JP4556624B2 - Sealing powder and sealing paste - Google Patents

Description

The present invention relates to sealing powders and pastes Ru is used for the sealing glass for sealing the electronic components of the IC package and a display device or the like.

  Sealing glass using low melting point glass is known as sealing glass for various materials such as glass, ceramic, metal, etc., and flat display devices such as plasma display panels (PDP), fluorescent display tubes (VFD), and FED In order to improve the mechanical strength and adjust the thermal expansion coefficient, ceramic fillers are used for panel sealing and air-tight sealing of highly reliable packages equipped with elements such as semiconductor integrated circuits, crystal resonators, and SAW filters. The powder is mixed into the low melting glass.

  In order to obtain a strong seal, it is necessary to heat the sealing glass to a temperature sufficient to wet the adhesion surface of the object to be sealed. However, the sealing of electronic components is performed at the lowest possible temperature in order to reduce the influence on the device. Conventionally, materials using lead boric acid-based low melting glass (for example, see Patent Document 1) have been widely used for such applications.

However, in recent years, from the viewpoint of environmental problems, it is required to remove lead from the sealing glass. Therefore, instead of lead borate glass, Ag ₂ O—P ₂ O ₅ glass (for example, see Patent Document 2), P ₂ O ₅ —SnO glass (for example, see Patent Document 3), Bi _2. Lead-free glass such as O ₃ glass (see, for example, Patent Document 4) is used.
Japanese Patent Laid-Open No. 07-196338 JP 2000-290007 A JP 2001-19472 A JP 2000-128574 A

Until now, as a glass substrate for PDP, soda-lime glass (thermal expansion coefficient: 80 to 90 × 10 ⁻⁷ / ° C.) and high strain point glass developed as a glass substrate for PDP (thermal expansion coefficient: 80 to 85 × 10 ⁻⁷ / ° C.) is used. In order to produce a PDP, a heat treatment step such as sealing glass substrates is necessary, but a thermal shock is easily applied to the substrate by heating and cooling before and after the heat treatment step. Therefore, in order to reduce thermal shock, a glass substrate having a thermal expansion coefficient of 60 to 80 × 10 ⁻⁷ / ° C. has been developed.

The thermal expansion coefficient of low-melting glass such as Ag ₂ O—P ₂ O ₅ glass, P ₂ O ₅ —SnO glass or Bi ₂ O ₃ glass is as large as about 100 to 110 × 10 ⁻⁷ / ° C. Therefore, by mixing ceramic filler powder with a small thermal expansion coefficient, the mixing ratio of the glass powder and ceramic filler powder is adjusted to match the thermal expansion coefficient of the glass substrate that has been conventionally used. I was making it.

  If the difference between the thermal expansion coefficients of the sealing glass and the glass substrate is large, leakage or breakage of the glass substrate may occur at the sealing portion. However, in order to match with a glass substrate having a low thermal expansion coefficient, it is necessary to increase the content of a ceramic filler powder such as cordierite or willemite having a low thermal expansion coefficient. It was difficult to hermetically seal because of its low nature.

An object of the present invention is to provide a which has a thermal expansion coefficient that matches with the article to be sealed, has excellent fluidity, sealing powders and pastes Ru used sealing glass that can hermetically sealed.

  As a result of various studies, the present inventors have found that a decrease in the fluidity of the sealing glass is caused by a reaction between the ceramic filler powder and the glass powder to cause devitrification.

  Further, the present inventors have found that the reactivity with glass powder can be suppressed by covering the surface of the ceramic filler powder with refractory fine powder, and is proposed as the present invention.

The sealing powder of the present invention is a sealing powder containing a glass powder and a filler powder. As the glass powder, Bi ₂ O ₃ —B ₂ O ₃ glass, P ₂ O ₅ —SnO glass, P ₂ O ₅ — It contains any one of Ag ₂ O glass, P ₂ O ₅ —CuO glass, V ₂ O ₅ —BaO glass, ceramic filler powder coated with refractory fine powder as filler powder, , Cordierite, willemite, NbZr (PO ₄ ) ₃ or more, refractory fine powder is one or more of Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , ceramic The average particle size of the filler powder is 10 to 500 times the average particle size of the refractory fine powder.

