JP2006143479A - Glass for forming barrier rib, and plasma display panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass capable of forming a plasma display panel (PDP) and also a dense barrier rib for PDP or the like, and containing neither PbO nor F. <P>SOLUTION: The glass for forming barrier ribs comprises, by mol, 24-50% SiO<SB>2</SB>, 13-23% B<SB>2</SB>O<SB>3</SB>, 10-32% ZnO, 3-20% Li<SB>2</SB>O, 1-9% Na<SB>2</SB>O, 1-15% Al<SB>2</SB>O<SB>3</SB>, 0-20% (MgO+CaO+SrO+BaO) and 0-9% Bi<SB>2</SB>O<SB>3</SB>, contains neither PbO nor F, and satisfies the inequality, [(B<SB>2</SB>O<SB>3</SB>+ZnO)-Al<SB>2</SB>O<SB>3</SB>]≥24%. When ZrO<SB>2</SB>is contained, its content is ≤2%. The softening point of the glass is ≤615°C. This invention also relates to a PDP having the barrier rib formed by using the glass. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a glass and a PDP that are baked and used to form a partition such as a plasma display panel (PDP).

  In recent years, PDPs have attracted attention as large thin flat color display devices. PDP forms a large number of cells (micro discharge spaces) partitioned by partition walls (barrier ribs) between two glass substrates, arranges phosphor on the inner surface of each cell, and fills the cells with discharge gas It has a structure. A discharge is caused between the electrodes in the cell to excite a discharge gas, and a phosphor in a ground state is caused to emit light by ultraviolet rays generated at that time to form a pixel. Such a PDP is a self-luminous flat display, has excellent characteristics such as light weight and thinness, a high viewing angle and the like, and is one of the most promising display devices because it can be enlarged.

This partition wall forming material is required to be able to be fired at a low temperature such as 615 ° C. or lower, 600 ° C. or lower, for example, in order to prevent deformation of the glass substrate. Conventionally, glass containing a large amount of lead oxide (PbO) or bismuth oxide (Bi ₂ O ₃ ), which is a component that lowers the softening point, has been used for such materials.
In recent years, there has been a demand for glass for forming partition walls that does not contain PbO and Bi ₂ O ₃ , or does not contain PbO and does not contain a large amount of Bi ₂ O ₃ , and is based on the ZnO—B ₂ O ₃ —SiO ₂ system. Glass (for example, refer to Patent Document 1), ZnO—B ₂ O ₃ —BaO-based glass (for example, refer to Patent Document 2), and the like have been proposed.

JP 2001-130926 A Japanese Patent Laid-Open No. 11-228178

  All the glasses proposed in Patent Documents 1 and 2 contain F, and F volatilization at the time of glass melting may cause a problem. The object of the present invention is to propose a glass for forming a partition wall that can solve the above-described problems without containing F.

The present invention is expressed in terms of mol% based on the following oxides: SiO ₂ 24-50%, B ₂ O ₃ 13-23%, ZnO 10-32%, Li ₂ O 3-20%, Na ₂ O 1-9 %, Al ₂ O ₃ 1-15%, MgO + CaO + SrO + BaO 0-20%, Bi ₂ O ₃ 0-9%, and [(B ₂ O ₃ + ZnO) —Al ₂ O ₃ ] is 24 mol%. As described above, when ZrO ₂ is contained, the content is 2 mol% or less, and a partition wall forming glass (first glass of the present invention) containing neither PbO nor F is provided.

Further, in mole% based on the following _{oxides, SiO 2 24~50%, B 2} O 3 13~32%, ZnO 15~32%, Li 2 O 3~20%, Na 2 O 1~15%, It consists essentially of Al ₂ O ₃ 1-15%, MgO + CaO + SrO + BaO 0-20%, Bi ₂ O ₃ 0-9%, and [(B ₂ O ₃ + ZnO) —Al ₂ O ₃ ] is 24 mol% or more, When (Na ₂ O—Li ₂ O) is 4 mol% or less and ZrO ₂ is contained, the content thereof is 2 mol% or less, and glass for forming a partition wall containing neither PbO nor F (present) The second glass of the invention).

