WO2008007504A1 - Glass composition for sealing and sealed material - Google Patents

Abstract

[PROBLEMS] To obtain a glass composition for sealing that not only improves the water resistance of tin phosphate glass but also attains appropriate sealing in low-oxygen atmosphere, especially vacuum atmosphere, and that further allows sealing at low temperature such as 490°C or below, excelling in thermal stability, and obtain a relevant sealed material. [MEANS FOR SOLVING PROBLEMS] There is provided a glass composition for sealing characterized by having a glass composition containing, by molar percentage in terms of oxide, 30 to 80% SnO, 10 to 25% (not including 25%) P2O5, 0 to 20% B2O3, 0 to 20% ZnO, 0 to 10% SiO2, 0 to 10% Al2O3, 0 to 20% WO3 and 0 to 20% R2O (R represents at least one of Li, Na, K and Cs) and characterized by being employed in sealing in low-oxygen atmosphere, especially vacuum atmosphere.

Description

 Specification

 Sealing glass composition and sealing material

 Technical field

 TECHNICAL FIELD [0001] The present invention relates to a glass composition for sealing and a sealing material using the same, a plasma display panel (hereinafter referred to as PDP), a field emission display (hereinafter referred to as FED), a fluorescent display tube. (Hereinafter referred to as VFD) sealing of flat display devices, sealing of optical components such as lens caps, LD caps, etc., electronic components such as IC packages, piezoelectric resonators such as crystal resonators and surface acoustic wave devices The present invention relates to a sealing glass composition and a sealing material suitable for sealing (including electronic component storage containers).

 Background art

 Conventionally, glass has been used as a sealing material for flat display devices and the like. Glass has superior chemical durability and heat resistance compared to resin adhesives, and is suitable for ensuring airtightness of flat display devices.

 [0003] These glasses are required to have various properties such as mechanical strength, fluidity, and electrical insulation depending on the application, but at least the fluorescence properties of phosphors used in flat display devices are inferior. It is required to be usable at a temperature that does not allow them to be used. Therefore, as a glass satisfying the above characteristics, a lead fluoric acid-based glass containing a large amount of PbO (see, for example, Patent Document 1) has been widely used.

 [0004] However, recently, environmental problems have been pointed out with respect to PbO contained in lead borate glass, and it is desired to replace the lead borate glass power with glass containing no PbO. For this reason, various low-melting-point glasses have been developed as substitutes for lead borate glasses. Among them, tin phosphate glass (SnO—PO) described in Patent Documents 2 and 3, etc.

 (Also referred to as 25-type glass) is expected to be an alternative candidate because it has characteristics similar to those of lead borate glass in terms of various properties such as thermal expansion coefficient. The reality is that the characteristics such as stability still do not reach the characteristics of lead borate glass.

[0005] By the way, the sealing material used for the PDP undergoes the following heat treatment process. First, P After the sealing paste is applied to the outer periphery of the back substrate of the DP, primary firing (also referred to as glaze process or temporary firing process) is performed. The primary firing is performed under a temperature condition in which the resin contained in the vehicle is completely pyrolyzed. Next, secondary firing of the sealing material (also referred to as a sealing process or a sealing process) is performed to seal the front and back substrates of the PDP. Finally, after evacuating the inside of the PDP through the exhaust pipe, the required amount of rare gas is injected and the exhaust pipe is sealed. In this way, the PDP is produced.

[0006] FED is a display device in which the inside of the device is kept in a high vacuum, and a phosphor is excited by an electron beam generated by applying an electric field in the high vacuum to emit visible light. is there . Even in FED, there is a process of sealing the exhaust pipe after exhausting the inside of the apparatus to a high vacuum through the exhaust pipe in the final manufacturing process after primary firing and secondary firing.

 Patent Document 1: Japanese Patent Laid-Open No. 2-2229738

 Patent Document 2: JP-A-7-69672

 Patent Document 3: Japanese Patent Laid-Open No. 9-227154

 Disclosure of the invention

 Problems to be solved by the invention

[0007] Conventional tin phosphate glass contains a large amount of PO as a glass component.

 twenty five

 Compared to lead borate glass, the flat panel display devices such as PDP, FED, etc., which require high water resistance that is not sufficient in water resistance, could not secure long-term reliability. Specifically, tin phosphate glass described in Patent Documents 2 and 3 contains 25 mol% or more of PO.

 twenty five

 Contains. In tin phosphate glass, the Po content is the main factor that determines the water resistance of the glass.

 twenty five

 It is an important factor, and if the PO content is 25 mol% or more, the water resistance of the glass is secured.

 twenty five

 It becomes difficult.

 [0008] On the other hand, in the tin phosphate glass, if the PO content is less than 25 mol%,

 twenty five

 Although the water resistance can be improved, since the glass constituents are reduced, the thermal stability of the glass tends to be impaired, especially when firing in an air atmosphere, and it should be used as a sealing material. It becomes difficult.

[0009] As described above, the PDP is manufactured through a primary firing process, a secondary firing process, and a vacuum exhaust process. Usually, the primary firing process and the secondary firing process are performed in the atmosphere, and the vacuum exhaust process is performed. The process is performed in a high vacuum reduced pressure atmosphere. The evacuation process is a process that requires a high temperature and a long period of time (usually 5 hours or more) to make the inside of the apparatus into a high vacuum, which is a cause of lowering the production efficiency of PDP and the like. Under these circumstances, various attempts have been made to shorten the evacuation process. However, an effective improvement measure has yet to be found.

 [0010] Currently, the secondary firing process and the vacuum exhaust process cannot be performed at the same time, but if the secondary firing process and the vacuum exhaust process can be performed at the same time, the manufacturing process of the PDP can be dramatically increased. The product cost of PDP can be greatly reduced. In order to perform the secondary firing process and the vacuum exhaust process at the same time, it is necessary to perform the secondary firing in a reduced pressure (vacuum), but the conventional tin phosphate glass has a PO content of 25 mol% or more. Because it is sealed under reduced pressure

 twenty five

 Then, unacceptable bubbles are generated in the sealing layer, and the hermeticity of the PDP cannot be secured, and at the same time, the adhesive strength of the sealing layer is significantly reduced. Furthermore, when tin phosphate glass is used and sealed under reduced pressure, the glass tends to be devitrified, and a predetermined sealing thickness cannot be formed. At the same time, there is a possibility that the airtightness of the PDP cannot be ensured.

 [0011] On the other hand, since FED also has a process of keeping the inside of the apparatus in a high vacuum, if it can be sealed under reduced pressure as in the case of PDP, the manufacturing efficiency can be dramatically increased and the product cost can be reduced. Can be cheap. In addition, FED is required to be sealed at a low temperature of 490 ° C or lower because the heat resistance of phosphors, devices, etc. is poor compared to PDP.

 [0012] The present invention improves the water resistance of tin phosphate glass and at the same time improves the production efficiency of PDP and the like, and can be well sealed in a low oxygen atmosphere, particularly under reduced pressure, and has a low temperature of 490 ° C or lower. It is a technical problem to obtain a sealing glass composition and a sealing material which can be sealed with a good thermal stability.

 Means for solving the problem

[0013] As a result of diligent efforts, the inventor of the present invention expressed SnO in terms of mol% as follows: SnO 30-80%, PO 10-25% (however, 25% not included), BO 0-20% ZnO 0-20%,

 2 5 2 3

 SiO 0-10%, Al O 0-10%, WO 0-20%, R O (R is Li ゝ Na ゝ K, Cs

2 2 3 3 2

The present invention proposes that the present invention can solve the above problems by regulating the glass composition to 0 to 20%. That is, first, book The glass composition for sealing of the invention is a glass composition, expressed in mol% in terms of the following oxides.

, SnO 30-80%, P O 10-25% (excluding 25%), B O 0-20%,

 2 5 2 3

 ZnO 0-20%, SiO 0-10%, Α1 Ο 0-10%, WO 0-20%, R O (R is Li

 2 2 3 3 2

, Na, K, Cs) 0 to 20%, and used for sealing in a low oxygen atmosphere. Here, the “low oxygen atmosphere” in the present invention means an atmosphere having an oxygen concentration of 15% by volume or less (preferably 10% by volume or less, more preferably 5% by volume or less, and further preferably 1% by volume or less). For example, high vacuum atmosphere, Ar atmosphere, N atmosphere

 2 Atmosphere of neutral gas, etc., and atmosphere in which 11% by volume of 11 gas is mixed in N atmosphere

 twenty two

 And a reducing gas atmosphere. The residual oxygen concentration in the atmosphere can be measured with, for example, LC-750 manufactured by Toray Engineering Co., Ltd.

