JP2002160940A - Glass for forming partition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass which is used for forming a partition of a plasma display panel or the like and is free from lead and which is low in dielectric constant. SOLUTION: The glass for forming a partition comprises Bi2O3 of 20-60 mass%, B2O3 of 20-55%, SiO2 of 0-15 mass%, Al2O3 of 0-15 mass%, SrO of 0-30 mass%, BaO of 0-30 mass%, Li2O of 0-6 mass%, Na2O of 0-8 mass%, K2O of 0-10 mass%, CuO of 0-3 mass% and CeO2 of 0-3 mass%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to glass used for forming partition walls of a plasma display panel (PDP), a fluorescent display tube (VFD), and the like.

[0002]

2. Description of the Related Art In recent years, attention has been paid to PDPs, VFDs, and the like, which are thin flat panel color display devices. PDP, VFD
One of the features of such a panel structure is a partition partitioning a pixel. The partition walls are formed at equal intervals over the entire screen, and the width and height thereof are, for example, 80, respectively, in PDP.
μm and 150 μm. As the partition wall forming material, a glass ceramic composition including a low expansion ceramic filler for maintaining the partition wall shape, a heat-resistant pigment for adjusting the color tone, a glass powder as a fixing material, and the like is used.

[0003]

The glass powder is required to have a low softening point, and lead-containing glasses have hitherto been widely used. However, recently, lead-free glass (lead-free glass) has been strongly demanded as the glass powder. On the other hand, conventionally known lead-free glass has a high dielectric constant, and therefore has a problem in that the power consumption of PDPs, VFDs and the like increases. An object of the present invention is to provide a partition wall forming glass that solves the above problems.

[0004]

Means for Solving the Problems The present invention, in mass percentage based on the following _{oxides, Bi 2 O 3 20~60%,} B 2 O 3 20~55%, SiO 2 0~15%, Al 2 _{O 3 0~15%, SrO 0~30%} , BaO 0~30%, Li 2 O 0~6%, Na 2 O 0~8%, K 2 O 0~10%, 0~3% CuO, CeO The present invention provides a glass for forming a partition wall (hereinafter, referred to as a glass of the present invention expressed by mass percentage) consisting essentially of _{20 to} 3%.

Further, the present invention relates to the following oxide-based mol%
In _{view, Bi 2 O 3 6~22%,} B 2 O 3 35~80%, SiO 2 0~30%, Al 2 O 3 0~20%, SrO 0~40%, BaO 0~30%, Li _{2 O 0~9%, Na 2 O} 0~9%, K 2 O 0~9%, 0~5% CuO, CeO 2 0~5%, essentially consisting barrier-forming glass (hereinafter mol% from Of the present invention.).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The glass of the present invention in terms of mass percentage and the glass of the present invention in terms of mol% are simply referred to as the glass of the present invention. The glass of the present invention is usually used in powder form. The glass powder of the present invention is, for example,
Mixed with low expansion ceramic filler, heat resistant pigment, etc.
Next, it is made into a paste. This glass paste is applied to a predetermined portion of the underlying glass and fired. The base glass is a glass substrate or the like, but also includes a glass substrate coated with a transparent conductive film, an opaque conductive film, or the like. Further, the vehicle is usually one in which a resin is dissolved in a solvent. When the glass of the present invention is used for partition walls such as PDP and VFD, the glass powder of the present invention is preferably used as a mixture with at least one of a low-expansion ceramic filler and a heat-resistant pigment.

The low-expansion ceramic filler is a component for obtaining a desired partition shape and also has an effect of increasing the strength of the partition, and its average linear expansion coefficient α at 50 to 350 ° C. is typically 70 ×. 10 ^{- 7} / ° C. or less. One or more powders selected from alumina, mullite, zircon, cordierite, aluminum titanate, β-spodumene, α-quartz, fused silica, β-quartz solid solution, and β-eucryptite are easy to handle. Or it is preferable from the point of availability.

