JP2001172046A - Low melting point glass for forming bulkhead - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide low melting point glass useful for forming bulkheads which can solve the problem of brightness lowering in plasma display panels. SOLUTION: This low melting point glass useful for forming bulkheads, characterized by containing one or more element selected from the group consisting of Cu, Mo, Sn, Sb and Ce, wherein the total amount of the CuO- converted content of Cu, the MoO3-converted content of Mo, the SnO2-converted content of Sn, the Sb2O3-converted content of Sb and the CeO2-converted content of Ce is in the range of 0.01 to 5 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lead-free low-melting glass suitable for forming a partition in a plasma display panel (PDP), a fluorescent display tube (VFD) and the like.

[0002]

2. Description of the Related Art In recent years, PDPs have attracted attention as large, thin, flat panel color display devices. One of the features of the PDP panel structure is a partition for partitioning pixels. The partition has a width of, for example, 80 μm and a height of, for example, 150 μm, and is formed at equal intervals over the entire screen. As a material for the partition wall, a glass-ceramic composition obtained by mixing a low-expansion ceramic filler for maintaining the partition wall shape and / or a heat-resistant pigment or the like for color tone adjustment to a low-melting glass powder as a fixing material is usually used. Used. The glass-ceramic composition is usually used as a paste with an organic vehicle.

[0003]

In a PDP, the luminance may decrease with the passage of time, and it is required to solve this problem. A similar problem also occurs in VFD. An object of the present invention is to provide a low-melting glass for forming a partition to solve the problem of lowering luminance.

[0004]

SUMMARY OF THE INVENTION The present invention provides Cu, Mo,
It contains at least one member selected from the group consisting of Sn, Sb and Ce, and contains, in terms of mol%, Cu content in terms of CuO, M
o in terms of MoO ₃ , Sn in terms of SnO ₂ , S
Provided is a low-melting-point glass for forming a partition wall, wherein the total content of b in Sb ₂ O ₃ and Ce in CeO ₂ is in the range of 0.01 to 5%.

[0005] The present inventors have presumed that one of the causes of the luminance reduction in PDPs is residual carbon-containing impurities described below on the partition walls, and have reached the present invention. Even if the partition wall obtained by firing does not contain a coloring component such as a transition metal,
It is often colored black. This phenomenon is considered to be a phenomenon in which carbon-containing impurities contained in the organic vehicle and the like remain in the partition walls, and the residual carbon-containing impurities blacken the partition walls. It is considered that when the plasma is generated in the PDP, the residual carbon-containing impurities react with water or the like present in the electrode-coated glass layer and are released from the partition walls as carbon dioxide gas, thereby lowering the brightness of the PDP.

It is considered that the cause of the luminance drop in the VFD is that the residual carbon-containing impurities are released from the partition walls as carbon dioxide gas.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The low-melting glass for forming partition walls of the present invention (hereinafter simply referred to as the glass of the present invention) is typically a silicate glass, more typically a zinc borosilicate glass. It is usually used in powder form. The powdered glass is usually mixed with a low-expansion ceramic filler, a heat-resistant pigment, or the like, if necessary, and then kneaded with an organic vehicle to form a paste. This glass paste is applied to a predetermined portion of the underlying glass, for example, 500 to 6
Fired at 20 ° C. The base glass referred to here 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. The organic vehicle is obtained by dissolving a binder such as ethyl cellulose in an organic solvent such as α-terpineol.

The softening point of the glass of the present invention is 450 to 650.
C. is preferred. 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. 6
If it is higher than 50 ° C., the fluidity of the glass at the time of firing may decrease, and a dense partition wall may not be obtained. It is more preferably at most 620 ° C, particularly preferably at most 600 ° C.

The glass substrate is usually 50 to 3
The average linear expansion coefficient at 50 ° C. is 80 × 10^-7~ 90x
10^-7/ ° C is used. So like this
By matching the expansion characteristics with the glass substrate,
In order to prevent warpage and decrease in strength, the glass of the present invention is used.
Has an average linear expansion coefficient of 60 × 10^-7~ 100 × 10 ^-7
/ ° C. More preferably 65 × 10
^-7~ 95 × 10^-7/ ° C, particularly preferably 70 × 10^-7~
90 × 10^-7/ ° C. In addition, at 50-350 ° C
Hereinafter, the average linear expansion coefficient is simply referred to as an expansion coefficient.