Further, in mole% based on the following _{oxides, SiO 2 21~50%, B 2} O 3 12~35%, ZnO 15~37%, Li 2 O 1~25%, Na 2 O 0~21%, It consists essentially of Al ₂ O ₃ 1-25%, MgO + CaO + SrO + BaO 0-20%, Bi ₂ O ₃ 0-9%, and (B ₂ O ₃ + ZnO) is 50 mol% or less, [(B ₂ O ₃ + ZnO ) -Al ₂ O ₃ ] is 24 mol% or more, and when K ₂ O is contained, the content thereof is 5 mol% or less, and the partition wall forming glass contains neither PbO nor F (the present invention). A third glass).
In addition, a PDP having a partition wall formed using the partition wall forming glass is provided.

Even when neither PbO nor F is contained and Bi ₂ O ₃ is contained, a dense partition such as PDP can be formed with a material whose content is as small as 9 mol% or less.
Further, in one embodiment of the present invention, generation of H ₂ O gas at the time of manufacturing or using a PDP can be suppressed, so that the initial luminance of the PDP can be increased or the life of the PDP can be extended.
Moreover, in the preferable aspect of this invention, the partition which has a cross-sectional shape that the upper end part of trapezoid is rounded can be obtained.

  The partition wall forming glass 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 is usually mixed with a ceramic filler, a heat-resistant pigment, or the like as necessary, and further kneaded with a vehicle in which a resin is dissolved in an organic solvent to form a glass paste. This glass paste is applied to the base, and then is made into unfired partition walls having a predetermined pattern by sandblasting or the like, and then fired to form partition walls. Examples of the resin include ethyl cellulose, polyacrylate, polyvinyl butyral, and nitrocellulose, and examples of the organic solvent include α-terpineol, butyl carbitol acetate, and isopentyl acetate.

The glass of the present invention is used for forming partition walls such as PDP and VFD (fluorescent display tube).
When the glass of the present invention is used for the formation of a PDP partition wall, the base is a glass substrate. Usually, an address data electrode is formed on the glass substrate, and an erroneous discharge prevention is formed on the address electrode. A dielectric layer that is an insulating coating layer is formed.
The maximum temperature for firing performed on the unfired partition walls is usually 500 to 600 ° C. If the temperature is lower than 500 ° C., the resin in the vehicle remains on the fired partition walls, and the residual resin may be released as a gas when the panel is sealed during PDP production or when panel discharge occurs. If it exceeds 600 ° C., the glass substrate may be deformed.
The PDP having the partition wall formed in this way is the PDP of the present invention.

The softening point Ts of the glass of the present invention is preferably 615 ° C. or lower. If it exceeds 615 ° C., the fluidity of the glass at the time of firing is lowered, and there is a possibility that a dense partition cannot be obtained. More preferably, it is 600 degrees C or less, More preferably, it is 590 degrees C or less.
The average linear expansion coefficient α of the glass of the present invention at 50 to 350 ° C. is preferably 65 × 10 ^{−7 to} 95 × 10 ⁻⁷ / ° C. Outside this range, the average linear expansion coefficient of the partition wall (fired body) obtained by mixing the powder with a ceramic filler and firing is a preferred range, that is, 65 × 10 ^{−7 to} 85 × 10 ⁻⁷ / ° C. It becomes difficult. α is more preferably 75 × 10 ^{−7 to} 90 × 10 ⁻⁷ / ° C., particularly preferably 70 × 10 ⁻⁷ to 80 × 10 ⁻⁷ / ° C. The average linear expansion coefficient of the glass substrate is typically 80 × 10 ^{−7 to} 90 × 10 ⁻⁷ / ° C.
The relative dielectric constant ε at 20 ° C. and 1 MHz of the glass of the present invention is preferably 11 or less. If it exceeds 11, the power consumption of the PDP may increase. More preferably, it is 10 or less.

The “calcination amount of H ₂ O gas generated during firing” w measured for the glass of the present invention as follows is preferably 4 × 10 ⁻¹⁰ A or less. If it exceeds 4 × 10 ⁻¹⁰ A, the generation of H ₂ O gas during production of PDP or use of PDP increases, and the brightness of PDP may be insufficient. More preferably, it is 3.5 × 10 ⁻¹⁰ A or less, particularly preferably 3 × 10 ⁻¹⁰ A or less, and most preferably 2.5 × 10 ⁻¹⁰ A or less.

