KR100882769B1 - Lead free glass for forming barrier rib, glass ceramics composition for forming barrier rib and plasma display panel - Google Patents

Abstract

[PROBLEMS] even when containing a Li ₂ O content is that provided for the lead-free glass barrier ribs is less than 0.5% form.

[Measures] In terms of mass percentages based on the following oxides, B ₂ O ₃ 20 to 35%, ZnO 25 to 60%, SiO _{2 0 to} 6%, Al ₂ O ₃ 0.1 to 10%, MgO + CaO + SrO + Lead-free glass for partition formation which consists essentially of BaO 3 to 38%, Li ₂ O 0 to 0.3%, and Na ₂ O + K ₂ O 0.1 to 6%. The lead-free glass for partition formation of which ZnO is 28 to 58%, SiO ₂ is 0.3 to 5%, Al ₂ O ₃ is 0.5 to 8%, BaO is 10 to 38%, and Na ₂ O is 1 to 5%.

Description

Lead-free glass for partition wall formation, glass ceramic composition and plasma display panel for partition wall formation {LEAD FREE GLASS FOR FORMING BARRIER RIB

TECHNICAL FIELD This invention relates to the glass, glass ceramics composition, and PDP which are baked and used for formation of partitions, such as a plasma display panel (henceforth PDP).

In recent years, PDP has attracted attention as a large, thin flat panel color display device. The PDP has a structure in which a plurality of cells (microdischarge spaces) divided by barrier ribs (barrier ribs) are formed between two glass substrates, a phosphor is disposed on the surface of each cell, and a discharge gas is filled in the cells. have. Discharge is caused between the electrodes in the cell to excite the discharge gas, and the phosphor in the ground state is caused to emit light by ultraviolet rays generated at that time to form the pixel. Such a PDP is a self-luminous flat display, and is one of the most promising display devices because it has excellent characteristics such as light weight, high viewing angle, and can be enlarged.

For the material forming the partition wall, in order to prevent the deformation of the glass substrate during firing, for example, the softening point Ts should be 450 to 600 ° C and the average linear expansion coefficient (α) at 50 to 350 ° C. It is required that it is 6Ox10 <^-7> -85 * 10 <^-7> / degreeC.

Conventionally, as such a material, glass containing a large amount of lead oxide (PbO), which is a component for lowering Ts, has been used, but recently, a material containing no lead has been requested. As such weight percentage composition displays a _{B 2 O 3 15~35%, ZnO} 30~6O%, SiO 2 3~20%, BaO 3~25%, Li 2 O 0.5~6%, Li 2 O + Na 2 O A lead-free glass having + K ₂ O 1 to 12% has been proposed (see Patent Document 1).

Patent Document 1: Japanese Unexamined Patent Publication No. 2002-326839

Lead-free glass disclosed in Patent Document 1, and the greater the effect of lowering the Ts containing Li ₂ O 0.5% or more. However, with those containing a Li ₂ O 0.5% or more to form the partition wall there is a fear that problems arise such that the characteristics of the panel of the PDP decreases.

The invention, its content even when containing Li ₂ O is intended to provide a lead-free glass for forming the partition wall is less than 0.5%.

The present invention is expressed by the following percentage by mass based on the following oxide, B ₂ O ₃ 20-35%, ZnO 25-60%, SiO ₂ 0-6%, Al ₂ O ₃ 0.1-10%, MgO + CaO + SrO + It provides _{BaO 3~38%, Li 2 O 0~0.3} %, Na 2 O + K 2 for the essentially lead-free partition wall formation made of 0.1~6% O glass.

Moreover, the glass ceramic composition for partition formation containing the powder of the said lead free glass for partition formation and the inorganic oxide powder in the ratio of 0.1-40 mass parts with respect to 100 mass parts of the powder is provided.

In addition, the inorganic oxide powder is selected from the group consisting of TiO ₂ , ZnO, SiO ₂ , Al ₂ O ₃ , ZrO ₂ , P ₂ O ₅ , Fe ₂ O ₃ , MnO ₂ , Cr ₂ O ₃ and Co ₂ O ₃ . The said glass ceramic composition for partition formation which is powder of 1 or more types of inorganic oxides is provided.