[0010] The glass of the present invention contains Cu, M, and C for the purpose of reducing the amount of residual carbon-containing impurities in the partition walls.
It contains at least one member selected from the group consisting of o, Sn, Sb and Ce. These elements are usually present in the glass of the present invention in an oxide state. In terms of mol%, Cu-equivalent content of Cu (hereinafter referred to as CuO content), Mo-equivalent content of MoO ₃ (hereinafter referred to as MoO ₃ content), Sn-equivalent content of SnO ₂ (hereinafter SnO ₂ content) ), The content of Sb in terms of Sb ₂ O ₃ (hereinafter referred to as Sb
_It is called ₂ O ₃ content. ) And CeO ₂ in terms of the content of Ce (hereinafter CeO ₂ content of. The total is less than 0.01%), there is a possibility that the effect of reducing the residual carbon-containing impurities becomes too small. It is preferably at least 0.1%, more preferably at least 0.5%. If more than 5%, C
The coloring due to u, Mo, Sn, Sb, and Ce may be too dark. It is preferably at most 4%, more preferably at most 3%. Hereinafter, the content is represented by mol%.

The CuO content is preferably at most 3%, more preferably at most 2%. When Cu is contained, the CuO content is preferably at least 0.1%, more preferably at least 0.5%.

The MoO ₃ content is preferably at most 3%, more preferably at most 2%. When Mo is contained, the MoO ₃ content is preferably 0.1% or more. It is more preferably at least 0.5%, particularly preferably at least 1%.

The SnO ₂ content is preferably at most 4%, more preferably at most 3%. When Sn is contained, the SnO ₂ content is preferably 0.1% or more. It is more preferably at least 0.5%, particularly preferably at least 1%.

The Sb ₂ O ₃ content is preferably at most 4%, more preferably at most 3%. When Sb is contained, the Sb ₂ O ₃ content is preferably 0.5% or more. It is more preferably at least 1%, particularly preferably at least 2%.

The CeO ₂ content is preferably at most 3%, more preferably at most 1%. When Ce is contained, the CeO ₂ content is preferably at least 0.1%, more preferably at least 0.3%.

The glass of the present invention is based on the following oxides: SiO ₂ 0-45%, B ₂ O ₃ 0-80%, ZnO 20-70%, MgO 0-50%, CaO 0-50%, SrO 0 ~50%, BaO 0~50%, Li 2 O 0~30%, Na 2 O 0~30%, K 2 O 0~30%, Al 2 O 3 0~15%, ZrO 2 0~15%, _{Bi 2 O 3 0~20%, 0~5} % CuO, MoO 3 0~5%, SnO 2 0~5%, Sb 2 O 3 0~5%, CeO 2 0~5%, substantially consist , SiO ₂ + B ₂ O ₃ is 25 to 80%,
0-50% of MgO + CaO + SrO + BaO, Li ₂
0 + 30% of O + Na ₂ O + K ₂ O, Al ₂ O ₃ + ZrO ₂
Is preferably 0 to 15%.

Next, the preferred composition will be described. Incidentally, CuO, MoO ₃ , SnO ₂ , Sb ₂ O ₃ , Ce
O ₂ has been described above and will not be described. At least one of SiO _{2 and} B ₂ O ₃ must be contained. It may contain only SiO _2, may contain only B ₂ O _3, or may contain both. Si
The total content of O ₂ and B ₂ O ₃ is is 25 to 80%, preferably 28 to 55%, more preferably 30% to 45%.

SiO ₂ is a network former.
You may contain up to 5%. If it exceeds 45%, the softening point becomes too high. It is more preferably at most 35%, particularly preferably at most 20%. When SiO ₂ is contained, its content is preferably at least 1%. More preferably 3
% Or more, particularly preferably 5% or more, and most preferably 10% or more.
% Or more.

B ₂ O ₃ is a component for stabilizing the glass and increasing the fluidity, and may be contained up to 80%. 8
If it exceeds 0%, the chemical durability decreases. More preferably 6
0% or less, particularly preferably 40% or less. When B ₂ O ₃ is contained, its content is preferably at least 5%. More preferably 10% or more, particularly preferably 15% or more.
% Or more.