Furthermore, sealing paste of the present invention is characterized by comprising kneading a said sealing powder and vehicles.

In the filler powder according to the present invention, the ceramic filler powder is covered with the fire-resistant fine powder. Therefore, when the sealing powder or paste is used as the sealing glass, the sealing glass is composed of the filler powder and the glass powder. Even when the filler powder content is high, sufficient fluidity can be obtained for sealing.

  Moreover, since the allowable range of the filler powder contained in the sealing glass is widened, the sealing glass can be easily adjusted to a thermal expansion coefficient that matches the sealing material.

Examples of the ceramic filler powder include cordierite, willemite, alumina, zircon, tin oxide, β-eucryptite, KZr ₂ (PO ₄ ) ₃ (hereinafter referred to as KZP), NbZr (PO ₄ ) ₃ (hereinafter referred to as NZP). 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 _0.5 Zr ₂ (PO ₄ ) ₃ , WO ₄ Zr ₂ (PO ₄ ) ₂ or the like can be used , but cordierite, willemite or NZP having a small thermal expansion coefficient can be easily matched with the thermal expansion coefficient of the object to be sealed .

In the filler powder according to the present invention , the coverage of the refractory fine powder on the surface of the ceramic filler powder is preferably 50% or more. If it is less than 50%, the glass and the ceramic filler powder are likely to come into contact with each other and thus tend to react to cause devitrification. Preferably it is 70% or more, More preferably, it is 80% or more.

  The coverage was measured by taking an image of 100 randomly selected filler powders using a scanning electron microscope (SEM) at a magnification of 5000 times, and measuring the projected area of the filler powder and the adhesion area of the fine powder. Calculated. Similarly, the coating thickness was obtained by taking an image of 100 randomly selected filler powders using a scanning electron microscope (SEM) at a magnification of 5000 times, and measuring the adhesion thickness of fine powder.

In addition, the filler powder according to the present invention preferably has a thickness of 0.1 to 10 μm of a film formed of refractory fine powder. If it is thicker than 10 μm, the thermal expansion coefficient is hardly affected by the fireproof fine powder, and if it is thinner than 0.1 μm, the reaction with glass tends to be difficult to sufficiently suppress. Preferably it is 0.2-3 micrometers, More preferably, it is 0.3-1 micrometers.

The filler powder according to the present invention is produced as follows.

  First, 0.1 to 30 parts by mass of refractory fine powder is added to 100 parts by mass of the ceramic filler powder, and the mixture is uniformly stirred and mixed.

  Subsequently, the filler powder is produced by firing at 700 to 1400 ° C. for 2 to 20 hours according to the kind of the ceramic filler powder so that the ceramic filler powder is not softened and fused.

  In addition, when ceramic filler powder aggregates through a fireproof fine powder, an aggregate is crushed as needed and classification is performed.

  The classification is performed in order to remove refractory fine powder that is generated by pulverization or that does not adhere to the ceramic filler powder even after firing.

  The average particle size of the ceramic filler powder is preferably 2 to 60 μm because the fluidity of the glass is hardly inhibited. When the average particle size of the ceramic filler powder is smaller than 2 μm, the surface area of the ceramic filler powder increases, so that it tends to react with glass during sealing. For this reason, the fluidity of the sealing glass tends to be lowered, and it is difficult to seal and seal. On the other hand, if it is larger than 60 μm, the mechanical strength after sealing of the sealing glass tends to be low, and there is a possibility of leakage at the sealing portion.

  As the refractory fine powder, alumina, silica, zircon, titania, zirconia and the like can be used. In particular, alumina, silica, and zircon are preferable because of low reactivity with glass. In the present invention, different types of materials are used for the ceramic filler powder and the refractory fine powder.