The heat-resistant pigment is a color tone adjusting component, for example, a white pigment such as titania, a Fe—Mn double oxide,
Black pigments such as e-Co-Cr double oxides and Fe-Mn-Al double oxides are exemplified. As the vehicle,
Resin such as ethyl cellulose, nitrocellulose, etc.
-A solution dissolved in a solvent such as terpineol, butyl carbitol acetate, isopentyl acetate or the like is usually used.

[0009] baking temperature T _B of said firing is performed 500
It is preferable that it is -620 degreeC. Below 500 ° C,
A resin component may partially remain on the partition walls, and the resin component may be released from the partition walls after the panel is sealed with PDP, VFD, or the like. If it exceeds 620 ° C., the glass substrate may be deformed.

The softening point T _S of the glass of the present invention is 450 to 6
Preferably it is 50 ° C. If the temperature is lower than 450 ° C., the glass may flow too much during firing, and a desired partition shape may not be obtained. It is more preferably at least 500 ° C. If it exceeds 650 ° C., the fluidity of the glass at the time of firing may be reduced, and a dense partition wall may not be obtained. It is more preferably at most 620 ° C, particularly preferably less than 600 ° C.

The relative permittivity ε at 1 MHz of the glass of the present invention is preferably 10.5 or less. 10.5
Above this, the power consumption of PDP, VFD, etc. may increase. More preferably, it is 10 or less.

The α of the glass of the present invention is 65 × 10 ^{−7 to} 85.
It is preferably × 10 ⁻⁷ / ° C. Outside this range,
Base glass (α is typically 65 × 10 ^{−7 to} 85 × 1
0 ⁻⁷ / ° C.). More preferably, it is 70 × 10 ⁻⁷ to 80 × 10 ⁻⁷ / ° C.

Next, the glass of the present invention in terms of mass percentage will be described in terms of mass percentage, and the glass of the present invention in terms of mol% will be described in terms of mol%. The content of mol% in the description of the glass of the present invention in mol% is indicated by brackets [··%]. Bi ₂ O ₃ has the effect of lowering T _S or increasing α, and is essential. 6
If it exceeds 0% [22%], α increases or ε increases. Preferably it is 55% [20%] or less, more preferably 53% [18%] or less. If it is less than 20% [6%], T _S becomes high. It is preferably at least 30% [10%], more preferably at least 35% [11%].

B ₂ O ₃ has an effect of stabilizing glass and is essential. If it exceeds 55% [80%], T _S becomes high or phase separation occurs. It is preferably at most 45% [70%], more preferably at most 40% [65%]. 20
% [35%], the amount of Bi ₂ O ₃ becomes too large, and yellow coloring becomes remarkable. It is preferably at least 24% [40%].

[0015] SiO ₂ is not essential, but may be contained up to 15% [30%] to stabilize the glass.
If it exceeds 15% [30%], T _S may increase.
Preferably it is 10% [20%] or less. When SiO ₂ is contained, its content is preferably at least 2% [4%]. More preferably, it is at least 4% [8%].

Al ₂ O ₃ is not essential, but may be contained up to 15% [20%] to stabilize the glass.
If it exceeds 15% [20%], devitrification may occur. Preferably it is 10% [15%] or less. When Al ₂ O ₃ is contained, the content is preferably 0.5% [1%] or more. More preferably, it is 2% [3%] or more.

SrO is not essential, but may be contained up to 30% [40%] for improving water resistance or suppressing phase separation. If it exceeds 30% [40%], devitrification may occur. Preferably 25% [30%] or less, particularly preferably 15%
[20%] or less.

Although BaO is not essential, it is 30% [30%] in order to improve water resistance or suppress phase separation.
%]. If it exceeds 30% [30%], devitrification may occur. Preferably 25% [20%] or less,
More preferably, it is 20% [15%] or less. When BaO is contained, its content is preferably 5% [3%] or more. More preferably, it is 9% [6%] or more.

When one or more of SrO and BaO is contained, the total content of SrO and BaO is 5
% [5%] to 20% [15%].

