WO2006075561A1

WO2006075561A1 - Glass for coating electrode, front substrate of plasma display panel and back substrate of plasma display panel

Info

Publication number: WO2006075561A1
Application number: PCT/JP2006/300104
Authority: WO
Inventors: Satoshi Fujimine; Hiroyuki Yamamoto
Original assignee: Asahi Glass Company, Limited
Priority date: 2005-01-14
Filing date: 2006-01-06
Publication date: 2006-07-20
Also published as: KR20070086978A; JP2006193385A; KR100895226B1

Abstract

A glass for coating an electrode which contains Cu in an amount of 0.05 to 2 mole % in terms of CuO and Co in an amount of 0.05 to 2 mole % in terms of CoO; and a glass for coating an electrode which consists essentially of, in mole % and in terms of the oxides described bellow, 20 to 60 % of B2O3, 5 to 50 % of SiO2, 10 to 40 % of PbO + ZnO, 0 to 15 % of Al2O3, 0 to 20 % of SrO + BaO, 0 to 10 % of TiO2, 0 to 9 % of Bi2O3, 0 to 16 % of Li2O + Na2O + K2O, 0.05 to 2 % of CuO, 0.05 to 2 % of CoO, 0 to 2 % of CeO2, and 0 to 2 % of MnO2.

Description

Specification

Electrode coating glass, plasma display panel front substrate and plasma display panel rear substrate

Technical field

The present invention relates to a front substrate and a rear substrate of a plasma display panel (hereinafter referred to as PDP), and an electrode coating glass suitable for electrode coating of these substrates.

Background art

In recent years, thin flat panel color display devices have attracted attention! In such a display device, an electrode is formed in each pixel in order to control the display state in the pixel forming the image. As such an electrode, a transparent electrode such as a thin film of ITO or tin oxide formed on a glass substrate is used in order to prevent deterioration in image quality.

[0003] A transparent electrode formed on the surface of a glass substrate used as a display surface of the display device is processed into a thin line shape in order to realize a fine image. And, in order to control each pixel independently, it is necessary to ensure the insulation between such finely covered transparent electrodes. However, when moisture is present on the surface of the glass substrate or when an alkali component is present in the glass substrate, a slight current may flow through the surface of the glass substrate. In order to prevent such a current, it is effective to form an insulating layer between the transparent electrodes. In addition, the insulating layer is preferably transparent in order to prevent deterioration in image quality due to the insulating layer formed between the transparent electrodes.

Among various known insulating materials for forming such an insulating layer, a transparent and highly reliable glass material which is an insulating material is widely used.

[0004] Recently, as a large flat color display device is expected! In a PDP, a front substrate used as a display surface and a rear substrate on which partition walls are formed are bonded together. A cell is defined by partition walls. Then, an image is formed by generating plasma discharge in the cell.

A transparent electrode is formed on the surface of the glass substrate of the front substrate, and in order to protect the transparent electrode from plasma, the transparent electrode is covered with glass having excellent plasma durability. It is essential to overturn.

Further, an address electrode is formed on the surface of the glass substrate of the rear substrate, and this address electrode is also covered with glass.

[0005] The glass used for such electrode coating is usually used as a glass powder. For example, after adding a filler or the like to the glass powder as necessary, it is mixed with a resin, a solvent or the like to form a glass paste, which is applied to a glass substrate on which an electrode such as a transparent electrode is formed. A post-firing, slurry obtained by mixing the glass powder with a resin and, if necessary, a filler is formed into a green sheet, and this is laminated on a glass substrate on which an electrode is formed, and then fired. The electrode is covered with glass by a method such as that described above.

[0006] The glass used for covering the transparent electrode of the PDP front substrate has, for example, a softening point (Ts) of 450 to 650 ° C in addition to the electrical insulation as described above. The average coefficient of linear expansion (α) at 350 ° C is 60 X 10 ^{_7 to} 90 X 10 ^_7 Z ° C, and the electrode-coated glass layer obtained by firing is highly transparent. Various glasses have been proposed in the past.