  The average particle size of the refractory fine powder is preferably 10 μm or less. If it is larger than 10 μm, the amount added for coating tends to be excessive, and the properties of the filler to be coated such as thermal expansion coefficient and strength tend to be impaired. Preferably it is 2 micrometers or less, More preferably, it is 1 micrometer or less.

Incidentally, sealing the powder of the present invention has an average particle size of the cell la Mick filler powder is 10 to 500 times the average particle size of the refractory fines are preferably If it is 20 to 300 times, formed by refractory fines The thickness of the coating tends to be in the above range.

  The sealing powder of the present invention is composed of the filler powder and glass powder as described above, and is preferably 10% to 55% filler powder and 45% to 90% glass powder, and 25% to 55% filler powder. The glass powder is more preferably 45 to 75%. In addition, you may add the powder of refractory fillers, such as a silica, an alumina, a titania, a tin oxide, a zirconia, a zircon, to 10%.

  If there is too much glass powder, the thermal expansion coefficient tends to be large and it tends to be difficult to match the thermal expansion coefficient of the object to be sealed, and if there is too much filler powder, the fluidity tends to deteriorate and air sealing tends to be difficult. is there.

The sealing powder of the present invention includes Bi ₂ O ₃ —B ₂ O ₃ glass, P ₂ O ₅ —SnO glass, P ₂ O ₅ —Ag ₂ O glass, and P ₂ O ₅ —CuO glass as glass powder. Glass or V ₂ O ₅ —BaO-based glass can be used. These glasses are preferable because they have a low melting point of 500 ° C. or lower. In particular, Bi ₂ O ₃ —B ₂ O ₃ glass and P ₂ O ₅ —SnO glass are preferable because they are excellent in weather resistance and fluidity.

  In each glass, it is preferable that PbO is not substantially contained since it is an environmental load substance. Note that “substantially not contained” means that the content is 0.1% or less.

Bi ₂ O ₃ —B ₂ O ₃ -based glass contains, by mol%, Bi ₂ O ₃ 30 to 50%, B ₂ O ₃ 10 to 40%, BaO + SrO 1 to 10%, ZnO 0 to 35%. It is preferable.

The reason why the Bi ₂ O ₃ —B ₂ O ₃ glass is limited to the above composition range will be described below.

Bi ₂ O ₃ is a main component for lowering the softening point of the glass, and its content is 30 to 50%, preferably 35 to 45%. When the content of Bi ₂ O ₃ is less than 30%, the transition point tends to be high, and there are cases where baking cannot be performed at 550 ° C. or less, and when it is more than 50%, stable glass tends to be difficult to obtain.

B ₂ O ₃ is essential as a glass forming component, and its content is 10 to 40%, preferably 18 to 40%. If the content of B ₂ O ₃ is less than 10%, the glass becomes unstable and tends to devitrify. Even when devitrification does not occur, the crystal deposition rate is extremely high at the time of firing, and the fluidity necessary for operations such as adhesion, sealing, and coating cannot be obtained. On the other hand, if B ₂ O ₃ exceeds 40%, the viscosity of the glass becomes too high and firing at a temperature of 500 ° C. or less becomes difficult.

  BaO and SrO have a great effect on the stabilization of the glass, and contain them in a total amount of 1 to 10%, preferably 2 to 9%. If the total amount of these components is less than 1%, the effect is not obtained, while if it exceeds 10%, the transition point becomes high. The BaO content is preferably 0 to 10%, particularly preferably 2 to 9%, and the SrO content is preferably 0 to 5%, particularly preferably 0 to 3%.

  ZnO has a great effect on stabilizing the glass, and its content is 0 to 30%, preferably 5 to 25%. When the content exceeds 30%, the glass is easily crystallized and the fluidity is deteriorated.

In the Bi ₂ O—B ₂ O ₃ glass, components other than those described above will be described.