[0014] The glass composition for sealing of the present invention can obtain desired characteristics by strictly regulating the glass composition range as described above. Specifically, by regulating the SnO content within a predetermined range, low-temperature sealing properties can be secured, and even when sealed during decompression, the airtight reliability of the flat panel display device is ensured. Can be maintained. P O

 By regulating the content of 25 to less than 25 mol%, the water resistance of the glass can be remarkably improved. If the P 2 O content is restricted to less than 25 mol%, the glass is thermally stable.

 twenty five

 In addition, a certain amount of B 2 O, SiO or the like is added to the glass composition.

 2 3 2

 If added, it is possible to maintain the thermal stability of the glass without impairing the low-temperature sealing property of the glass. Furthermore, if the PO content was regulated to less than 25 mol%, sealing was performed under reduced pressure.

 twenty five

 Even in this case, the reliability of the flat display device can be ensured. Therefore, if the glass composition for sealing of the present invention is used as a sealing material, sealing can be performed under reduced pressure, so that the manufacturing cost of a flat display device such as a PDP can be reduced.

[0015] The glass composition for sealing of the present invention can be satisfactorily sealed in a low oxygen atmosphere (depressurized atmosphere, neutral atmosphere, reducing atmosphere, etc.). The reason is as follows. In the glass composition, Sn becomes a stable glass forming component when the valence is divalent. On the other hand, when the valence of Sn becomes tetravalent, the glass tends to devitrify and become thermally unstable. Therefore, in a low-oxygen atmosphere, tin phosphate glass is less susceptible to devitrification because SnO in the glass composition is oxidized during firing and the reaction to become SnO hardly proceeds. Furthermore, the sealing of the present invention The glass composition for low-oxygen has a low oxygen content because the PO content is regulated to less than 25 mol%.

 twenty five

 When fired in an atmosphere, the glass is difficult to foam and has the advantages of both.

[0016] Secondly, a sealing glass composition of the present invention, in addition to the above glass composition, in mole _^0/0 in terms of oxide, MoO, Nb O, TiO, ZrO, CuO, MnO, MgO , CaO, S

 3 2 5 2 2

 It is characterized by containing 0 to 35% of total amount of rO and BaO.

Thirdly, in addition to the above glass composition, the glass composition for sealing of the present invention is represented by MoO 0-5%, NbO 0-15%, TiO 0- 15%, ZrO

 3 2 5 2 2

0-15%, CuO 0-10%, MnO 0-15%, R, 0 (R ¾Mg, refers to at least one of Ca ゝ Sr ゝ Ba) 0-15%.

[0018] Fourth, the sealing glass composition of the present invention has a glass composition, in molar _^0/0 in terms of oxide, SnO 30~80%, PO 10~25% ( however, 25% Not included), BO

 2 5 2 3

0.1 to 10% (excluding 10%), ZnO 0 to 20%, SiO 0 to 10%, Al O 0

 2 2 3

~ 10%, WO 0-20%, R O (R is at least l of Li, Na, K, Cs) 0-2

 3 2

 0%, MoO 0-5%, NbO 0-15%, TiO 0-15%, ZrO 0-15%, CuO

 3 2 5 2 2

0 to 15%, MnO 0 to 15%, R, 0 (R, indicates at least one of Mg ゝ Ca ゝ Sr ゝ Ba) 0-15%.

[0019] Fifth, the sealing glass composition of the present invention is characterized by containing F in an amount of 0 to 10% in terms of the following oxide% in addition to the above glass composition.

 2

 [0020] Sixth, the sealing material of the present invention is characterized in that it contains 50 to 100% by volume of a glass powder comprising the above glass composition for sealing and 0 to 50% by volume of a refractory filler powder. It is possible.

[0021] Seventh, the sealing material of the present invention is characterized in that when fired in a reduced pressure atmosphere, the surface of the fired body is bright and devitrification is not observed. Here, as to “the surface of the fired body is glossy and devitrification is not recognized when fired in a reduced pressure atmosphere” in the present invention, the suitability is judged by the following procedure. First, dry seal the sealing material to 2cmφ to make a button-shaped sample. Next, after placing the prepared sample on a high strain point glass substrate, 1. OX IOTorrd. 33kPa) under reduced pressure (soft spot of the sealing material + 30 °) Bake for 30 minutes at the temperature of C). The heating / cooling speed is 5 ° CZ, Samples are loaded into and removed from the reactor at room temperature. The gloss is evaluated by measuring the average surface roughness Ra of the prepared button-shaped sample surface. The average surface roughness Ra is measured by a method based on JIS-R 3502. When the average surface roughness Ra of the button surface is 100 μm or less, it is evaluated as “shiny”. Further, the sample after firing was observed, and crystals were deposited on the surface of the button-shaped sample produced, and the product was evaluated as “no devitrification”. Devitrification is evaluated by observing crystals on the button surface using a stereomicroscope.

 Eighth, the sealing material of the present invention is characterized in that the surface of the fired body is glossy and devitrification is not observed when fired in a neutral or reducing atmosphere. Here, with regard to “the surface of the fired body is glossy and devitrification is not observed when fired in a neutral or reducing atmosphere” in the present invention, the suitability is determined by the following procedure. To do. First, dry-press the sealing material to 2cmφ to make a button-shaped sample. Next, after placing the prepared sample on a high strain point glass substrate, using an atmosphere firing furnace, N

 2 Atmosphere or atmosphere containing 1% H gas in N atmosphere (softening point of sealing material + 3

 twenty two

 Bake for 30 minutes at a temperature of 0 ° C). The temperature raising and lowering speed is 5 ° CZ, and the sample is put into and out of the firing furnace at room temperature. The gloss is evaluated by measuring the average surface roughness Ra of the prepared button-shaped sample surface. When the average surface roughness Ra of the button surface is 100 m or less, it is evaluated as “shiny”. The average surface roughness Ra is measured by a method based on JIS-R3502. In addition, the fired sample is observed, and if no crystal is deposited on the surface of the button-shaped sample produced, it is evaluated that “devitrification is not observed”. Devitrification is evaluated by observing crystals on the button surface using a stereomicroscope.

Ninth, in the sealing material of the present invention, the refractory filler contains tin oxide, niobium oxide, zirconium phosphate, cordierite, Na Nb Zr (PO 4), KZr (PO 4), Ca N

 0. 5 0. 5 1. 5 4 3 2 4 3 0. 25 b Zr (PO), NbZr (PO), K Nb Zr (PO), Zr WO (PO) group forces

0. 5 1. 5 4 3 4 3 0. 5 0. 5 1. 5 4 3 2 4 4 2 It is characterized by containing 1 type or 2 types or more selected from.

 Tenth, the sealing material of the present invention includes PDP, FED, VFD, CRT (Cathode Ray Tube

), Used for sealing either electronic parts or optical parts.

Eleventh, the sealing tablet of the present invention is a sealing tab in which a sealing material is sintered into a predetermined shape. In the case of a let, the sealing material is characterized by the aforementioned sealing material.

 Twelfth, the sealing paste of the present invention is characterized in that the sealing material is the aforementioned sealing material in the sealing paste in which the sealing material is dispersed in a vehicle. Here, the “vehicle” in the present invention is a constituent material of a sealing paste containing a solvent, a resin binder, and the like, and the solvent is an essential component, but the resin binder is an optional component.

 Thirteenthly, the sealing paste of the present invention comprises vehicle toluene, N, N, dimethylformamide, 1,3-dimethyl-2-imidazolidinone, dimethyl carbonate, butyl carbitol acetate, isoamyl acetate, propylene. Carbonate, N-methyl-2-pyrrolidone acetate nitrile, dimethyl sulfoxide, acetone, methyl ethyl ketone, isododecyl alcohol, isotridecyl alcohol, pentanediol, pentanediol derivative, CC n 2n +

It is characterized by containing one or more selected from the group of higher alcohols represented by OH (n = 8-20).

[0028] Fourteenth, the sealing paste of the present invention is characterized in that it contains one or more selected from the group consisting of vehicle nitrocellulose, polyethylene glycol derivatives, and polyethylene carbonate.

 Fifteenthly, the PDP or FED manufacturing method of the present invention is a PDP or FED manufacturing method including a sealing step using the sealing material, and is a whole or a part of the sealing step. Is characterized in that it is carried out in a reduced pressure atmosphere. The “reduced pressure atmosphere” as used in the present invention refers to the case where the atmospheric pressure is 1. O X IOTorrd.