[0007] Normally, a color filter layer is formed on an electrode-coated glass layer on the electrode-coated glass substrate for the purpose of improving contrast, but recently, as an electrode-coated glass layer, the formation of this color filter layer is unnecessary. It has been proposed to use colored glass to improve the contrast of the screen (see Table 1 of JP-A-2000-226229).

Disclosure of the invention

Problems to be solved by the invention

[0008] As described above, it has been proposed to use colored glass as the electrode-coated glass layer so as to eliminate the need for forming a color filter layer, but it has not been widely used yet.

The cause is not necessarily clear, but the electrode coating glass disclosed in JP-A-2000-226229 contains only CoO and NiO as coloring components, which may be the cause. is there.

An object of the present invention is to provide a glass for electrode coating that can eliminate such possibility, and a PDP front substrate and a PDP rear substrate using such glass for electrode coating. To do.

Means for solving the problem

[0009] The present invention contains Cu and Co, the electrode covering is 05-2 mol ^_0/0 0. CuO converted content is terms of CoO content of 0.05 to 2 mol% and Co in Cu A glass (first glass of the present invention) is provided.

In addition, B O 20-60%, SiO 5-50%

2 3 2

, PbO + ZnO 10-40%, Α1 Ο 0-15%, SrO + BaO 0-20%, TiO 0-1

2 3 2

0%, BiO 0-9%, Li O + Na O + K Ο 0-16%, CuO 0.05--2%, CoO

2 3 2 2 2

0.05-2%, CeO 0-2%, ΜηΟ 0-2%, force

twenty two

(Second glass of the present invention) is provided.

[0010] In addition, a transparent electrode is formed! A PD front substrate in which the glass substrate is covered with a glass layer, and the glass in the glass layer is the first or second glass of the present invention.

A glass substrate on which an electrode is formed is covered with a glass layer, and a partition wall is formed on the glass layer, wherein the glass of the glass layer is the first or second glass of the present invention. A glass PDP back substrate is provided.

The invention's effect

[0011] A PDP front substrate on which no color filter layer is formed, in which the electrode-coated glass layer does not contain only CoO and NiO as coloring components, is obtained. Further, a silver electrode is used as a bus electrode or the like, and it is possible to suppress the yellowing phenomenon in the peripheral portion of the silver electrode of the electrode-covered glass layer of the PDP front substrate.

BEST MODE FOR CARRYING OUT THE INVENTION

The following description will focus on the case where the electrode coating glass of the present invention (hereinafter simply referred to as the glass of the present invention) is used as the electrode coating glass layer of the PDP front substrate. The present invention is not limited to this case.

[0013] The glass of the present invention is usually used as a glass powder. For example, the glass powder of the present invention is made into a glass paste using an organic vehicle or the like for imparting printability, and the glass paste is applied onto an electrode formed on a glass substrate and baked to coat the electrode. To do. The organic vehicle referred to here is obtained by dissolving a binder such as ethyl cellulose in an organic solvent such as α-tervineol. Alternatively, a slurry obtained by mixing the glass powder of the present invention with a resin and, if necessary, a filler is formed into a green sheet, which is laminated on a glass substrate on which electrodes are formed. After firing, the electrode is coated.

[0014] The Ts of the glass of the present invention is preferably 450 to 650 ° C. If Ts exceeds 650 ° C, the glass substrate (glass transition point: 550 to 620 ° C) that is normally used may be deformed during firing.

When a glass substrate having a glass transition point of 610 to 630 ° C is used, the Ts is preferably 630 ° C or less, more preferably 550 to 600 ° C.

In addition, when used for an electrode-coated glass layer having a single layer structure, Ts is preferably 520 ° C or higher, more preferably 550 ° C or higher, and a glass transition point of 610 to 630 ° C. When using a substrate, the Ts is particularly preferably 580 ° C or higher.