The present invention also provides a plasma display panel having a partition wall formed by using the powder of lead-free glass for partition wall formation or the glass ceramic mix composition for partition wall formation.

According to the invention, it included in an amount of not more than 0.3% or not, or contain Li ₂ O, and the lead-free glass-forming difficult to further crystallize the partition wall can be obtained.

The lead-free glass for partition formation of the present invention (hereinafter, simply referred to as the glass of the present invention) is usually pulverized and classified and used as a glass powder. The glass powder produced in this way is normally mixed with a ceramic filler, a heat-resistant pigment, etc. as needed, and knead | mixed with the vehicle which melt | dissolved resin in the organic solvent, and turns into a paste or a green sheet. In the case of using the sand blasting method, the paste or the green sheet is unbaked partition walls of a predetermined pattern by sand blasting or the like after application or attachment to the base, and then it is fired to form partition walls. In addition, an etching method or the like is known as a method other than the sand blasting method, and as the resin, ethyl cellulose, polyacrylate, polyvinyl butyral, nitrocellulose, and the like, and the organic solvents include α-terpineol, Butyl carbitol acetate, isopentyl acetate, etc. are illustrated, In addition, a ceramic filler is an inorganic oxide powder, and a heat resistant pigment is an inorganic oxide powder normally.

The glass of this invention is used for formation of partitions, such as PDP and VFD (fluorescent display tube).

In the case where the glass of the present invention is used for forming a barrier rib of a PDP, the base is a glass substrate, but an address data electrode is usually formed thereon, and a dielectric layer, which is an insulating coating layer for preventing mis-discharge, is formed thereon. do.

The maximum temperature of baking performed with respect to the said unbaked partition is normally 500-600 degreeC. If it is less than 500 degreeC, resin in the said vehicle remains in the partition after baking, and there exists a possibility that these residual resin may become a gas and discharge | emit when sealing a panel at the time of PDP manufacture, or a panel discharge occurs. If it is more than 600 degreeC, there exists a possibility that a glass substrate may deform | transform.

Manufacturing of PDP using the glass of this invention is performed as follows, if it is an alternating current system, for example.

A patterned transparent electrode and a bus line (typically a silver wire) are formed on the surface of the glass substrate, and the powder of the transparent electrode coating glass is applied or adhered to it by the glass paste method or the green sheet method, and then fired. Finally, a magnesium oxide layer is formed as a protective film to form a front substrate.

On the other hand, a patterned addressing electrode is formed on the surface of another glass substrate, and a glass paste of the present invention or a mixture of the powder of the present invention and the inorganic oxide powder (glass ceramic composition) is applied thereon. -It bakes and forms a glass layer or a glass containing layer (henceforth this may also be called a glass layer), and forms a partition by sandblasting method, an etching method, etc. on it.

A phosphor layer is printed and fired on a glass substrate having such a partition to form a back substrate. In addition, you may use the green sheet method etc. without using a glass paste to form the said glass layer.

A sealing material is applied to the periphery of the front substrate and the rear substrate by a dispenser, and the transparent electrode and the address electrode are assembled to face each other, and then fired to obtain a PDP. The inside of the PDP is exhausted and a discharge gas such as Ne or He-Xe is sealed in the discharge space (cell).

In addition, although the said example is a thing of alternating current system, the glass of this invention is applicable also to the thing of a direct current | flow system.

It is preferable that Ts of the glass of this invention is 600 degrees C or less. When it exceeds 600 degreeC, there exists a possibility that the glass substrate (glass transition point: 550-620 degreeC) normally used may deform | transform at the time of baking. Ts is typically 450 to 600 ° C, more typically 480 to 590 ° C.

As said glass substrate, the thing whose (alpha) is 80 * 10 <^-7> -9O * 10 <^-7> / degreeC is used normally. Therefore, in order to match such a glass substrate and an expansion characteristic, and to prevent the curvature and the fall of strength of a glass substrate, (alpha) of the glass of this invention or the fired body of the ceramic composition of this invention becomes like this. Preferably it is 60x10 <^-7> -85 It is x10 <^-7> / degreeC, More preferably, it is 65 * 10 <^-7> -82 * 10 <^-7> / degrees C.