 [0030] Sixteenthly, the method for manufacturing an optical component or electronic component according to the present invention is a method for manufacturing an optical component or electronic component having a sealing step using the above-mentioned sealing material. All or part of the process is characterized by being carried out in a neutral or reducing atmosphere. As used herein, the term “neutral atmosphere” refers to a neutral gas atmosphere such as an Ar atmosphere or an N atmosphere.

 2

 The As used herein, the term “reducing atmosphere” refers to an atmosphere in which 11% by volume of 11 gas is mixed in an N atmosphere.

 twenty two

 Reducing gas atmosphere such as atmosphere.

 The invention's effect

[0031] The glass composition for sealing of the present invention has significantly improved water resistance, and at the same time, can be sealed well even under reduced pressure, thus greatly improving the production efficiency of flat display devices such as PDPs. Can do. That is, in the case of a flat display device such as a PDP, if it can be sealed in a reduced pressure, it is not necessary to evacuate the inside of the device for a long time of 5 hours or more through the exhaust pipe. The manufacturing efficiency of the display device can be dramatically increased. Furthermore, the sealing glass composition of the present invention has an advantage of good thermal stability even though it can be sealed at a low temperature of 490 ° C. or lower. Generally, low temperature of glass and thermal stability of glass are characteristics that are difficult to achieve at the same time, but the glass composition for sealing of the present invention can achieve both at a high level.

 Brief Description of Drawings

FIG. 1 is an explanatory view showing a configuration of an optical cap component.

 Explanation of symbols

[0033] 1 Optical cap member

 2 Metal shell

 3 Sealing material

 4 Light-transmissive glass member (spherical lens member)

 BEST MODE FOR CARRYING OUT THE INVENTION

 [0034] The reason why the glass composition range of the glass composition for sealing of 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.

 [0035] SnO is an essential component that lowers the melting point of glass, and its content is 30 to 80%, preferably 40 to 70%, more preferably 50 to 66%. In particular, if SnO is 40% or more, the glass has excellent fluidity and high airtightness can be secured. If SnO is less than 30%, the viscosity of the glass becomes too high, and the sealing temperature may be increased. If SnO is more than 80%, vitrification tends to be difficult. In the case of tin phosphate glass, if SnO exceeds 70%, the ability of the glass to be easily altered when fired in an air atmosphere, and in a low oxygen atmosphere, even if SnO is in the range of 70-80%, Glass is difficult to change during firing.

 [0036] PO is a glass-forming oxide and is an essential component. Its content is 10-25% (伹

 twenty five

25% is not included), preferably 11 to 24%, more preferably 13 to 23%, and still more preferably 15 to 20%. If the PO force is ¾5% or more, the water resistance of the glass decreases, and It becomes difficult to ensure long-term reliability of the display device. Meanwhile, Po force

 If it is less than 2 5 sio%, the thermal stability of the glass will be poor. In general, the glass-forming oxide Po is low.

 As the glass composition for sealing of the present invention regulates the glass composition within a predetermined range, even if PO is less than 25%,

 twenty five

 Good thermal stability. In particular, since the content of Po is low, the firing atmosphere is reduced in pressure.

 twenty five

 Even in an atmosphere, it can be fired satisfactorily.

[0037] B 2 O is a glass-forming oxide and is a component that stabilizes the glass. Its content

 twenty three

 Is 0 to 20%, preferably 0.1 to 16%, more preferably 2 to 15%, still more preferably 3 to 11.8%, most preferably 3 to 10% (however, 10% is not included) ). In particular, when performing low-temperature sealing, the glass can be cooled at a low temperature if the content of BO is 1 to 5%.

 twenty three

 Also, in general, as the glass-forming oxide, B 2 O, decreases, the thermal

 twenty three

 The stability will be poor, but if the firing atmosphere is a low oxygen atmosphere, the content of B 2 O will be low.

 twenty three

 Even if it is a case, it can bake favorably. If B O is more than 20%, the glass

 twenty three

 The balance of composition is not achieved, and the glass is separated when the glass is melted, and a scum is likely to be generated on the surface of the glass melt. On the other hand, if you add a small amount of B 2 O, for example, about 2%,

 twenty three

 Generation of scum can be suppressed. Furthermore, if the B 2 O is more than 20%, the viscosity of the glass

 twenty three

 Becomes too high, and the fluidity of the glass deteriorates.

 [0038] ZnO is an intermediate oxide and a component that stabilizes the glass. The content is 0 to 20%, preferably 0 to 15%, more preferably 0 to 10%, still more preferably 3 to 10%. In particular, if the ZnO content is 3% or more, the thermal stability of the glass can be improved, and devitrification hardly occurs on the glass surface during sealing. On the other hand, when ZnO is more than 20%, the balance of the glass composition is lacking, and conversely, the thermal stability of the glass tends to decrease.

 [0039] SiO is a glass-forming oxide and is a component that stabilizes the glass. Its content

 2

 Is 0 to 10%, preferably 0.5 to 5%. In particular, a small amount of SiO added, for example about 0.5%

 2

 If added once, the thermal stability of the glass is improved, and the glass becomes difficult to devitrify during sealing. If SiO is 5% or less, the soft temperature of the glass will not rise so much, and low-temperature sealing can be performed.

2

 it can. On the other hand, if SiO is more than 10%, the soft temperature of the glass rises and low temperature sealing is difficult.

 2

At the same time, the fluidity of the glass is impaired. [0040] Al O is an intermediate oxide, a component that stabilizes the glass, and heat of the glass.

twenty three

 It is a component that lowers the expansion coefficient. Its content is 0 to 10%, more preferably 0 to 5%, still more preferably 0.1 to 5%. In particular, if the content of Al 2 O is 0.5 to 5%,

 twenty three

 This makes it easier to adjust the thermal stability and coefficient of thermal expansion. On the other hand, if Al O is more than 10%,

 twenty three

 The soft temperature of the glass rises, making it difficult to seal at low temperatures and impairing the fluidity of the glass.

 [0041] Although WO is not an essential component, it has an effect of improving the adhesive force with an object to be sealed.

 Three

 In addition, it is a component that improves the weather resistance of glass, and an appropriate amount of WO is added to the glass composition.

 Three

 If added, a highly reliable sealing layer can be formed over a long period of time. WO

 3 Content is 0 to 20%, preferably 0 to 15%, more preferably 1.2 to 15%, still more preferably 3 to 10%. In order to enjoy the above effects accurately, WO should be 0.1%, especially 3% or less.

 Three

 You can do it above. In addition, WO is a relatively expensive raw material and the fluidity of glass

 Three

 Considering it, it is preferable to set WO to 10% or less. On the other hand, if the WO power is more than ¾0%,

 3 3

 In addition to incurring higher material costs, the soft spot of glass rises, making it difficult to seal at low temperatures

In the present invention, R 2 O is not an essential component, but at least one of R 2 O is glass.

 twenty two

 If added during the composition, the adhesive strength with a glass substrate or the like can be increased. Its content is

0 to 20%, preferably 0 to 10%. In particular, when considering the thermal stability of the glass, such as surface devitrification at the time of sealing and the fluidity of the glass, R O

 The total amount of 2 is preferably 10% or less. If the total amount of R 2 O exceeds 20%, the glass tends to devitrify during sealing. In addition,

 2

 Among R 2 O, Li O has the highest ability to improve adhesion to glass substrates, etc.

2 2 2

During the firing, ion exchange with an alkali element contained in an object to be sealed such as a glass substrate is likely to cause microcracks in the glass substrate. Therefore, the Li O content is 3% or less

 2

 Is preferable.

 [0043] MoO, NbO, TiO, ZrO, CuO, MnO, MgO, CaO, SrO, BaO are glass

 3 2 5 2 2

Is a component that stabilizes the amount, and the total content thereof is 0 to 35%, preferably 0 to 25%. If the total amount of these components exceeds 35%, the glass becomes thermally unstable, making it difficult to produce the glass stably. [0044] MoO is not an essential component, but if it is added in a small amount to the glass composition, it will wet with the material to be sealed.

Three

 It is a component that can improve the properties. Its content is 0-5%, more preferably 0.1-3%. If it exceeds the MoO force, the glass will become devitrified due to the increased viscosity when the glass melts.

Three

 It becomes easy.

 [0045] Nb 2 O, TiO and ZrO are components that improve the stability of the glass, and

 2 5 2 2

 It is a component that improves the weather resistance of laths. The content of these components is 0 to 15%, preferably 0 to 10%. If these components exceed 15%, the glass will melt and the glass tends to become unstable.

