming an insulating layer of a substrate on which an electric wiring such as FED or PDP is formed, a material for forming a partition wall of a PDP, a sealing material for an IC package or a lamp. In addition to the above, the powder material using the vanadium phosphate glass according to the present invention is applicable as a substitute for a material containing lead-containing glass used in various electronic components.

Claims (7)

  1. It is a powder material including a glass powder made of vanadium phosphate glass and a refractory filler powder, and the vanadium phosphate glass is expressed in terms of mol% in terms of the following oxide, and the glass composition is V 2 O 5 10 to 45 %, P 2 O 5 5~40% , Bi 2 O 3 1~30%, 0~40% ZnO, 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), Sb 2 O 3 0-20% (except when Sb 2 O 3 is 0.5 wt% or more) A powder material containing and substantially free of PbO.
  2.   The refractory filler powder includes one or more of zircon (zirconium silicate), zirconium oxide, tin oxide, niobium oxide, zirconium phosphate, willemite, mullite, cordierite, and alumina. Powder material.
  3. 3. The powder material according to claim 1, wherein the refractory filler powder has an average particle size (D 50 ) of 1.0 to 15.0 μm.
  4.   The powder material according to any one of claims 1 to 3, wherein the powder material is used for sealing a display device or an electronic component.
  5.   The powder material according to claim 1, which is used for forming an insulating layer of a display device or an electronic component.
  6.   The powder material according to any one of claims 1 to 3, wherein the powder material is used for forming a partition wall of a display device or an electronic component.
  7.   A paste material comprising the powder material according to any one of claims 1 to 6, a resin binder, and a solvent.
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