Although Li ₂ O, Na ₂ O and K ₂ O are not essential, they are each 6 to reduce T _S.
% [9%], 8% [9%], and 10% [9%]. If the content exceeds this, the electrical insulation may be reduced. Preferably, they are respectively 2% [5%] or less, 3% [5%] or less, and 3% [5%] or less. When it is desired to improve the electrical insulation, Li ₂ O, Na ₂ O and K
The total content of ₂ O is preferably 0% [0%] to 2% [5%]. More preferably, 0% [0%] to 1%
[2%], and it is particularly preferable that none of Li ₂ O, Na ₂ O and K ₂ O be contained.

[0021] While CuO and CeO ₂ is not essential, but may be contained up respectively 3% [5%] in order to reduce coloring due to Bi ₂ O ₃ content. 3% [5%]
In the case of exceeding, coloring caused by CuO or CeO ₂ becomes remarkable. It is preferably 2% [3%] or less, more preferably 0.5% [1%] or less. When containing CuO or CeO ₂ , the CuO content or CeO ₂
It is preferable that each content is 0.1% [0.1%] or more.

Bi ₂ O ₃ is reduced from 35% [11%] to 55% [2
0%], B ₂ O ₃ 24% [40%] 40% [65
%], 2% [4%] to 10% [20%] of SiO ₂ , A
l ₂ O ₃ is 2% [3%] to 10% [15%], and at least one of SrO and BaO is 5% [5%] to 2 in total.
0% [15%], 0.1% [0.1%] of CeO ₂
It is preferable to contain 0.5% [0.5%].

The glass of the present invention consists essentially of the above components, but may contain other components as long as the object of the present invention is not impaired. The total content of the other components is preferably 10% [10%] or less, more preferably 5% [5%] or less. Examples of the other components include the following. That is, ZnO, TiO, and the like are used to adjust T _S , adjust α, improve glass stability, and improve chemical durability.
₂ , ZrO ₂ , La ₂ O _{3 and the} like. Also, T _S
In order to reduce the electric resistance, F
And the like.

[0024]

EXAMPLES Raw materials were prepared and mixed so as to have a composition shown by mass percentage in the column from Bi ₂ O ₃ to CeO _{2 in} Table 1 and then mixed with a platinum crucible in an electric furnace at 1200 to 1350 ° C. Melted for 1 hour. Next, the molten glass was formed into a sheet glass, and the sheet glass was pulverized with a ball mill to obtain glass powder having an average particle size of 2.0 μm. Examples 1 to 3 are Examples and Examples 4 and 5 are Comparative Examples. In addition, mol% of Examples 1-5.
The indicated composition is shown in Table 2.

[0025] Examples 1 to 5 of the T _S (Unit: ℃), α (unit:
10 ⁻⁷ / ° C.) and ε were measured by the following methods. Table 1 shows the results. T _S : Measured using a differential thermal analyzer. α: firing temperature T _B shown in Table 1 after pressure molding of glass powder
A fired body obtained by firing at (unit: ° C) for 10 minutes has a diameter of 5 m.
m, processed into a column with a length of 2 cm to make a sample, 50
The average coefficient of linear expansion α at 350 ° C. was measured. ε: The fired body was processed into 50 mm × 50 mm × 5 mm thick, an electrode was deposited on the surface thereof, and the relative dielectric constant ε was measured at a frequency of 1 MHz.

Next, 77 parts by mass of each of the glass powders of Examples 1 to 5 and 1 part of alumina powder having an average particle size of 3.0 μm were added.
Glass ceramic composition 100 in which 7 parts by mass and 6 parts by mass of titania powder having an average particle size of 0.1 μm are mixed.
g was kneaded with a vehicle consisting of 23 to 27 g of α-terpineol and 1 to 5 g of ethyl cellulose to obtain a glass paste.

This glass paste is applied to 100 mm × 10
A soda lime silica glass substrate having a thickness of 0 mm and a thickness of 2.8 mm was coated with a blade and dried at 120 ° C for 30 minutes to obtain an unfired partition wall layer having a thickness of 200 µm.

After laminating a dry film resist on the unfired partition layer, exposure was performed by setting an exposure mask for the partition pattern. Thereafter, development was performed with a 3 g / L aqueous solution of sodium carbonate to form a partition pattern having a line width of 100 μm and a space width of 150 μm on the unfired partition layer.