Next, the composition of the glass of this invention is demonstrated using a mass percentage display.

B ₂ O ₃ is an essential component to stabilize the glass. If it is less than 20%, glass will become unstable. Preferably it is 22% or more. If it exceeds 35%, Ts will become too high. Preferably it is 33% or less.

ZnO is essential as a component for lowering Ts. If it is less than 25%, Ts will become high. Preferably it is 28% or more. If it exceeds 60%, the glass becomes unstable. Preferably it is 58% or less. Typically it is 40% or less.

SiO ₂ is not required, but may contain up to 6% in order to stabilize the glass. If it is more than 6%, Ts will become high too much. Preferably it is 5% or less, typically 2% or less. If containing a SiO ₂ content thereof is typically more than 0.3%.

Al ₂ O ₃ is an essential component for stabilizing the glass. If it is less than 0.1%, glass will become unstable. Preferably it is 0.5% or more. If it exceeds 10%, the glass becomes rather unstable. Preferably it is 8% or less.

MgO, CaO, SrO and BaO are components which lower Ts and should contain any one or more types. If the total of these four components is less than 3%, Ts becomes too high. Preferably it is 10% or more, typically 25% or more. If it is more than 38%, α becomes too large.

It is preferable to contain BaO among these, and it is preferable that content in that case is 10 to 38%. More preferably, it is 15% or more, Especially preferably, it is 20% or more. Moreover, More preferably, it is 35% or less, Especially preferably, it is 33% or less.

Li ₂ O is not essential, but may be contained up to 0.3% in order to lower Ts. If it exceeds 0.3%, the difference between the crystallization temperature (Tc) and Ts which will be described later becomes small, that is, the crystallization becomes easy.

Na ₂ O and K ₂ O are components that lower Ts and should contain any one or more thereof. Ts becomes too high when the sum total of content of these two components is less than 0.1%. Preferably it is 1% or more. If it exceeds 6%, α becomes too large. Preferably it is 4% or less, More preferably, it is 3% or less.

If containing a Na ₂ O content thereof is typically from 1 to 5%, more typically is 1~2.5%.

The ratio of mole percentage indicated content b of B ₂ O ₃ to the sum of the molar percentage indicated contents of Li ₂ O, Na ₂ O and K ₂ O, l, n, k (l + n + k) b / (l + n + k) is typically 8.1 or more.

In the glass of the present invention, ZnO is preferably 28 to 58%, SiO ₂ is 0.3 to 5%, A1 ₂ O ₃ is 0.5 to 8%, BaO is 10 to 38%, and Na ₂ O is 1 to 5%. Do.

Although the glass of this invention consists essentially of the said component, you may contain other components in the range which does not impair the objective of this invention. When it contains such a component, the sum total of those content becomes like this. Preferably it is 10% or less, More preferably, it is 5% or less.

As such a component, the following is illustrated. That is, there is a case that for the coloring of such a glass, CoO, CuO, CeO _2, MnO _2, and may contain from the group consisting of SnO ₂ to 3% in total of one or more selected components. In addition, rare earth oxides such as La ₂ O ₃ (excluding CeO ₂ ), Bi ₂ O ₃ , Fe ₂ O ₃ , NiO, GeO ₂ , Y ₂ O ₃ , MoO ₃ , Rh ₂ O ₃ , Ag ₂ O, In ₂ O ₃ , TeO ₂ , WO ₃ , ReO ₂ , V ₂ O ₅ , PdO, TiO ₂ , ZrO _2, and the like are exemplified.

In addition, the glass of this invention does not contain PbO. In addition, P ₂ O ₅ is sometimes preferred not to contain it may cause to destabilize a glass.