ZnO is a component that lowers the softening point and suppresses devitrification, and is essential. If it is less than 20%, the softening point becomes too high, and devitrification tends to occur. Preferably 30%
Or more, more preferably 35% or more. If it exceeds 70%, vitrification becomes difficult. It is preferably at most 60%, more preferably at most 50%.

Each of MgO, CaO, SrO and BaO is not essential, but may be contained up to 50% each for suppressing devitrification or for suppressing crystallization during firing. If it exceeds 50%, vitrification may be difficult, or the softening point may be too high. More preferably, each is 30% or less, particularly preferably 10% or less. MgO, CaO, SrO
Alternatively, when BaO is contained, the content of each of the components is preferably 1% or more, preferably 2% or more.
% Is more preferable.

When one or more of MgO, CaO, SrO and BaO is contained, the total content thereof must be 50% or less. If it exceeds 50%, vitrification may be difficult, or the softening point may be too high. Preferably not more than 30%, more preferably 15%
% Or less, particularly preferably 13% or less. Further, the total of the contents is preferably 2% or more, more preferably 4% or more.

Li_TwoO, Na_TwoO and K_TwoO is any
Although not required, to lower the softening point and increase liquidity
To 30% each. More than 30%
Has reduced chemical durability or reduced electrical insulation
And the expansion coefficient may become too large.
You. Preferably each is less than 25%, more preferably that
Each is 15% or less, particularly preferably 10% or less.
Li_TwoO, Na_TwoO or K _TwoWhen O is contained,
For each of the components, the content must be 1% or more.
Is preferred. More preferably 2% or more, particularly preferably
Is 3% or more.

One of Li ₂ O, Na ₂ O and K ₂ O
If it contains more than one species, the total content must be less than 30%. If it exceeds 30%, the chemical durability may be reduced, the electrical insulation may be reduced, and the coefficient of expansion may be too large. Preferably 25%
Or less, more preferably 15% or less. Further, the total content is preferably 3% or more. It is more preferably at least 6%, particularly preferably at least 8%.

Although neither Al ₂ O ₃ nor ZrO ₂ is essential, they have the effect of increasing the chemical durability, and may each contain up to 15%. If it exceeds 15%, the softening point may be too high. It is preferably at most 5%, more preferably at most 3%, particularly preferably at most 2%.
When containing Al ₂ O ₃ and / or ZrO ₂ , the content of each is preferably 0.2% or more,
More preferably, it is 0.5% or more.

When at least one of Al ₂ O ₃ and ZrO ₂ is contained, the total content thereof must be 15% or less. If it exceeds 15%, the softening point may be too high. It is preferably at most 10%, more preferably at most 7%, particularly preferably at most 3%.

Bi ₂ O ₃ is not essential, but may be contained up to 20% in order to lower the softening point and increase the fluidity. If it exceeds 20%, deep coloring may occur, or chemical durability may decrease. Preferably 10
%, More preferably 5% or less. When Bi ₂ O ₃ is contained, its content is preferably 0.2% or more. It is more preferably at least 0.5%, particularly preferably at least 0.8%.

The glass of the present invention consists essentially of the above components.
However, even if other components are contained up to 5 mol% in total,
Good. As such a component, La_TwoO_ThreeRare earth oxidation
Thing, P_TwoO_Five, TiO_Two, MnO, Fe_TwoO_Three, CoO, N
iO, GeO_Two, Y_TwoO_Three, Rh _TwoO_Three, Ag_TwoO, In
_TwoO_Three, TeO_Two, WO_Three, ReO_Two, V_TwoO_Five, PdO,
Is exemplified. In addition, for PbO and CdO,
It is not substantially contained and is below the impurity level.

[0029]

EXAMPLES Raw materials were prepared and mixed so as to have a composition shown by mol% in the column of SiO _{2 to} CeO _{2 in} Table 1, put into a platinum crucible, heated to 1200 ° C. and melted for 30 minutes. Next, the molten glass was poured into a stainless steel roller to form flakes. The obtained flaky glass was wet-pulverized with an alumina ball mill for 18 hours to obtain glass powder.
Examples 1 to 5 are working examples, and example 6 is a comparative example. The softening point (unit: ° C.) and the average linear expansion coefficient at 50 to 350 ° C. (unit: 10 ⁻⁷ / ° C.) were each calculated from the composition. The results are shown in the columns of softening point and expansion coefficient in the table, respectively.