Each of SiO ₂ and Al ₂ O ₃ is a component that is contained in order to further stabilize the glass, and the total amount is 5% or less, preferably 2% or less. If these components exceed the above range, the viscosity of the glass becomes too high, which is not preferable. Incidentally, it is preferable that the content of SiO ₂ and Al ₂ O ₃ is 0-2%, respectively.

  CuO is a component for stabilizing the glass, and its content is 0 to 20%, preferably 0 to 15%. If CuO exceeds 20%, the precipitation rate of crystals tends to be extremely high and the fluidity tends to deteriorate, which is not preferable.

Fe ₂ O ₃ is a component for stabilizing the glass, and its content is 0 to 5%, preferably 0 to 2%. If Fe ₂ O ₃ exceeds 5%, the glass becomes unstable.

Cs ₂ O and F ₂ are components that lower the viscosity of the glass. The content of Cs ₂ O is 0 to 5%, preferably 0 to 3%, and the content of F ₂ is 0 to 20%, preferably 0 to 10%. When these components exceed the above range, the chemical durability of the glass is lowered.

In addition to the above components, MgO, La ₂ O ₃ , TiO ₂ , ZrO ₂ , V ₂ O ₅ , Nb ₂ O ₅ , MoO ₃ , WO ₃ , WO ₃ , TeO ₂ , Ag ₂ O, Na ₂ O, K ₂ O, Li ₂ O and the like can be added at 5% or less.

P The ₂ O ₅ -SnO-based glass, in mol% _{display, P 2 O 5 18~45%,} SnO 35~60%, B 2 O 3 0~30%, 0~20% ZnO, Al 2 O 3 0-10%, and a glass having a composition of SiO ₂ 0 to 15%.

The reason why the P ₂ O ₅ —SnO glass is limited to the above composition range is shown below.

P ₂ O ₅ is a glass forming oxide. If the P ₂ O ₅ content is less than 18%, it is difficult to obtain sufficient glass stability. If it is in the range of 18 to 45%, sufficient stability can be obtained for the glass, but if it exceeds 45%, the moisture resistance tends to deteriorate. Further, if P ₂ O ₅ is 20% or more, the glass is further stabilized, but if it exceeds 35%, the weather resistance of the sealing glass tends to be slightly deteriorated, so it is 20 to 35%. Is more preferable.

  SnO is a component that lowers the melting point of glass. If the SnO content is less than 35%, the viscosity of the glass increases and the sealing temperature tends to increase, and if it exceeds 60%, vitrification becomes difficult. In addition, since it will become easy to devitrify at the time of sealing when there is much SnO, it is preferable that it is 55% or less. Moreover, if it is 40% or more, since it is excellent in fluidity | liquidity and high airtightness is obtained, it is preferable.

B ₂ O ₃ is a glass forming oxide. B ₂ O ₃ is not an essential component but has an effect of stabilizing the glass. However, if it exceeds 30%, the viscosity of the glass becomes too high, the fluidity at the time of sealing is remarkably deteriorated, and the airtightness of the sealing part tends to be impaired. A preferable range of B ₂ O ₃ is 0 to 25%. Since B ₂ O ₃ has a strong tendency to increase the viscosity of glass, it is required to have very high fluidity, and when it is necessary to significantly lower the softening point, B ₂ O ₃ should not be contained.

  ZnO is an intermediate oxide. ZnO is not an essential component, but is desirably 4% or more because it has a great effect of stabilizing the glass. However, if ZnO exceeds 20%, devitrification tends to occur on the glass surface during sealing. The ZnO content is desirably 5 to 15%.

Al ₂ O ₃ is an intermediate oxide. Al ₂ O ₃ is not an essential component, but it is desirable to contain Al ₂ O _{3 because} it has the effect of stabilizing the glass and the effect of reducing the thermal expansion coefficient. However, if it exceeds 10%, the softening temperature rises and the sealing temperature tends to increase. In addition, when the stability of glass, a thermal expansion coefficient, fluidity | liquidity, etc. are considered, the range of 0.5 to 5% is more preferable.