(Measurement method of w)
Glass is pulverized to obtain a powder having a mass average particle diameter of 1.5 to 3.0 μm.
30 g of this powder, 4 g of silica filler (typically crushed), 9.6 g of ethyl cellulose (eg STD100 manufactured by Dow Chemical Company) and 2.4 g of acrylic resin (eg BR101 manufactured by Mitsubishi Rayon Co., Ltd.) are mixed with terpineol (for example, Japan) Terpineol C manufactured by Terpene Co.) was stirred in a mortar after being dissolved in 88 g of terpineol C) at 80 ° C. for 2 hours, and then kneaded using a three roll to obtain a glass paste.
Next, a glass substrate (for example, PD200 manufactured by Asahi Glass Co., Ltd.) is prepared, the glass paste is blade-coated on the glass substrate using a spacer having a thickness of 400 μm, held at 120 ° C. for 90 minutes, dried, and then heated to 560 ° C. A glass substrate with a fired body is obtained by firing for a minute.
The glass substrate with the fired body was heated to 800 ° C. at a rate of 60 ° C./min under a high vacuum of 1 × 10 ⁻⁷ Pa, and the amount of H ₂ O gas generated in the temperature rising process was ionized H ₂ O. Measurement is performed using a quadrupole mass spectrometer (for example, QMG 421C manufactured by BALZERS) as the current. A graph in which temperature is plotted on the horizontal axis and the current I per 100 mg of glass is plotted on the vertical axis, the minimum value I _min of I in the temperature range of 300 to 750 ° C., and a temperature equal to or higher than the temperature at which I becomes I _min 750 The maximum value I _max of I in the range of ° C. or lower is read, I _max −I _min is calculated, and this is set as w.

The cross-sectional shape of the partition formed using the glass powder of the present invention is generally trapezoidal. The cross-sectional shape is preferably a trapezoid or a trapezoid whose upper side end (upper end) is rounded. On the other hand, it is not preferable that the shape is substantially trapezoidal but the upper side is higher than the center at both ends and the upper side and the side side form a sharp acute angle.
The cross-sectional shape of the partition is observed as follows.

(Partition wall shape observation method)
Prepare the same glass paste as used for the measurement of w.
Next, a glass substrate having a size of 100 mm × 100 mm (for example, PD200 manufactured by Asahi Glass Co., Ltd.) is prepared, and the glass paste is blade-coated on the glass substrate using a spacer having a thickness of 400 μm and held at 120 ° C. for 90 minutes. And dried to obtain a glass substrate with a dry film.
A dry film (for example, dry film BF704 manufactured by Tokyo Ohka Kogyo Co., Ltd.) is cut into 4 cm × 5 cm, and the glass substrate with the dry film is once applied under the conditions of a roll temperature of 110 ° C., a roll pressure of 150 kPa, and a substrate transport speed of 0.45 m / min. Pass through the laminator.
Thereafter, an exposure mask having a stripe pattern with a line width of 110 μm is set, exposed at 250 mJ / cm ² , developed with a 0.3% sodium carbonate aqueous solution, and dried in a dryer at 50 ° C. for 15 minutes. This was blasted using a sand blasting device (model ELP-1TR) manufactured by Elfotec Co., Ltd. under conditions of abrasive supply air pressure 140 kPa, pumping air pressure 160 kPa, roller rotation speed 35 rpm, and peeled off with 1% NaOH solution, and 80 ° C. For 30 minutes.
This is placed in an electric furnace and held at 560 ° C. for 30 minutes and fired to produce a glass substrate on which partition walls are formed, and the section of the partition walls is observed using a scanning electron microscope.

  The first and second glasses of the present invention are suitable for the case where it is desired to enhance the sinterability.