As the glass substrate, those having α of 80 ^× 10 ⁷ to 90 ^× 10 ^_7 Z ° C are usually used. Therefore, in order to match the expansion characteristics with such a glass substrate and prevent warpage of the glass substrate and a decrease in strength, a of the glass of the present invention is preferably 60 X 10 ^{_7 to} 90 X 10 "V ° C, More preferably 70 X ^{10_7 to} 85 X ^10_7 Z. C.

The glass of the present invention preferably has a Ts force of 50 to 650 ° C and an a force of ^{½ 0} X 10 ^{_7 to} 90 X 10 ^_7 / ° C.

[0016] The relative dielectric constant of the glass of the present invention at 1 MHz is typically 8 to 13.

When the glass of the present invention is formed as a glass layer having a thickness of 30 to 35 μm on a glass substrate used as a PDP glass substrate, the wavelength of the glass substrate on which the glass layer is formed is 450 nm. , 550 nm, each light transmittance of 630 nm (unit: ^_0/0), respectively T

45

, Τ, Τ, Τ> Τ> Τ or 1% (Τ — Τ) <0%

Ο 550 630 450 550 630 450 550

Is preferred.

Also Τ

450 、 Τ

Both 550 and 550 are preferably 65% or more.

630

An example of the glass substrate is PD200 glass substrate (T = 89%, T = 90%, T = 88%) manufactured by Asahi Glass Co., Ltd. having a thickness of 2.8 mm.

450 550 630

[0018] When the glass of the present invention is used in a glass layer covering the silver electrode, the periphery of the silver electrode It is preferable that the yellowing phenomenon of the portion hardly occurs or does not occur. This yellowing phenomenon is a phenomenon in which the glass is colored brown or yellow and the image quality of the PDP is lowered. It is considered that the silver of the electrode diffuses into the glass layer covering the silver electrode.

Next, the components of the glass of the present invention will be described. For example, Cu is treated as a component in the form of V and CuO in the glass, CuO is treated as a component !, CuO equivalent content is abbreviated as Cu O, and the content of each component is excluding that for Ni Expressed in mole percentage.

[0020] CuO is used to realize the preferred relationship shown above for T, T and Τ

450 550 630

It is a component, or a component that makes the yellowing phenomenon difficult or does not occur, and is essential. If CuO is less than 0.05%, it is difficult to realize the preferable relationship or the yellowing phenomenon is likely to occur, and is preferably 0.1% or more. If CuO exceeds 2%, the transmittance of the glass is lowered, particularly T is lowered, preferably 0.9% or less.

550

When the content of PbO is 24% or more, it is typically 0.4% or less.

[0021] CoO is a component for realizing the preferable relationship and is essential. If the CoO is less than 0.05%, the above-mentioned preferable relationship is difficult to be realized, preferably 0.1% or more, and if it exceeds 2%, the transmittance of the glass is lowered, particularly T is lowered, preferably less than 1%. It is.

630

[0022] CeO is not essential, but in the case of adjusting the color of the glass in the yellow direction, etc., 2%

2

May be contained. If the CeO force exceeds 2%, the transmittance of the glass decreases, and in particular, T decreases.

2 450

Preferably, it is 1% or less. When it contains CeO, its content is 0.1% or more

2

It is preferable.

[0023] MnO is not essential, but in the case of adjusting the color of the glass in the red direction, etc., 2

2

It may be contained up to%. If the MnO force is exceeded, the transmittance of the glass will decrease, and in particular, T will be low.

2 550, preferably 1% or less. If it contains MnO, its content should be 0.1% or more.

2

It is typically more than 0.2%.

[0024] The glass of the present invention typically does not contain NiO, or when NiO is contained, its content is less than 0.005% in terms of mass percentage.

[0025] The first glass of the present invention is typically a B 2 O 3 —SiO glass.

2 3 2

Next, components of the second glass of the present invention will be described. CuO, CoO, CeO

Since 2 and MnO overlap with the above description, the description is omitted. BO is a glass network structure forming component and is essential. Glass with BO less than 20%

2 3 2 3

Becomes unstable, preferably 26% or more, and if it exceeds 60%, Ts becomes too high, preferably 55% or less, typically 50% or less.