SiO ₂ is a glass forming oxide. Although SiO ₂ is not an essential component, it is desirable to contain it because it has an effect of suppressing devitrification. If it exceeds 15%, the softening temperature rises and the sealing temperature tends to be high.

In addition to the above, the P ₂ O ₅ —SnO-based glass may contain the following components.

R ₂ O (R is Li, Na, K and Cs) is not an essential component, but there is a tendency that the adhesive force is improved by adding at least one of the R ₂ O components in the composition. However, if the total amount exceeds 10%, devitrification tends to occur during sealing. Of R ₂ O, Li ₂ O is most likely to improve the adhesive strength.

Although lanthanoid oxides such as La ₂ O ₃ and CeO ₂ are not essential components, the weather resistance of the glass tends to be improved by containing a total amount of 0.1% or more in the glass component.

In addition to the lanthanoid oxide, the use of other rare earths such as Y ₂ O ₃ is effective for improving the weather resistance of the glass. The amount of rare earth added excluding the lanthanoid oxide is preferably 0 to 5%.

  R′O (R ′ is Mg, Ca, Sr, and Ba) is not an essential component, but is useful as a component that stabilizes the glass. When the total amount of R′O exceeds 15%, devitrification tends to occur. Therefore, the content of R′O is desirably 15% or less, more preferably 10% or less.

In addition, for example, components that stabilize the glass, such as Nb ₂ O ₅ , TiO ₂ , ZrO ₂ , CuO, MnO, In ₂ O _3, can be contained in a total amount of up to 20%. In addition, when content of these stabilization components exceeds 20%, glass will become unstable and it will become difficult to manufacture. In order to obtain a more stable glass, the content is preferably 15% or less.

The contents of Nb ₂ O ₅ , TiO ₂ , and ZrO ₂ are all 0 to 15%, particularly preferably 0 to 10%. If the content of any component exceeds 15%, the glass tends to be unstable.

  The contents of CuO and MnO are both 0 to 10%, particularly preferably 0 to 5%. If the content of any component exceeds 10%, the glass tends to be unstable.

In ₂ O ₃ can be used for the purpose of obtaining high weather resistance. The content of In ₂ O ₃ is preferably 0 to 5%.

  Further, it is preferable that halogens such as F and Cl are not substantially contained since there is a risk of lowering the display luminance.

The P ₂ O ₅ -Ag ₂ O-based glass, in mol% _{display, Ag 2 O 5~70%, P} 2 O 5 5~55%, AgI 0~30%, ZnO 0~55%, Nb 2 O _{5 0~15%, B 2 O 3} 0~15%, include glass having a composition of TeO ₂ 0 to 65%.

The reason why the P ₂ O ₅ —Ag ₂ O glass is limited to the above composition range is shown below.

Ag ₂ O is a main component constituting the glass. When Ag ₂ O is less than 5%, the stability of the glass is hardly obtained and the melting point tends to be too high. On the other hand, if it exceeds 70%, the stability tends to deteriorate. Therefore, it is preferably 5 to 70% and more preferably 15 to 50%.

P ₂ O ₅ is a glass forming oxide. If the P ₂ O ₅ content is less than 5%, the glass stability tends to be difficult to obtain. On the other hand, if it exceeds 55%, the moisture resistance tends to deteriorate. Therefore, it is preferable in it being 5-55%, and more preferable in it being 5-40%.

  AgI is a component that lowers the melting point of glass. When AgI exceeds 30%, vitrification tends to be difficult. Therefore, 0 to 30% is preferable, and 0 to 25% is more preferable.

  ZnO is a glass forming oxide. If ZnO is contained, the glass tends to be more stabilized, but if it exceeds 55%, it tends to be difficult to vitrify. Therefore, 0 to 55% is preferable, and 0 to 35% is more preferable.