Next, unnecessary portions were cut by sand blasting to obtain unfired partition walls. The dry film remaining on the yet-fired barrier ribs, after removal by aqueous sodium hydroxide solution having a concentration of 10 g / L, to obtain a partition wall and fired at T _B.

The partition was cut in a direction perpendicular to the line of the partition pattern, and the cross section of the obtained partition was examined by an electron microscope for the presence of a void having a size of 3 μm or more. Table 1 shows the results. The presence or absence of the void is an index of the denseness of the partition wall, and it is preferable that there is no void. Further, with respect to the partition wall cross section, the width W and the partition height H at half the height of the partition wall were measured. Table 1 shows the results. Preferably, W / H is less than 0.7. If it is 0.7 or more, the partition shape may not be maintained.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

By using the glass of the present invention, P
Partition walls in DP, VFD and the like can be made lead-free and dense. In addition, the ε of the partition can be lowered, and PDP, VFD
And other power consumption can be reduced.

Continued on the front page F-term (reference) 4G062 AA08 AA09 AA15 BB01 BB05 BB08 DA01 DA02 DA03 DA04 DB01 DB02 DB03 DB04 DC04 DC05 DC06 DC07 DD01 DE01 DF01 EA01 EA02 EA03 EA10 EB01 EB02 EB03 EC01 EC02 EC03 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EG03 EG04 FA01 FA10 FB01 FC01 FD01 FE01 FF01 FG01 FH01 FJ01 FK01 FL01 FL02 FL03 GA03 GA04 GA05 GA06 GB01 GC01 GD01 GE01 HH01 HH03 HH04 HH05 HH07 HH09 HH11 HH13 HH15 HH17 KK JJ JJ KK JJ01 KK 5C040 GF18 KA10 KB03 KB19 KB28 MA12 MA30

Claims (8)

[Claims] In 1. A following oxides in mass _{percentage, Bi 2 O 3 20~60%,} B 2 O 3 20~55%, SiO 2 0~15%, Al 2 O 3 0~15%, SrO 0~30%, BaO 0~30%, Li 2 O 0~6%, Na 2 O 0~8%, K 2 O 0~10%, 0~3% CuO, CeO 2 0~3%, essentially from Glass for forming barrier ribs. 2. A Bi ₂ O ₃ 30 to 60% by the mass percentage
The glass for forming a partition wall according to claim 1, which contains the glass. 3. The glass for forming a partition wall according to claim 1, wherein the total content of Li ₂ O, Na ₂ O and K ₂ O is 0 to 2% by mass percentage. 4. The method according to claim 1, wherein the mass percentage is Bi_TwoO_Three35 to 55
%, B_TwoO_ThreeFrom 24 to 40%, SiO _TwoFrom 2 to 10%, A
l_TwoO_ThreeFrom 2 to 10%, one of SrO and BaO
5% to 20% in total, CeO or more_Two0.1 to 0.5
4. The barrier rib forming gas according to claim 1, wherein
Russ. In 5. A following oxides in _{mol%, Bi 2 O 3 6~22%,} B 2 O 3 35~80%, SiO 2 0~30%, Al 2 O 3 0~20%, SrO 0-40%, BaO 0-30%, Li ₂ O 0-9%, Na ₂ O 0-9%, K ₂ O 0-9%, CuO 0-5%, CeO ₂ 0-5% Glass for forming barrier ribs. 6. The glass for forming a partition wall according to claim 5, which contains 10 to 22% or more of Bi ₂ O ₃ by mol%. 7. The total content of Li ₂ O, Na ₂ O and K ₂ O is 0 to 5% by mol%.
The glass for forming a partition wall according to the above. In 8. mol%, the Bi ₂ O ₃ 11 to 20%,
B ₂ O ₃ of 40-65%, the SiO ₂ 4~20%, Al ₂ O
8. The partition wall-forming member according to claim 6, wherein ₃ to ₃ % of SrO and BaO are contained in a total of 5 to 15%, and CeO ₂ is 0.1 to 0.5%. Glass.