SiO is a glass network structure forming component and is essential. Less than SiO power%

twenty two

It becomes unstable, typically above 7%, above 50%, the Ts becomes too high, preferably below 35%, typically below 26%.

[0027] PbO and ZnO are components having an effect of lowering Ts and must contain at least one of them. If the total content of PbO and ZnO is less than 10%, the above effect is small, typically 18% or more.If it exceeds 40%, α may be too large, or the glass tends to crystallize. , Preferably 35% or less, typically 30% or less.

When PbO is contained, its content is preferably 10 to 35%, typically 21 to 29%. If PbO exceeds 35% (X may become too large.

When ZnO is contained, its content is preferably 10-30%, typically 15-25%. If ZnO exceeds 30%, the glass tends to crystallize.

[0028] Al O is not indispensable, but up to 15% is included for more stable glass.

twenty three

May be. If AlO exceeds 15%, the glass tends to crystallize, preferably 10% or less,

twenty three

Typically less than 8%. When Al O is contained, its content is preferably 1% or more

twenty three

Typically 3% or more.

[0029] SrO and BaO are !, and the deviation is not essential, but if a is increased, etc., it may be contained in a total range of up to 20%. If the total exceeds 20%, a may be too large, preferably 16% or less. When at least one of SrO and BaO is contained, the total content of SrO and BaO is preferably 5% or more, and typically 8% or more. In that case, BaO is preferably contained.

When BaO is contained, its content is typically 8 to 16%.

When SrO is contained, its content is typically 10% or less.

[0030] TiO is not essential, but if you want to increase the relative dielectric constant, etc., up to 10% is included.

2

Also good. If TiO exceeds 10%, the glass tends to crystallize, typically 7% or less. . When TiO is contained, its content is preferably 1% or more, typically 3% or more.

2

The

Bi O is not essential, but you want to lower Ts or increase the relative permittivity.

twenty three

May contain up to 9%. If the Bi O force exceeds S9%, there is a risk that the strain will be too large.

twenty three

The type is 4% or less. If it contains BiO, its content is preferably 1% or more.

twenty three

is there.

[0031] Li 0, Na O and Κ いずれ are not essential, but you want to lower Ts

2 2 2

May contain up to 16% in total. If the total exceeds 16%, α may be too large, preferably 9% or less. Li 0, Na O and Κ Izu no Izu

In the case of containing one or more of 2 2 2, the total content of these three components is preferably 2% or more, and typically 3% or more. In that case, it typically contains Li 2 O.

2

When Li 2 O is contained, its content is typically 2-9%.

2

When containing at least one of Na 2 O and K 2 O

twenty two

The total is typically less than 10%.

[0032] The second glass of the present invention has essentially the above component force.

V, may contain other components in the range! / ,. In that case, the total content of such components is preferably 10% or less.

[0033] As a preferred embodiment of the second glass of the present invention, B 2 O force 0-55%, PbO 10-35

twenty three

%, ZnO is 0 to 10%, and SrO is 0 to 15%.

Further, as another preferred embodiment, B 2 O force 20 to 50%, SiO force ~ 35%, ZnO 10 ~

2 3 2

30%, Al O force ^ ~ 10%, SrO force ^) ~ 10%, BaO 0 ~ 16%, Na O + K O 0 ~ 1

2 3 2 2

Examples include 0% and no PbO.

Next, a method for manufacturing the PDP front substrate of the present invention will be described.

A layer containing the glass powder of the present invention is formed so as to cover the transparent electrode and the bus electrode formed on the glass substrate.

The transparent electrode has, for example, a strip shape with a width of 0.5 mm, and is formed so that the strip electrodes are parallel to each other. The distance between each strip electrode center line is, for example, 0.83 ~: L Omm. In this case, the ratio of the transparent electrode to the glass substrate surface is 50 ~ 60%. The

The bus electrode is formed to correspond to the transparent electrode and is generally made of silver or Cr—Cu—Cr.