Nb ₂ O ₅ , B ₂ O ₃ , and TeO ₂ are all components that stabilize the glass, but if the content exceeds the limited range, the melting point of the glass tends to increase, which is not preferable. Therefore, the content of Nb ₂ O ₅ is preferably 0 to 15%, and more preferably 0 to 10%. Further, the content of B ₂ O ₃ is preferably 0 to 15%, and more preferably 0 to 10%. TeO ₂ is preferably 0 to 65%, and more preferably 0 to 45%.

In the P ₂ O ₅ —Ag ₂ O-based glass, in addition to the above, components such as GeO ₂ , WO ₃ , and MoO ₃ may be contained within a range in which the melting point of the glass does not become too high.

The P ₂ O ₅ -CuO glass, in mol% _{display, P 2 O 5 25~75%,} CuO 25~75%, include glass having a composition MO 10 to 60%. Note that MO refers to one or more oxides selected from the group consisting of ZnO, BaO, CaO, MgO, SrO, NiO, MnO, and FeO.

The reason why the P ₂ O ₅ —CuO-based glass is limited to the above composition range is shown below.

P ₂ O ₅ is a glass forming oxide. If the P ₂ O ₅ content is less than 55%, the glass stability tends to be difficult to obtain. On the other hand, if it exceeds 75%, the moisture resistance tends to deteriorate. Therefore, it is preferable in it being 55 to 75%, and more preferable in it being 55 to 70%.

  CuO is a main component constituting the glass and a component that stabilizes the glass. If the CuO content is less than 25%, the glass stability tends to be hardly obtained. If it exceeds 75%, the melting point tends to be too high. Therefore, it is preferable in it being 25-75%, and more preferable in it being 25-45%.

  MO is a glass forming oxide. If 10% or more of MO is contained, the glass tends to be stabilized, but if it exceeds 60%, the melting point becomes too high and vitrification tends to be difficult. Therefore, it is preferably 10 to 60%, more preferably 10 to 45%.

In addition to the above, the P ₂ O ₅ —CuO-based glass contains components such as Al ₂ O ₃ , SiO ₂ , and B ₂ O _{3 in a} range in which the melting point of the glass does not become too high. May be.

The V ₂ O ₅ -BaO-based glass, in mol% _{display, V 2 O 5 30~80%,} BaO 20~55%, include glass having a composition 0 to 50% ZnO.

The reason why the V ₂ O ₅ —BaO-based glass is limited to the above composition range is shown below.

V ₂ O ₅ is a main component constituting glass. When V ₂ O ₅ is less than 30%, it becomes difficult to obtain glass stability and the melting point tends to be too high. If it exceeds 80%, the stability of the glass tends to deteriorate. Therefore, it is preferably 30 to 80%, and more preferably 30 to 70%.

  BaO is also a main component constituting the glass. When BaO is less than 20%, the stability of the glass tends to be difficult to obtain. If it exceeds 55%, the melting point becomes too high and the stability of the glass tends to deteriorate. Therefore, it is preferable in it being 20-55%, and it is more preferable in it being 20-45%.

  ZnO is a glass forming oxide. If ZnO is contained, the glass tends to be more stabilized, but if it exceeds 50%, vitrification tends to be difficult. Therefore, 0 to 50% is preferable, and 0 to 40% is more preferable.

In the V ₂ O ₅ —BaO-based glass, in addition to the above, Bi ₂ O ₃ , Nb ₂ O ₅ , CuO, Fe ₂ O _{3 and the} like may be contained within a range in which the glass characteristics are not impaired.

Cordierite filler powder is preferable for Bi ₂ O ₃ glass.

Further, for the P ₂ O ₅ —SnO glass, KZP or NZP filler powder is preferable.

For P ₂ O ₅ —Ag ₂ O glass, KZP or NZP filler powder is preferred.

For P ₂ O ₅ —CuO-based glass, KZP or NZP-based filler powder is preferable.