 [0046] The CuO content is preferably 0 to 10%, particularly preferably 0 to 5%. If CuO exceeds 10%, the glass tends to become thermally unstable.

 [0047] The MnO content is preferably 0 to 15%, particularly preferably 0 to 8%. If MnO exceeds 15%, the glass tends to become thermally unstable. In addition, it is possible to use both MnO and MnO as the raw material for introducing MnO. When MnO is used as the raw material for introduction, the thermal stability of the glass is improved. preferable.

 [0048] R'O is an alkaline earth oxide, and is a network-modified acid oxide. These components are not essential components, but their total content is preferably 0 to 15%, particularly preferably 0 to 5%. If R'O exceeds 15%, the glass tends to become thermally unstable. In particular, among R'O, MgO and BaO are preferred because they have a high effect of low temperature in addition to stabilizing the glass.

 [0049] In O is a component that improves the weather resistance of glass, and its content is preferably 0 to 10%.

 twenty three

 0 to 5%. However, since In O is a noble metal oxide, the In O force is more than 10%.

 2 3 2 3

 In this case, the cost of the raw material for the glass is increased, and the use is restricted.

[0050] The lanthanoid acid oxide is a network-modified oxide, and is not an essential component in the present invention! / Reinforcement A lanthanoid acid oxide is contained in a glass component in a total amount of 0.1% or more. By doing so, the weather resistance of the glass is improved. On the other hand, if the lanthanoid oxide exceeds 15%, the sealing temperature tends to increase. Therefore, considering the balance between weather resistance and sealing temperature, the content of the lanthanoid compound is 0 to 15% in total, preferably 0.5 to 15%, more preferably 1 to 15%. As the lanthanoid oxide, La 2 O, CeO, Nd 2 O and the like can be used. In addition In addition to lanthanoid oxides, the addition of other rare earth oxides such as Yo

 twenty three

 The weather resistance of the glass can be further improved. The rare earth oxide content excluding the lanthanoid oxide is preferably 0 to 5%.

[0051] Ta 2 O has an effect of improving weather resistance, and its content is preferably 0 to 10%. Ta

 twenty five

 If O exceeds 10%, the soft spot of the glass becomes too high.

 twenty five

 [0052] TeO is a component that has an effect of lowering the soft saddle point, and its content is preferably 0 to 15%.

 2

 Good. If TeO exceeds 15%, the thermal stability of the glass is impaired.

 2

 [0053] F may adversely affect the fluorescence characteristics of phosphors included in flat display devices and the like.

 2

 Although it is a certain component, it is a component that is effective in defoaming if the glass is low temperature. The content is preferably 0 to 10%, more preferably 0 to 5%, and even more preferably 0 to 3%. If F exceeds 10%, there is a high possibility that the fluorescent properties of the phosphor will be adversely affected.

 2

 [0054] It is preferable that the sealing glass composition of the present invention does not substantially contain PbO. Here, “substantially does not contain PbO” means that the PbO content contained in the glass composition is 100 Oppm or less. If the glass composition for sealing does not contain PbO, it can accurately meet recent environmental demands.

 [0055] In addition, the glass composition for sealing of the present invention may further contain up to 10% of other components in addition to the above components as long as the effects of the present invention are not impaired.

 [0056] In the above composition range, it is naturally possible to select a preferred composition range by arbitrarily combining the preferred and range of each component. As a more preferable composition range, it is expressed in mol% in terms of the following oxides: SnO 30 to 80%, PO 10-25% (however, 25% is not included), BO 0.1 to 10% ( However, 10%

2 5 2 3

 Not including), ZnO 0-20%, SiO 0-10%, Α1 0〜10 0-10%, WO 0-20%,

 2 2 3 3

 R 0 (R indicates at least one of Li ゝ Na, K, Cs) 0-20%, MoO 0-5%, Nb

2 3 2

O 0-15%, TiO 0-15%, ZrO 0-15%, CuO 0-10%, MnO 0-15

5 2 2

%, R, 0 (R, represents at least one of Mg, Ca, Sr, Ba) 0-15% glass composition. If the composition range of the glass composition is regulated as described above, the water resistance of the glass can be greatly improved, and the thermal stability of the glass can be greatly improved. The glass composition is more suitable for sealing in a low oxygen atmosphere than in an atmospheric oxygen atmosphere. However, since the thermal stability of glass is greatly improved, it can be sealed even in an air atmosphere.

 In the tin phosphate glass according to the present invention, various raw materials such as oxides, hydroxides, nitrates, and phosphates can be used as glass raw materials. However, when raw materials having a low water content are used. The glass melt during melting can be blown out and foaming of the glass during firing can be suppressed, which is preferable. Furthermore, it is preferable to add one or more reducing agents such as metals such as Al and Si or carbon to the glass batch. If these are added to the glass notch, the melting atmosphere that can remove only the moisture in the glass can be reduced, and the reaction of SnO being oxidized to SnO during melting is suppressed, and as a result, the tin phosphate system Stable melting of glass

 2

 In addition, it can be used stably in the subsequent firing step.

[0058] A sealing glass composition having the above composition has a glass transition point of about 250 to 400 ° C, a softening point of about 360 to 440 ° C, and a temperature range of about 400 to 600 ° C. Good fluidity. In addition, it has a coefficient of thermal expansion of about 80 to ¹⁵⁰ X 10 ^_7 Z ° C in the temperature range of 30 to 250 ° C. The glass composition for sealing of the present invention having such properties can be used alone as a sealing material for a material having a suitable thermal expansion coefficient.

[0059] The glass composition for sealing of the present invention can be processed into a powder form by a ball mill, a jet mill or the like and used as a sealing material. Moreover, if the glass composition for sealing is made of glass powder, it becomes easy to adjust the mechanical strength and thermal expansion coefficient by mixing with a refractory filler powder, etc., and is mixed with a vehicle etc. It becomes easy to use as a material.

[0060] The coefficient of thermal expansion does not fit! Encapsulate materials such as alumina (70 X 10 "V ° O, high strain point glass (85 X 10" V ° O or soda flat glass (90 X 10 "V ° O)) In the case of wearing, it can be used appropriately by adding a fireproof filler powder, which is a low expansion material, and combining it.The thermal expansion coefficient of the composite (composite) is 10 ~ It is important to design it as low as 30 X 10 ^_7 Z ° C. Generally, the sealing material is weaker than the object to be sealed, so the stress remaining in the sealing material part constituting the sealing layer is The compression (compression) side is desirable, so that it is possible to prevent the occurrence of an airtight leak or peeling of the sealing layer due to the destruction of the sealing interface. [0061] The sealing material of the present invention preferably contains 50 to 50% by volume of glass powder and 0 to 50% by volume of refractory filler powder, in particular, FED, PDP, VFD, In the case of CRT sealing, it is preferable to contain 60 to 80% by volume of glass powder and 20 to 40% by volume of refractory filler powder. In the case of sealing FED, PDP, VFD, and CRT, it is preferable to adjust the thermal expansion coefficient to be about 60 to 90 ^× 10 ^_7 Z ° C. When the amount of the refractory filler powder is more than 50 volume%, the ratio of the glass powder becomes relatively low, and it becomes difficult to obtain the desired fluidity. The particle size of the glass powder and refractory filler powder is determined by the average particle size D using a laser diffraction particle size distribution analyzer (SALD-2000J, manufactured by Shimadzu Corporation).

 50 is preferably 1.0 · 15 to 15. O / z m. If the average particle size D is less than 1 · O / z m,

 50

 If the average particle diameter D exceeds 15 m, sealing will be achieved.

 50

 The fluidity of the material is obstructed and the airtight reliability of the flat display device or the like is obtained.

[0062] Further, the glass composition for sealing may be formed into a predetermined shape, for example, a ball shape, a rod shape or a plate shape, and used as a sealing material.

[0063] When the sealing material of the present invention is fired in a reduced-pressure atmosphere, it is preferable that the surface of the fired body is glossy and devitrification is not observed. When sealing in a reduced pressure atmosphere, the sealing material is more easily foamed than in the atmosphere, but the sealing material of the present invention regulates the glass composition of the glass powder to a predetermined range. Therefore, it can be fired well in this atmosphere. As a result, even if the PDP secondary firing process and the vacuum exhaust process are performed simultaneously, the sealing layer is not devitrified, and foaming that impairs the hermeticity of the PDP can be suppressed, improving the production efficiency of the PDP, This can contribute to cost reduction. In the reduced-pressure atmosphere, devitrification and bubbles are more likely to occur in the sealing material as the atmospheric pressure decreases. Therefore, the lower the atmospheric pressure, the more the advantages of the present invention can be enjoyed. Specifically, the atmospheric pressure is preferably 1. OX 10 ^_1 Torr or less (13.3 Pa or less) as a reduced pressure atmosphere, and 1. OX 10 ^_3 Torr or less (0.133 Pa or less) is more preferable 1.0 X 10 ^_5 Torr or less (0. 00133Pa hereinafter) is more preferable.