EXAMPLE

The raw materials are prepared and mixed in the column from B ₂ O ₃ to CuO in Tables 1 and 2 so as to have a composition represented by mass percentage display, melted for 1 hour using a platinum crucible in an electric furnace at 1200 to 1350 ° C, and After molding to glass, it was ground with a ball mill to obtain a glass powder.

Examples 1-10 are Examples, and Examples 11-13 are comparative examples. In addition, the glass powder of Example 10 was not manufactured.

In addition, the composition of the molar percentage display of the glass powder of Examples 1-10 in Table 3 is shown.

For these glass powder, softening point Ts (unit: ℃), crystallization temperature Tc (unit: ℃), the average linear expansion coefficient α (unit: 1O ^-7 / ℃) was measured as described under a. Although a result is shown to a table | surface, "-" in a table | surface shows that it was not measured.

Ts: It measured using the differential thermal analyzer in the range up to 800 degreeC. In addition, Ts of Example 7 was calculated | required by calculation from a composition.

Tc: The first exothermic peak, ie, the first crystallization peak temperature, was read from the data measured using the differential thermal analyzer, and this was defined as Tc. It is preferable that (Tc-Ts) is 30 degreeC or more.

(alpha): After the press molding of glass powder, the baking body obtained by baking for 10 minutes at temperature 30 degreeC higher than Ts is processed into the column shape of diameter 5mm and length 2cm. The average linear expansion coefficient of 50-350 degreeC was measured with the thermal expansion system. In addition, Ts, (alpha) of Example 10 and (alpha) of Example 11 were calculated | required by calculation from a composition.

In addition, the sinterability was evaluated as follows. That is, 35 g of each glass powder and 5% terpineol solution of ethyl cellulose were mixed, kneaded in three roll mills, and pasted. Next, this paste was blade-coated on the glass substrate PD200 manufactured by Asahi Glass Co., Ltd. to form a coating film having a film thickness of 400 μm. Furthermore, it baked in the electric furnace at 560 degreeC for 10 minutes, and obtained the glass film. The cross section of this glass film | membrane was observed by SEM, and it was made into (circle) that what was sintered fully and was densified, and that which was sintered but insufficient was made into (triangle | delta).

Example 11 which is a comparative example has high Ts, Example 12 has large (alpha), and Example 13 was small (Tc-Ts), and was easy to crystallize.

It can be used to form partition walls of the PDP.

Claims (8)

In terms of mass percentages based on the following oxides, B ₂ O ₃ is 20 to 35%, ZnO is 28 to 58%, SiO ₂ is 0.3 to 5%, A1 ₂ O ₃ is 0.5 to 8% and BaO is 10 to 38% , MgO + CaO + SrO + BaO is 38% or less and contains K ₂ O when 0 to 0.3% of Li ₂ O and 1 to 5% of Na ₂ O are contained, and MgO, CaO or SrO is contained. In the case, lead-free glass for forming a partition having Na ₂ O + K ₂ O of 6% or less. The method of claim 1, Lead-free glass for forming partition walls with a BaO content of 10 to 35% or less. The method of claim 1, The lead-free glass for partition formation whose softening point is 600 degrees C or less, and the average linear expansion coefficient in 50-350 degreeC is 60 * 10 <^-7> -85 * 10 <^-7> / degreeC. The glass ceramic composition for partition formation containing the powder of the lead-free glass for partition formation of Claim 1, and the inorganic oxide powder in the ratio of 0.1-40 mass parts with respect to 100 mass parts of the powder. The method of claim 4, wherein The inorganic oxide powder is one selected from the group consisting of TiO ₂ , ZnO, SiO ₂ , Al ₂ O ₃ , ZrO ₂ , P ₂ O ₅ , Fe ₂ O ₃ , MnO ₂ , Cr ₂ O ₃ and Co ₂ O ₃ . The glass ceramic composition for partition formation containing the powder of the above inorganic oxide. A plasma display panel having a partition wall formed by using the powder of lead-free glass for partition wall formation according to claim 1. A plasma display panel having a partition formed by using the glass ceramic composition for forming a partition of claim 4. A plasma display panel having a partition wall formed by using the powder of lead-free glass for partition wall formation of claim 3.