Further, cordierite filler powder is preferable for the V ₂ O ₅ —BaO glass.

  It is preferable that the sealing powder of the present invention has an average particle size of 2 to 50 μm because the glass is easily melted at a low temperature.

  Below, the preparation methods of the paste for sealing are demonstrated.

  First, glass powder and filler powder having the above composition and average particle diameter are prepared.

  Next, it mixes so that glass powder may be 45-90% and filler powder may be 10-55% by volume% display, and the powder for sealing is produced.

  Subsequently, after adding 7 to 80 parts by mass of the vehicle to 100 parts by mass of the sealing powder and stirring so that the sealing powder is uniformly dispersed, the powder aggregates and bubbles are removed using a roll mill and sealed. Make a wearing paste.

  The viscosity of the sealing paste is preferably 200 to 1500 poise. If it is smaller than 200 poise, the glass powder or filler powder constituting the paste tends to settle, and if it is larger than 1500 poise, it tends to be difficult to uniformly apply to the glass substrate.

  The vehicle is obtained by uniformly mixing a binder resin and a solvent.

  The binder resin is a component that adjusts the viscosity of the vehicle. As the binder resin, ethyl cellulose (ECL), polyethylene glycol derivative (PEGD), nitrocellulose (NCL), polymethylstyrene (PMS), polyethylene carbonate (PEC) Methacrylic acid ester (MAE) can be used.

  The solvent is a component for diluting the sealing glass into a paste, and as the solvent, N, N′-dimethylformamide (DMF), terpineol (TPO), γ-butyrolactone (γ-BL), tetralin, butyl carbitol acetate (BCA), ethyl acetate (EA), diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, benzyl alcohol (BZA), toluene, 3-methoxy-3-methylbutanol, water, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether , Dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, propylene Carbonate (PRC), dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone and the like can be used.

  When the vehicle is less than 7 parts by mass, it does not become a paste and tends to be difficult to handle. On the other hand, when the amount is more than 80 parts by mass, the vehicle component is burned or volatilized at the time of sealing, so that microbubbles are likely to be contained in the sealed part and the sealed part tends to leak.

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

Tables 1-3 show filler powder samples, and Tables 4 and 5 show glass powder samples. Tables 6 and 7 show sealing powders composed of a filler powder sample and a glass powder sample, and Tables 8 and 9 show pastes. Sample d in Table 1, Sample l in Table 3, Sample 6 in Table 6, Sample 7 in Table 7, Sample 8 in Table 8 are reference examples.

  The filler powder samples shown in Tables 1 to 3 were produced as follows.

  First, raw materials were prepared so as to have the composition in the table, and mixed for 1 hour using an alumina ball mill.

  Next, the mixed powder was put into an alumina crucible and fired at the temperature and time described in Tables 1 to 3.

  Finally, the fired product was taken out from the crucible, pulverized using an alumina ball mill, and crushed using a 150 mesh sieve to prepare a filler sample.

  The coverage was measured using the method described above.

  The average particle diameter was measured using a laser diffraction type particle size distribution measuring apparatus (SALD2000 manufactured by Shimadzu Corporation).

  The film thickness is obtained by calculating the thickness of the film using the same method as the comparison rate.

  The glass powder samples shown in Tables 4 and 5 were prepared as follows.

  First, glass raw materials were prepared so as to have the composition shown in the table, put into a platinum crucible, and melted at the temperature shown in the table for 2 hours using an electric furnace.

  Subsequently, the molten glass was passed between water-cooled rollers, formed into a thin plate shape, pulverized with a ball mill, and passed through a 150 mesh sieve to produce a glass sample.

  The glass transition point was determined by a differential thermal analyzer (DTA).

  For the softening point, the temperature at the bottom of the second absorption peak of DTA was read.

  The thermal expansion coefficient was measured using a push rod type thermal expansion coefficient measuring device after polishing the molded glass body into a cylindrical shape having a diameter of 4 mm and a length of 40 mm.