[0064] When the sealing material of the present invention is fired in a neutral atmosphere or a reducing atmosphere, it is preferable that the surface of the fired body is glossy and devitrification is not observed. The sealing glass composition of the present invention does not impair the fluidity and wettability even when sealed in a reducing atmosphere, but rather when sealed in a reducing atmosphere, the atmosphere contains a certain amount of oxygen. Fluidity and wettability are improved as compared to sealing in an atmosphere. This is because the tin contained as the main component of the glass composition is more divalent (SnO) than tetravalent (SnO).

 2

 This is because the glass is thermally stable as glass. In other words, when sealing in a reducing atmosphere, the proportion of SnO that SnO hardly oxidizes to SnO increases, and as a result

 2

 The thermal stability of the glass is maintained without loss. Also, neutral atmosphere such as N atmosphere

 2

 Even in the atmosphere, SnO force SnO is not easily oxidized to SnO

 2

 As a result, the thermal stability of the glass is maintained. Furthermore, since the sealing material of the present invention regulates the glass composition of the glass powder within a predetermined range, the glass has good thermal stability and low-temperature sealing properties. Can be fired well.

 [0065] Various materials can be used as the refractory filler powder, and examples thereof include cordierite, zircon (zirconium silicate), tin oxide, niobium oxide, zirconium phosphate, willemite, and mullite. Also, use a fireproof filler with the basic structure of [AB (MO)].

 2 4 3

 Is available. 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 compatible with elements such as P, Si, W, and Mo.

[0066] Among these refractory fillers, tin oxide, cordierite, niobium oxide, Na Nb

 0. 5 0.

Zr (PO), KZr (PO), Ca Nb Zr (PO), NbZr (PO), Zr WO (

5 1. 5 4 3 2 4 3 0. 25 0. 5 1. 5 4 3 4 3 2 4

PO), K Nb Zr (PO), and Ca Nb Zr (PO) are well suited. In particular,

4 2 0. 5 0. 5 1. 5 4 3 0. 25 0. 5 1. 5 4 3

 Na Nb Zr (PO), KZr (PO), Ca Nb Zr (PO), Zr WO (PO

0. 5 0. 5 1. 5 4 3 2 4 3 0. 25 0. 5 1. 5 4 3 2 4 4

2) The coefficient of thermal expansion can be lowered with a small amount of content that greatly reduces the effect of low expansion.

. Also, if necessary, a refractory white pigment (e.g. TiO) or a refractory black pigment (e.g.

 2

 For example, Fe-Mn, Fe-Co-Cr, and Fe-Mn-Al pigments) can be added.

[0067] It is preferable that the sealing material of the present invention does not substantially contain PbO. If the sealing material does not contain PbO, it can accurately meet recent environmental requirements.

[0068] In the sealing material of the present invention, the object to be sealed is a metal (for example, stainless steel, Kovar, etc.), that is, It is preferably used for metal sealing. As described above, the sealing material of the present invention can be satisfactorily sealed without oxidizing the metal in the sealing step because it can be used favorably in a low oxygen atmosphere.

 [0069] The sealing material of the present invention can be processed into a sealing tablet sintered in a predetermined shape and used. With a sealing tablet, it is possible to accurately seal desired parts such as optical components, and to reduce the number of manufacturing processes that do not require the application of sealing paste with a dispenser or screen printer. This can contribute to lower product costs. Sealed tablets are manufactured through multiple independent thermal processes as follows. First, a solvent resin binder is added to the glass powder to form a slurry. Then, this slurry is put into a granulator such as a spray dryer to produce glass powder granules. At this time, the glass powder granules are heat-treated at a temperature at which the solvent volatilizes (about 100 to 200 ° C.). Further, the produced glass powder granules are put into a mold designed to have a predetermined size and, for example, dry press-molded into a ring shape to produce a pressed body. Next, the resin binder remaining in the pressed body is decomposed and volatilized in a baking furnace such as a belt furnace and sintered at a temperature of about the soft point of the glass powder to produce a sealed tablet. . In addition, the firing in the firing furnace may be performed a plurality of times. When the firing is performed a plurality of times, the sintering strength of the glass tablet is improved, and the glass tablet can be prevented from being broken or broken. In the sealed tablet of the present invention, the shape of the tablet is not particularly limited. For example, ring shapes, plate shapes, columnar shapes, frame shapes, tubular shapes, and the like can be used. In addition, the below-mentioned thing can be used for a solvent and a resin binder.

 [0070] The sealing material of the present invention is preferably mixed with a vehicle and used as a sealing paste. If the sealing material is processed into a sealing paste, a sealing pattern can be formed with high accuracy by a coating machine such as a dispenser or a screen printer. A vehicle is a material containing components such as a solvent, a resin binder, a surfactant, a pigment, a thickener, and a plasticizer.

 [0071] The glass powder according to the present invention is a tin phosphate glass mainly containing SnO. In general, tin phosphate glass reacts with the resin binder contained in the vehicle during firing due to its low melting point. Specifically, SnO is oxidized and becomes SnO. ,Liquidity

 2

Is lost. Therefore, the vehicle according to the present invention is a solvent that volatilizes at a low temperature, a resin fat resin. In addition to using a binder, it is highly necessary to use a solvent and a resin binder that do not alter the tin phosphate glass.

 [0072] The solvent is preferably a solvent that does not denature the tin phosphate glass having a low boiling point and a small amount of residue after firing. That is, it is preferable to use a solvent having a boiling point of 300 ° C. or less. Specifically, toluene, N, N, -dimethylformamide (DMF), 1,3 dimethyl-2 imidazolidinone (DMI), dimethyl carbonate, butyl carbitol acetate (BCA), isoamyl acetate, propylene carbonate, N-methyl 2-Pyrrolidoneacetonitrile, dimethyl sulfoxide, acetone, methyl ethyl ketone and the like can be preferably used. Moreover, it is preferable to use a higher alcohol as the solvent. Higher alcohols can be used as sealing pastes without adding a resin binder to the vehicle because the solvent itself has viscosity. When the vehicle does not contain a resin binder, it is possible to suppress the situation where SnO is oxidized and SnO is formed, and the glass is denatured during sealing. Representative luxury

2

 As the alcohol, either isohexyl alcohol represented by c C OH (n = 8 to 20) or n 2n + l

 Isoeicosyl alcohol can be used. In particular, from the viewpoint of the viscosity of the solvent, when mixed with a higher alcohol force sealing material having a molecular weight equal to or higher than isodecyl alcohol (n = 10), an appropriate viscosity is secured and it is immediately preferred. From the viewpoint of the amount of residue after firing, those having a molecular weight of isohexadecyl alcohol (n = 16) or less are preferred. Therefore, the higher alcohol is most preferably the total balance power isotridecyl alcohol. Furthermore, pentanediol and its derivatives can also be used as a solvent. Specifically, jetylpentanediol (C 3 H 2 O 3) has excellent viscosity characteristics.

 9 20 2

[0073] As the resin binder, in addition to a low decomposition temperature, a resin that does not denature the tin phosphate glass with few residues after firing is preferable. Nitrocellulose, polyethylene glycol derivatives, and polyethylene carbonate are suitable as resin binders because they do not alter the tin phosphate glass, which has low decomposition temperature and little residue after firing. Excellent degradability and viscosity characteristics. Polyethylene strength-N, N, -dimethylformamide (DMF), dimethyl carbonate, propylene carbonate, N-methyl-2-pyrrolidone, acetonitrile, dimethyl sulfoxide, acetone Soluble in methyl ethyl ketone. In particular, dimethyl carbonate, propylene carbonate, and N-methyl-2-pyrrolidone are preferable because they do not dry in a short time and the coating workability is excellent in leveling. When polyethylene carbonate is used by dissolving it in DMF, it must be dissolved at a higher concentration than the polyethylene glycol derivative, and the optimum concentration is 10 to 30% by weight. The optimal concentration when dissolved in dimethyl carbonate is 5 to 10 weight _^0/0. When propylene carbonate or N-methyl-2-pyrrolidone is used, the content is 10 to 30% by weight.