These glass powder and ethylcellulose were weighed and mixed in a mass ratio of 96: 4, and 2 g of the obtained mixture was placed in a cylindrical mold having a diameter of 12 mm and molded to obtain a cylindrical sample. This cylindrical sample was fired at 540 ° C. for 30 minutes to obtain a disk-shaped fired body. The color of this fired body is shown in the table. It is considered that the fired body having a black color has a large amount of carbon-containing impurities in the fired body. Therefore, Example 1
It is considered that the amount of the carbon-containing impurities in the fired bodies of Nos. To 5 is smaller than that of the fired body of Example 6.

[0031]

[Table 1]

[0032]

By using the glass of the present invention, P
The residual amount of carbon-containing impurities in the partition walls such as DP is reduced and PDP
And the like, it is unlikely that the brightness will decrease.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Tsuneo Manabe 1150 Hazawacho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture F-term (reference) 4G062 AA09 BB01 BB05 CC04 CC08 CC10 DA01 DA02 DA03 DA04 DA05 DB01 DB02 DB03 DB04 DC01 DC02 DC03 DC04 DC05 DC06 DC07 DD01 DE04 DE05 DE06 DF01 EA01 EA02 EA03 EA04 EA10 EB01 EB02 EB03 EB04 EC01 EC02 EC03 EC04 ED01 ED02 ED03 ED04 ED05 EE01 EE02 EE03 EE04 EE05 EF03 EF01 EF02 EF03 EF03 EF02 EF03 FC04 FD01 FE01 FE02 FE03 FF01 FG01 FH01 FJ01 FK01 FL01 FL02 FL03 GA01 GA02 GA03 GA04 GA10 GB01 GC01 GD01 GE01 HH01 HH03 HH04 HH05 HH07 HH08 HH09 HH11 HH13 HH15 HH17 HH20 KK01 JJ03 KK03 JJ01 JJ03 KK01 JJ01 JJ03 KK KA04 KA08 KA10 KB03 KB11 KB19 KB28 KB29 MA10 5C094 AA31 AA43 AA47 AA54 BA31 BA33 CA19 DA12 E B02 EC04 FA01 FA02 FB02 FB15 JA01 JA20

Claims (4)

[Claims] Claims: 1. An element containing at least one selected from the group consisting of Cu, Mo, Sn, Sb and Ce, and
u content in terms of CuO, Mo content in terms of MoO ₃ , S
The total of the content of n as SnO _{2, the} content of Sb as Sb ₂ O ₃ and the content of Ce as CeO ₂ is 0.01 to 5%.
Low melting point glass for forming a partition wall. 2. The method according to claim 1, wherein the softening point is 450 to 650 ° C.
4. The low-melting glass for forming a partition wall according to item 1. 3. The low-melting glass for forming a partition wall according to claim 1, wherein the average linear expansion coefficient at 50 to 350 ° C. is in the range of 60 × 10 ^{−7 to} 100 × 10 ⁻⁷ / ° C. In 4. following oxides represented by _{mol%, SiO 2 0~45%, B 2} O 3 0~80%, 20~70% ZnO, 0~50% MgO, CaO 0~50%, SrO 0~50%, BaO 0~50%, Li 2 O 0~30%, Na 2 O 0~30%, K 2 O 0~30%, Al 2 O 3 0~15%, ZrO 2 0~15% _{, Bi 2 O 3 0~20%,} 0~5% CuO, MoO 3 0~5%, SnO 2 0~5%, Sb 2 O 3 0~5%, CeO 2 0~5%, substantially from 25 to 80 mol% of SiO ₂ + B ₂ O _3, 0 to 50 mol% of MgO + CaO + SrO + BaO, 0 to 30 mol% of Li ₂ O + Na ₂ O + K ₂ O, Al ₂
The low-melting glass for forming a partition according to claim 1, wherein O ₃ + ZrO ₂ is 0 to 15 mol%.