  The sealing powders shown in Tables 6 and 7 were prepared by uniformly mixing the filler powder samples prepared in Tables 1 to 3 and the glass powder samples prepared in Tables 4 and 5 at the ratios shown in the tables.

  The fluidity was evaluated as follows.

  First, a mass corresponding to the density of the obtained sealing powder was put into a mold and press-molded to prepare a button (cylindrical shape) having an outer diameter of 20 mm.

  Next, the button was placed on the window glass, heated to the firing temperature described in the table in the air at a rate of 10 ° C./min and held for 10 minutes, and then the button diameter was measured. .

  The paste samples shown in Tables 8 and 9 were prepared as follows.

  First, the sealing powder samples and vehicles prepared in Tables 6 and 7 were prepared, and mixed and stirred so as to have the ratios in the table, to prepare a preliminary kneaded paste. In the vehicle, a resin and a solvent were mixed at a ratio described in the table.

  Next, a paste sample from which aggregates and bubbles were removed from the pre-kneaded paste using a roll mill was prepared.

  Next, each obtained glass paste was apply | coated to the uniform thickness by the screen-printing method on the soda glass plate.

  Finally, in order to volatilize the solvent, drying was performed at 150 ° C. for 10 minutes, and then the glass paste was heated to the firing temperature in air and held for 10 minutes to perform firing. Using the sample thus prepared, the leveling property and firing state of the paste were examined.

  As for the leveling property of the paste, the surface of the paste after application was observed, and “◯” if smooth and glossy, and “x” otherwise.

  In addition, the firing state was “◯” for smooth and glossy, and “x” for other cases.

As is apparent from Tables 6 and 7, the thermal expansion coefficient of the powder for sealing with the sample was 47-95 × 10 ⁻⁷ / ° C., and the flow diameter showing fluidity was also good, 20-24 mm. .

  Further, as is clear from Tables 8 and 9, the pastes of Samples A to C were good in both leveling property and fired state.

The sealing powder and sealing paste of the present invention are used for IC packages and display devices, specifically PDP, field emission display (FED), plasma addressed liquid crystal display (PALC), surface electric field display (SED) and fluorescent display. It can be suitably used for sealing electronic parts such as tubes (VFD) .

Claims (8)

In sealing powder containing glass powder and filler powder,
As the glass _{powder, Bi 2 O 3 -B 2 O} 3 based _glass, P ₂ O 5 -SnO-based _glass, P ₂ O 5 -Ag ₂ O-based _glass, P ₂ O 5 -CuO _glass, V 2 _{O 5} - Including any of BaO glass,
As the filler powder, including ceramic filler powder coated with refractory fine powder,
The ceramic filler powder is one or more of cordierite, willemite, NbZr (PO ₄ ) ₃ ,
The fireproof fine powder is one or more of Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO ₂ ,
A sealing powder, wherein the ceramic filler powder has an average particle size of 10 to 500 times the average particle size of the refractory fine powder.   2. The sealing powder according to claim 1, wherein the film thickness formed by the refractory fine powder is 0.1 to 10 [mu] m.   3. The sealing powder according to claim 1 or 2, wherein the coating rate of the film formed of the refractory fine powder is 50 to 100%.   The sealing powder according to any one of claims 1 to 3, wherein the average particle diameter of the fire-resistant fine powder is 10 µm or less. 5. The sealing powder according to claim 1, wherein the ceramic filler powder has an average particle size of 20 to 300 times that of the refractory fine powder.   6. The sealing powder according to claim 1, wherein a mixing ratio of the filler powder and the glass powder is 10% to 55% filler powder and 45 to 90% glass powder in terms of volume%. .   A sealing paste obtained by kneading the sealing powder according to any one of claims 1 to 6 and a vehicle.   The sealing paste according to claim 7, wherein 7 to 80 parts by mass of a vehicle is added to 100 parts by mass of the sealing powder.