[0075] Polyethylene glycol derivatives are HOCH CH 0 {(CH CH O) NCO [X] —CO

 2 2 2 2 m

— N} _n and X is a hydrophobic linear group. Polyethylene render derivatives having the above skeleton structure exhibit excellent viscosity characteristics in a small amount and have low-temperature decomposability characteristics. In particular, polyethylene glycol derivatives having a molecular weight of 100,000 to 500,000 have good low-temperature decomposability. For industrial use, polyethylene glycol derivative strength is suitable because of its low cost and availability. Polyethylene glycol derivatives dissolve well in N, N'-dimethylformamide (DMF), 1,3-dimethyl-2-imidazolidinone (DMI) and the like. These solvents are preferable because they do not dry in a short time at room temperature. When the polyethylene glycol derivative is dissolved in DMF and DMI, the optimum concentration is 0.5 to 5% by weight. Note that the use of DMI rather than DMF is suitable for cases where volatility is kept low and comparative work time is increased.

 [0076] Nitrocellulose has low-temperature decomposability and can be mixed with isoamyl acetate and used as a vehicle.

 [0077] In any case, when the amount of the resin binder is too much, specifically, when the resin binder content is 35% by weight or more, the viscosity becomes too high, and when applied with a dispenser or the like. It should be noted that force that cannot be pushed out at a given air pressure or that the residue after firing becomes too large and may cause alteration during firing.

 [0078] The vehicle and the sealing material can be kneaded using a kneader such as a three-roll mill.

[0079] The glass composition for sealing of the present invention can also be used as a binder for conductive powder. In this case, the glass powder comprising the glass composition for sealing of the present invention 10 to 60% by weight And a conductive material containing 40 to 90% by weight of metal powder and 0 to 20% by weight of refractory filler powder. 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 secured. Also, if the amount of the refractory filler powder is more than 20% by weight, the ratio of the glass powder becomes relatively low, and the necessary sealing properties can be obtained. Here, examples of the metal powder include Ag, Pd, Al, Ni, Cu, Au, and a mixture thereof. Further, as the refractory filler powder, the same refractory filler as described above can be used. In addition, if necessary, a refractory white pigment (eg TiO), a refractory black pigment

 2

 (For example, Fe-Mn, Fe-Co-Cr, and Fe-Mn-Al pigments) can be added. In order to form a conductor pattern using this conductive powder, it is preferable to form a sealing paste by appropriately covering the above-mentioned vehicle with the conductive powder material. The conductive paste thus obtained can be formed into a conductive pattern by baking in a vacuum at 400 to 900 ° C. for about 5 minutes to 1 hour.

 [0080] A method for producing a PDP or FED of the present invention is a method for producing a PDP or FED having a sealing step using the above-mentioned sealing material, wherein a part or all of the sealing step is a reduced-pressure atmosphere. It is executed with care. When the sealing process is performed in a reduced pressure atmosphere, as described above, the secondary firing process and the vacuum exhaust process can be performed simultaneously, which contributes to a low product cost. Further, since the sealing material of the present invention can be sealed at a low temperature and has good thermal stability, troubles caused by the properties of the sealing material can also be suppressed. Note that VFD and CRT have the same or similar manufacturing processes as PDP and FED, and have the benefit of diverting the above manufacturing method.

[0081] The optical component or electronic component manufacturing method of the present invention is a method for manufacturing an optical component or an electronic component having a sealing process using the above-described sealing material, wherein all or part of the sealing step is performed. It is carried out in a neutral or reducing atmosphere. If the sealing process is a neutral atmosphere or a reducing atmosphere, the metal members used in the optical component are not oxidized, and the elements such as the electronic component are not easily deteriorated. As a result, the manufacturing cost of the optical component is reduced. The reliability of electronic parts can be improved. In addition to being capable of being sealed at low temperatures, the sealing material of the present invention also has good thermal stability, so that it is due to the thermal characteristics of the sealing material. Rubble can be suppressed.

 [0082] The optical component will be specifically described by taking an optical cap component as an example. An optical cap component 1 shown in FIG. 1 is a metal having a cylindrical side wall portion 5 and an end wall portion 6 provided at the tip of the side wall portion 5 and having a lens holding hole at the center thereof. It is composed of a shell 2 made of light and a light-transmitting glass member (spherical lens member) 4 fixed to the lens holding hole of the metal shell 2 with a sealing material 3. In the optical cap component, the light-transmissive glass member and the metal shell are sealed with a sealing material. The sealing process is generally performed at a low temperature for the purpose of maintaining the product characteristics of the optical cap component. Specifically, the sealing temperature is not higher than the soft melting point of the light-transmitting glass member and not higher than the Curie point of the metal shell, and is normally set to a temperature of 550 ° C. or lower. Therefore, when the sealing material of the present invention is used, it can be satisfactorily sealed at a low temperature even in a reducing atmosphere or a neutral atmosphere, and it can suppress the oxidation of the metal shell, so that a special plating treatment is performed. The cost of the optical cap part which is not necessary can be reduced.

 Example

 Hereinafter, the sealing glass composition and sealing material of the present invention will be described in detail based on examples.

 [0084] Tables 1 to 3 show examples of the glass composition for sealing of the present invention (samples a to n), and Table 4 shows comparative examples (samples P and q).

[0085] [Table 1]

Example

 (Mol%) a b c d e

S n O 54 6 1 62 52 60 p ₂ o ₅ 20 20 21 19 19

B ₂ O a 4. 5 3 10 1 2 14

Z n O 5. 5 7 3. 5 6. 5 5

S i 0 ₂ 1 2

A 1, 0 ₃ 0. 7 1. 5 ― 1 2

WO 10 ― ― 5 ―

Mg O 1 ― ― 0.5 ―

B a O ― 0.5 ― ― ―

Mn O ― 2.5 ― ― ―

M o O a 0. 3 ― ― ― ―

_{Nb 2 0 5 - - 0. 5} - -

L i ₂ 0 ― ― ― 0.2.

N a 0 1. 5 2. 5 0. 5 1. 3 ― κ ₂ ο 1. 5 ― 2. 5 2. 5 ― Thermal expansion coefficient (X 10 ⁷ V) 1 1 2 108 1 16 104 1 10 Glass transition Point (° c) 322 335 339 355 330 Softening point ( ^c c) 38 7 395 391 409 397

N ₂ Medium 25. 2 24. 3 24. 6 22. 7 24. 0 Flow diameter (mm)

 During decompression 24. 5 23. 0 23. 2 2 1. 1 22. 8

N ₂ Medium ○ ○ ○ ○ ○ Surface condition after firing

During decompression ○ ○ ○ ○ ○ Water resistance ○ ○ ○ ○ ○ 2]

Example

 (Mol%) f g h 1 j

S n O 56 57 58 60 62 p ₂ o ₅ 20 21 24 13 20

B ₂ 0 ₃ 4. 5 7 3 4. 5 16

Z n O 4 8. 5 1 0 7 ―

S i 0 ₂ 0. 5 0. 5 3

A 1, 0 ₃ 1 1 0. 5 1 2

WO 3 10 5 ― 9 ―

Mg O ― 0. 5 1. 5 ― ―

L i ₂ 0 3 ― ― ― ―

N a ₂ 0 ― ― 2 2 ― κ ₂ ο 1 ― 0.5 5 0.5 ― Coefficient of thermal expansion 1 o― ⁷ Z ° c) 110 114 112 109 106 Glass transition point (° c) 326 333 325 323 330 Softening point (° c) 392 41 2 393 39 1 4 1 1

N ₂ Medium 24. 6 22. 3 24. 5 24. 7 22. 5 Flow diameter (mm)

 During decompression 22. 9 21. 6 23. 4 23. 6 2 1. 1

N ₂ Medium ○ ○ ○ ○ ○ Surface condition after firing

 Under decompression ○ ○ ○ ○ ○ Water resistance ○ ○ o ○ ○ 3] Example

 (Mol%) k 1 m n

S n O 65 56 56. 5 58 p ₂ o ₅ 22. 5 20. 5 20 21

BO _{: i} 8.5 3 ― 5

Z n O 3 4. 5 4 2

S io ₂ ― ― 4.5 ―

A 1 ₂ 0 ₃ 1 1 1 1. 5

WO a ― 1 0 10 5

Mg O ― 0.5 ― ―

L i ₂ 0 ― 0. 5 0. 5 0. 3

N a ₂ 0 ― 1 1. 5 1. 2

K ₂ O ― 1. 5 2 1

F ₂ ― 1.5 ― 5 Thermal expansion coefficient (X 10 V ° c) 1 10 1 1 2 1 1 1 1 1 8

 Glass transition point (° C) 3 10 322 33 1 302 Softening point (° C) 385 387 398 368

N ₂ Medium 25. 4 25. 1 23. 7 26.5 Flow diameter (mm)

 During decompression 23. 9 23. 7 22. 5 25. 4

N ₂ Medium ○ ○ ○ ○ Surface condition after firing

During decompression ○ ○ ○ ○ Water resistance ○ ○ ○ ○ [0088] [Table 4]

[0089] Each glass sample was prepared as follows. First, the notch raw materials were prepared so as to have the glass compositions shown in Tables 1 to 4, and N gas for a flow rate of 3 LZ was flown into the electric furnace, and then the flow rate was 1 LZ.