[0035] When the printing method is used, the layer containing the glass powder of the present invention is formed by adding a filler or the like to the glass powder of the present invention, if necessary, and then adding a resin, a solvent, etc. When a green sheet method is used, a resin is added to the glass powder and, if necessary, a filler, etc. The slurry obtained by mixing these is formed into a green sheet and laminated on a glass substrate on which an electrode is formed.

[0036] The glass substrate on which the layer containing the glass powder of the present invention is formed is heated, and the layer is baked to become an electrode-coated glass layer, and then as a protective film on the electrode-coated glass layer. A layer of magnesium oxide is formed and used as the PDP front substrate.

The configuration shown in the above description is an example, and the PDP front substrate of the present invention is not limited to this.

[0037] The PDP rear substrate of the present invention is manufactured according to the method for manufacturing the PDP front substrate of the present invention. That is, the layer containing the glass powder of the present invention that covers the address electrodes on the glass substrate is formed in the same manner as in the method for producing the PDP front substrate of the present invention. The address electrode is generally made of silver or Cr—Al.

[0038] In the case where the electrode-coated glass layer of the PDP back substrate of the present invention is provided with light reflectivity, light shielding property, etc., a filler (including a pigment) is added to the layer containing the glass powder of the present invention. It may be preferable to include it. The pigment generally contains one or more elements selected from the group force consisting of Al, Si, Ti, Cr, Mn, Co, and Cu. When the glass powder-containing layer contains a pigment as a filler, the glass powder of the present invention is preferably 100 parts by mass and the pigment is preferably contained in a proportion of 0.5 to 40 parts by mass.

Example

[0039] In the table, the raw materials are selected so that the composition is expressed in terms of mole percentage in the columns from BO to MnO. They were mixed and mixed, melted in a 1100-1350 ° C electric furnace using a platinum crucible for 1 hour, formed into a sheet glass, and then pulverized with a ball mill to obtain a glass powder. Examples 1 to 17 are working examples, and Example 18 is a comparative example.

[0040] For these glass powders, the softening point Ts (unit: C), the average linear ^expansion coefficient α (unit: 10 ^_7 Z ° C) at 50 to 350 ° C, and the relative dielectric constant ε at 1 MHz are as follows: Measurements were made as described. The results are shown in the table.

Ts: Measured with a differential thermal analyzer in the range up to 800 ° C.

a: After pressing the glass powder, the fired body obtained by firing for 10 minutes at a temperature 30 ° C higher than Ts is processed into a cylindrical shape with a diameter of 5mm and a length of 2cm. The average coefficient of linear expansion was measured.

ε: Glass powder was re-melted and formed into a plate shape, then calendered to obtain a measurement sample of 50 mm X 50 mm and thickness 3 mm. Aluminum electrodes were fabricated on both sides of the measurement sample by vapor deposition, and the relative dielectric constant at a frequency of 1 MHz was measured using an LCR meter.

[0041] Further, the glass powder lOOg was kneaded with 25 g of an organic vehicle to prepare a glass paste. The organic vehicle was prepared by dissolving 12% by mass percentage of ethyl cellulose in a tervineol.

Next, prepare a glass substrate (PD200 manufactured by Asahi Glass Co., Ltd.) with a size of 50mm x 75mm and a thickness of 2.8mm. Print a silver paste for screen printing on the 48mm x 73mm part of the surface of this glass substrate and burn it to form a silver layer. Formed. The glass substrate has a mass percentage display composition 1S SiO 58%, AlO 7%, NaO 4%, KO 6.5%, MgO 2%, CaO 5%

2 2 3 2 2

SrO 7%, BaO 7.5%, ZrO 3%, glass transition point 626 ° C, a 8

2

The glass power is also 3 X 10 "V ° C.