 2

 Using an alumina crucible while publishing the glass melt with N gas of

2 2 Melting in an atmosphere at 900 ° C for 2 hours, then reducing the pressure to 50 Torr (6.65kPa) while maintaining the inside of the electric furnace at 900 ° C, and maintaining the reduced pressure for 1 hour The gas component present in the liquid was removed.

[0090] Tin monoxide was used as a batch raw material of SnO. Orthophosphoric acid as a batch raw material for PO (

 twenty five

 Strong phosphoric acid (105 wt% phosphoric acid) was used without using (orthophosphoric acid). The reason for this is that strong phosphoric acid has a lower moisture content than normal phosphoric acid, which can be accompanied by a reduction in the moisture content of the glass batch, and glass melt spills during melting. 《N Reagent grade oxides were used as raw materials for the other components.

[0091] Next, the molten glass was passed through a water-cooled roller, formed into a thin plate shape, pulverized with a ball mill, passed through a sieve with a mesh size of 105 m, and a laser diffraction particle size distribution analyzer (Shimadzu Corporation). Glass powder with an average particle size of about 10 m was obtained at SALD-2000J

[0092] The glass transition point and the coefficient of thermal expansion were determined after pressing the molten glass into 20 X 5mm φ. It measured with the rod-type thermal expansion meter (TMA) (made by Rigaku Corporation).

[0093] The softening point was measured by a macro-type differential thermal analysis (DTA) apparatus (manufactured by Rigaku Corporation) while flowing nitrogen gas at a flow rate of lOOccZ during measurement.

[0094] The surface state after firing (in N) was evaluated by performing a well-known flow button test. First each trial

 2

 A powder having a weight corresponding to the true specific gravity of the material was dry-pressed into a button shape of φ2 cm with a mold to obtain a button-shaped powder compact. Next, this compact was placed on a soda glass substrate, and then heated in N to a firing temperature of 450 ° C at a rate of 10 ° CZ and held for 10 minutes. That

2

 Thereafter, the surface of the fired body was glossy and observed with a stereomicroscope, and no crystal was observed. When the surface of the fired body was not glossy or was observed with a stereomicroscope, a crystal was observed and evaluated as “X”. In addition, the diameter of the fired body was measured with a digital caliper to evaluate its fluidity.

 2

 [0095] The surface state after firing (under reduced pressure) was evaluated by performing a well-known flow button test. First, a powder with a weight corresponding to the true specific gravity of each sample was dry-pressed into a φ2cm button using a die.

A button-like powder compact was obtained. Next, after placing this compact on the various substrates in the table, 1. In a reduced pressure of OX 10 ^_1 Torr, the temperature was raised to a firing temperature of 470 ° C at a rate of 10 ° CZ and held for 10 minutes. did. Thereafter, the surface of the fired body was glossy and observed with a stereomicroscope. The surface of the fired body was not glossy or was observed with a stereomicroscope, and the crystal observed was evaluated as “X”. Further, the diameter of the fired body was measured with a digital caliper, and the fluidity (under reduced pressure) was evaluated.

[0096] For the water resistance, a button-shaped sample prepared by evaluating the surface state after firing (in N) was used.

 2

 After each sample was kept in a constant temperature and humidity chamber at 85 ° C and 85% humidity for 1000 hours, no white foreign matter was generated on the button surface. Although there was no leaching out of the phosphoric acid component or the like, “△” was assigned, and when white foreign matter was generated and the leaching out of the phosphoric acid component was found to be “X”.

As a result, the samples a to n of the examples have a thermal expansion coefficient of 106 to 118 × 10 ”V ° C glass transition point of 302 to 355 ° C., and have good characteristics as a sealing material. In addition, the samples a to n of the examples also had good surface conditions after firing, while the samples p and q of the comparative examples had poor surface conditions after firing (during decompression). Yes, function as a sealing material in a reduced-pressure atmosphere It is thought that it cannot be demonstrated. In addition, the samples p and q of the comparative example have poor water resistance, and it is considered that long-term reliability of a flat display device or the like cannot be ensured.

 [0098] Tables 5 and 6 show examples (sample Nos. 1 to 8) of the sealing material of the present invention.

 [0099] [Table 5]

[0100] [Table 6]

表中に記載のガラス粉末に表中に記載の耐火性フィラー粉末を混合して、被封着 物である基板の熱膨張係数と整合させた。表中に記載された NZPは NbZr (PO ) 、

The glass powder listed in the table was mixed with the refractory filler powder listed in the table to match the thermal expansion coefficient of the substrate to be sealed. NZP listed in the table is NbZr (PO),

 4 3

ZWP¾Zr WO (PO), KZP¾KZr (PO), KNbZPi or Na Nb Zr (PO)

2 4 4 2 2 4 3 0. 5 0. 5 1. 5 Abbreviation of 4. [0102] Next, a method for producing various filler powders will be described.

[0103] Acid-niobium (Nb 2 O 3) filler powder and di-acid niobium (SnO 3) filler

 2 5 2 One powder was prepared in the same way. First, 3 wt% of zinc oxide was added to the raw material powder as a sintering aid, mixed, and then fired at 1400 ° C for 16 hours in an alumina crucible. Subsequently, the sintered ingot was taken out and pulverized in an aluminum ball mill, and then passed through a metal 325 mesh sieve, and a niobium oxide (Nb 2 O 3) and tin dioxide (SnO 2) filter having an average particle size of 12 / z m.

 2 5 2 A powder was obtained.

 [0104] A method for producing Zr WO (PO) filler powder will be described. Zirconium phosphate as raw material:

 2 4 4 2

 26.5g of ZrP 2 O equivalent to lmol, zirconium hydroxide: 159 equivalent of 1 mol of Zr (OH)

2 7 4

 2g, acid tungsten: mix 231.8g of WO equivalent to lmol, acid as crystallization aid

 Three

 19.7 g of magnesium iodide corresponding to 3 wt% of the total amount was added and mixed for 1 hour with an alumina ball mill. Next, this mixed powder was fired at 1400 ° C. for 15 hours in an alumina crucible to synthesize Zr WO (PO 4). After cooling, remove the crucible force Zr WO (PO) sintered product

Then, it was pulverized and classified with an alumina ball mill, passed through a metal 325 mesh sieve, and Zr WO (PO 4) filler powder having an average particle diameter of 15 m was obtained.

 2 4 4 2

 [0105] The NbZr (PO) filler powder was produced as follows. First, niobium phosphate: NbPO

 4 3 5 is equivalent to lmol, zirconium phosphate: ZrP O lmol

 2 7

 2 wt% magnesium oxide was added to the total amount and used as a raw material. Next, after mixing these three kinds of powders, firing was carried out in an alumina crucible for 15 hours at 1400 ° C. After cooling, the sintered NbZr (PO) is removed from the crucible and pulverized with an alumina ball mill.

 4 3

 After that, it was classified with a metal 325 mesh sieve. Thus, NbZr (PO 4) filler powder having an average particle size of 14 / z m was obtained. In the same way, KZr (PO

 4 3 2 4

) Filler powder, Na Nb Zr (PO 4) filler powder was obtained.

 3 0. 5 0. 5 1. 5 4 3

 [0106] The surface state after firing (in N) was evaluated by the following method. First, the true specific gravity of each sample

 2

 Corresponding weight of powder was dry-pressed into a 2cm button shape with a mold to obtain a button-shaped powder compact. Next, this molded body was placed on the soda glass substrate in the table, and then N

In 2, the temperature was raised to the 480 ° C firing temperature at a rate of 10 ° CZ, held at the firing temperature for 10 minutes, and then cooled to room temperature at the rate of 10 ° CZ. Thereafter, the surface of the fired body was glossy and observed with a stereomicroscope, and no crystal was observed. The surface of this fired body When the crystal was not glossy and observed with a Z or a stereomicroscope, crystals were observed and evaluated as “χ”. In addition, the diameter of this fired body is measured with a digital caliper.