[0042] A glass substrate on which a silver layer is thus formed and a glass substrate on which no silver layer is formed are prepared, and the glass paste is uniformly screen-printed on each 50 mm x 50 mm portion, and then 120 ° Dry at C for 10 minutes. These glass substrates were heated at a temperature increase rate of 10 ° CZ until the temperature reached Ts, and the temperature was maintained at Ts for 30 minutes for firing. The thickness of the glass layer thus formed on the glass substrate was 30 to 35 μm.

[0043] A silver layer is formed! For a sample in which the glass layer is formed on a glass substrate! Te , Wavelength 450nm, 550nm, 630nm light transmittance T (unit: ⁰ /.), T (unit: ⁰ /.), Τ

450 550

(Unit:%) was measured as described below.

630

Τ, Τ, Τ: Using an integrating sphere self-recording spectrophotometer U-3500 manufactured by Hitachi, Ltd.

450 550 630

The transmittance of light having wavelengths of 450 nm, 550 nm, and 630 nm was measured (the state without the sample was taken as 100%).

[0044] Further, the presence or absence of the yellowing phenomenon was examined for the sample in which the glass layer was formed on the glass substrate on which the silver layer was formed. As a result, the color of any glass layer in Examples 1 to 18 was colorless, blue or turquoise, and no yellowing phenomenon was observed in which the color of the glass layer was brown or yellow.

[0045] [Table 1]

[0046] [Table 2]

Industrial applicability

The glass of the present invention can be used for electrode coating on the front or back substrate of a PDP.

Further, the PDP front substrate and the PDP rear substrate of the present invention can be used for manufacturing PDP. The entire contents of the specification, patent claims, drawings and abstract of Japanese Patent Application No. 2005-7898 filed on January 14, 2005 are incorporated herein by reference. And that is what we take in.

Claims

The scope of the claims

[1] contains Cu and Co, is from 0.05 to 2 moles calculated as CuO content of Cu ^_0/0 and glass for covering electrodes terms of CoO content of Co is 05 to 2 mol% 0.1.

[2] The electrode according to claim 1, which contains Ce and has a CeO equivalent content of 2 mol% or less.

2

Glass for coating.

[3] The composition according to claim 1 or 2, wherein Mn is contained and the MnO equivalent content is 2 mol% or less.

2

The electrode coating glass.

[4] The electrode coating glass according to claim 1, 2 or 3, wherein the glass is a B 2 O—SiO-based glass.

2 3 2

[5] In terms of mole percentages based on the following oxides, B O 20-60%, SiO 5-50%, PbO

2 3 2

+ ΖηΟ 10-40%, Α1 Ο 0-15%, SrO + BaO 0-20%, TiO 0-10%,

2 3 2

Bi O 0-9%, Li O + Na O + K O 0-16%, CuO 0.05--2%, CoO 0.0

2 3 2 2 2

5 to 2%, CeO 0 to 2%, MnO 0 to 2%, force Essential glass for electrode coating.

twenty two

[6] B O force ^ 20-55%, PbO force 0-35%, ZnO 0-10%, SrO 0-15%

twenty three

6. The electrode coating glass according to claim 5.

[7] B O force 0 ~ 50%, SiO power ~ 35%, ZnO 10 ~ 30%, Al O power ^ ~ 10%, SrO

2 3 2 2 3

Force S 0-10%, BaO 0-16%, Na O + K O 0-10%, not containing PbO

twenty two

6. The electrode coating glass according to claim 5.

[8] Does not contain Ni or contains Ni and its NiO equivalent content is 0.

The electrode coating glass according to any one of claims 1 to 7, which is less than 005%.

[9] The transparent electrode is formed, the glass substrate is covered with a glass layer, and is a plasma display panel front substrate, wherein the glass layer glass is the electrode according to any one of claims 1 to 8! Plasma display panel front substrate, which is glass for coating.

[10] A plasma display panel rear substrate in which a glass substrate on which an electrode is formed is covered with a glass layer, and a partition is formed on the glass layer, wherein the glass of the glass layer is a glass substrate. 8. A plasma display panel rear substrate, which is the electrode coating glass according to any one of 8 above.