 2 Evaluated.

[0107] The surface condition after firing (under reduced pressure) was evaluated by the following method. First, a powder having a weight corresponding to the true specific gravity of each sample was dry-pressed into a 2 cm button shape using a die to obtain a button-shaped powder compact. Next, this molded body was placed on the soda glass substrate in the table, 1. In a reduced pressure of OX 10 ^_1 Torr, the temperature was raised to a 490 ° C firing temperature at a rate of 10 ° C / min, After holding at the firing temperature for 10 minutes, the temperature was lowered to room temperature at a rate of 10 ° CZ. Thereafter, the surface of the fired body was glossy and observed with a stereomicroscope, and no crystal was observed. When the surface of the fired body was not glossy or was observed with a stereomicroscope, crystals that were observed were evaluated as “X”. Further, the diameter of the fired body was measured with a digital caliper, and the fluidity (under reduced pressure) was evaluated.

 [0108] Sealability (in N) was evaluated using a fired body after evaluation of the surface state after firing (in N).

 twenty two

 It was. When dropped from the upper lm of the concrete plate where there is no crack in the substrate, the button-like fired body that does not peel off the substrate force is marked as “◯”, and the substrate is cracked or the upper lm of the concrete plate. Force “X” indicates that the button-like fired body was peeled off when the substrate dropped.

 [0109] Sealability (under reduced pressure) was evaluated using a fired body after evaluation of the surface state after firing (under reduced pressure). When falling from the upper lm of the concrete board where there is no crack in the board, the button-like fired body does not peel off from the board, and the board is cracked, or the board is cracked or the upper lm force of the concrete board. When the button-like fired body and the substrate peeled when dropped, “X” was designated.

[0110] As a result, Sample Nos. 1 to 8 in the examples have a thermal expansion coefficient of 68.9 to 77 X 10 ^_7 Z ° C, and a flow diameter (in N) of ^{22.8 to 24.2} mm. The flow diameter (under reduced pressure) is 20. 0-21.7 mm

 2

 Therefore, it had good characteristics as a sealing material. The sealing property and the surface condition after firing were also good.

 Industrial applicability

[0111] The sealing glass composition and sealing material of the present invention have a PDP and various electron-emitting devices. Sealing of flat display devices such as various FEDs and VFDs to be sealed, sealing of optical parts such as lens caps and LD caps, and electronics such as IC packages, piezoelectric vibrators such as crystal resonators and surface acoustic wave elements, etc. It is suitable for sealing parts (including electronic component storage containers).

 [0112] In addition, the sealing glass composition and sealing material of the present invention can also be used in display devices such as CRTs and inorganic electoluminescence displays. It can also be used to seal lamps such as flat fluorescent lamps (FFL). Furthermore, it can be used for sealing optical components having optical fibers, ball lenses, and the like as constituent members.

 [0113] Furthermore, the sealing glass composition and the sealing material of the present invention can also be used in an organic electoluminescence display. Specifically, the sealing material of the present invention is processed into a sealing paste, a sealing tablet, a frit bar, etc., and the glass substrates are fixed to each other through these, and then a laser beam is applied to the sealing portion. By irradiating, the glass substrates are sealed together. As the laser beam, an excimer laser, a YAG laser, or the like can be used.

Claims

The scope of the claims [1] as a glass composition, in mol _^0/0 in terms of oxide, SnO 30 to 80%, PO 10  twenty five ~ 25% (excluding 25%), B O 0 ~ 20%, ZnO 0 ~ 20%, SiO 0 ~ 10  2 3 2  %, Al O 0-10%, WO 0-20%, R O (R is Li ゝ Na ゝ K, at least one of Cs 2 3 3 2  Pointing) A glass composition for sealing, which contains 0 to 20% and is used for sealing in a low oxygen atmosphere.  [2] Furthermore, the glass composition is expressed in terms of mol% in terms of the following oxides, MoO, Nb 2 O, TiO 2  3 2 5 2 , ZrO, CuO, MnO, MgO, CaO, SrO, BaO 2  The glass composition for sealing according to claim 1, wherein [3] Furthermore, as a glass composition, MoO 0 to 5% in terms of mol% in terms of the following oxide, Nb 2 O 3  3 2 5 0-15%, TiO 0-15%, ZrO 0-15%, CuO 0-10%, MnO 0-15%  twenty two  2. The sealing glass composition according to claim 1, wherein the glass composition is contained in an amount of 0 to 15%, wherein R, 0 (R represents at least one of Mg, Ca, Sr, and Ba). [4] as a glass composition, in mol _^0/0 in terms of oxide, SnO 30 to 80%, PO 10  twenty five ~ 25% (excluding 25%), B O 0.1 ~ 10% (excluding 10%), Zn  twenty three _{^{O 0~20 0/0, SiO 0~}} : L0 0 / o, Al O 0~: L0 0 / o, WO 0~20 0/0, R 0 (R «Li,  2 2 3 3 2  Na, K, Cs) 0-20%, MoO 0-5%, NbO 0-15%, TiO 0-15  3 2 5 2  %, ZrO 0-15%, CuO 0-10%, MnO 0-15%, R, 0 (R 'is Mg, Ca, Sr, 2  A glass composition for sealing, characterized in that it contains 0 to 15% [5] Furthermore, as a glass composition, F is 0 to 10 in terms of mol% in terms of the following oxides. %contains  2  The glass composition for sealing according to any one of claims 1 to 4, wherein the glass composition for sealing is used. [6] A glass powder 50 which also has a glass composition power for sealing according to any one of claims 1 to 5: L0 0% by volume and refractory filler powder 0 to 50% by volume Sealing material fee.  [7] The sealing material according to [6], wherein when fired in a reduced-pressure atmosphere, the surface of the fired body is glossy and devitrification is not observed. [8] When fired in a neutral or reducing atmosphere, the surface of the fired body is glossy, 7. The sealing material according to claim 6, wherein devitrification is not recognized. [9] Fire resistant fillers: tin oxide, niobium oxide, zirconium phosphate, cordierite, Na  Nb Zr (PO), KZr (PO), Ca Nb Zr (PO), NbZr (PO), K 0. 5 0. 5 1. 5 4 3 2 4 3 0. 25 0. 5 1. 5 4 3 4 3 0 Nb Zr (PO), Zr WO (PO) group force Contains one or more selected .5 0. 5 1. 5 4 3 2 4 4 2  The sealing material according to claim 6, wherein the sealing material has a sealing material.  [10] V according to claim 6-9, which is used for sealing any one of a plasma display panel, a field emission display, a fluorescent display tube, a CRT, an electronic component, and an optical component. Sealing material.  [11] A sealing tablet obtained by sintering a sealing material into a predetermined shape, wherein the sealing material is the sealing material according to any one of claims 6 to L0.  [12] The sealing paste, wherein the sealing material is the sealing material according to any one of claims 6 to 10, wherein the sealing material is dispersed in one crumb.  [13] Vehicle Toluene, Ν, Ν, —dimethylformamide, 1,3 dimethyl-2-imidazolidinone (DMI), dimethyl carbonate, butyl carbitol acetate, isoamyl acetate, propylene carbonate, Ν-methyl 2-pyrrolidoneacetonitrile , Dimethyl sulfoxide, acetone, methyl ethyl ketone, isododecyl alcohol, isotridecyl alcohol, pentanediol, pentanediol derivatives, CC OH (η = 8  13. The sealing paste according to claim 12, comprising one or two or more selected higher alcohol group powers represented by [eta] 2 [eta] +1 to 20). 14. The vehicle according to claim 1, wherein the vehicle contains one or more selected from the group strength of nitrocellulose, polyethylene glycol derivatives, and polyethylene carbonate. The sealing paste according to 2 or 13. [15] A method for manufacturing a plasma display panel or a field emission display, comprising a sealing step using the sealing material according to any one of claims 6 to 10, wherein a part or all of the sealing step is A method for manufacturing a plasma display panel or a field emission display, which is performed in a reduced-pressure atmosphere. [16] A method of manufacturing an optical component or an electronic component having a sealing step using the sealing material according to any one of claims 6 to 10, A method for producing an optical component or an electronic component, wherein a part or all of the sealing step is performed in a neutral atmosphere or a reducing atmosphere.