Next, the composition of the first glass of the present invention will be described by simply indicating mol% as%.
SiO ₂ is a network former and is essential. If it is less than 24%, Ts becomes too low, and it becomes difficult to maintain the shape as a partition when firing, or α becomes too large. Preferably it is 25% or more, more preferably 27% or more, and particularly preferably 30% or more. If it exceeds 50%, Ts tends to be too high. Preferably it is 47% or less, typically 45% or less.
B ₂ O ₃ is a component that stabilizes glass and enhances sinterability, and is essential. If it is less than 13%, the sinterability is lowered, and it may be difficult to obtain a dense partition. Preferably it is 14% or more. If it exceeds 23%, the alkali resistance or water resistance will decrease, or the w will increase. Preferably it is 21% or less.

ZnO is a component that enhances sinterability and is essential. If it is less than 10%, the sinterability is lowered, and it may be difficult to obtain a dense partition. Preferably it is 14% or more. If it exceeds 32%, the alkali resistance or water resistance is lowered, devitrification tends to occur, or the sinterability is lowered. Typically it is 27% or less, more typically 22% or less.
The total of B ₂ O ₃ and ZnO is preferably 50% or less. If it exceeds 50%, w may be large. More preferably, it is 45% or less.

Li ₂ O is a component that lowers Ts and increases sinterability, and is essential. If it is less than 3%, the sinterability decreases. Preferably it is 5% or more, more preferably 6% or more. If it exceeds 20%, α may be too large. Preferably it is 16% or less, More preferably, it is 14% or less.
Na ₂ O is a component that lowers Ts and increases sinterability, and is essential. If it is less than 1%, the sinterability decreases. Preferably it is 2% or more. If it exceeds 9%, α may be too large, or the sinterability may be reduced. Preferably it is 8% or less.
For such to be further enhanced _{sinterability, (Na 2 O-Li 2} O) is less than 4%, that is, whether the content of Li ₂ O is the content of Na ₂ O or more the content of Na ₂ O is Li ₂ It is preferable that it is larger than O content and the difference of both is 4% or less.

Al ₂ O ₃ has an effect of stabilizing the glass, increasing the chemical durability, or reducing the α, and is essential. If it is less than 1%, the effect is small. Preferably it is 2% or more. If it exceeds 15%, Ts increases and the sinterability decreases, or the glass becomes unstable. Preferably it is 13% or less. When it is desired to make the cross-sectional shape of the partition wall such that the upper end of the trapezoid is rounded, Al ₂ O ₃ is preferably more than 5%, more preferably 7% or more.
The total content of SiO ₂ and Al ₂ O ₃ SiO ₂ + Al ₂ O ₃ is preferably 55% or less. If it exceeds 55%, Ts tends to be high, or the glass tends to be unstable. More preferably, it is 51% or less. Further, SiO ₂ + Al ₂ O ₃ is preferably 30% or more, more preferably 33% or more.
[(B ₂ O ₃ + ZnO) —Al ₂ O ₃ ] is made 24% or more in order to stabilize the glass or enhance the sinterability.

(ZnO—Al ₂ O ₃ ) is preferably 4% or more. If it is less than 4%, the phase may be easily separated. More preferably, it is 5% or more.

MgO, CaO, SrO and BaO are not essential, but contain up to 20% in total to reduce Ts, suppress devitrification, adjust α, suppress crystal precipitation during firing, and the like. May be. If it exceeds 20%, the sinterability may be reduced. Preferably it is 16% or less. In the case of not containing Bi ₂ O ₃ , the total is preferably 10% or less.

When ZnO is less than 15% and contains MgO, the MgO content is preferably 2% or less, more preferably 1% or less. If it exceeds 2%, the glass tends to undergo phase separation. When ZnO is less than 15%, it is particularly preferable not to contain MgO.
When MgO, CaO, SrO or BaO is contained when Bi ₂ O ₃ is not contained, the content of the contained components is preferably 8% or less.

Bi ₂ O ₃ is not essential, but may be contained up to 9% in order to increase the sinterability. If it exceeds 9%, Ts or ε may be high. When Bi ₂ O ₃ is contained, the content is preferably 0.1% or more.
When it is desired to lower Ts, (Li ₂ O + Na ₂ O + Bi ₂ O ₃ ) is preferably 11% or more, that is, when Bi ₂ O ₃ is contained, Li ₂ O, Na ₂ O and Bi ₂ O ₃ total content is preferably in case of not containing the _Bi 2 _{O 3} total content of Li ₂ O and Na ₂ O is respectively 11% or more.

The first 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. Thus, when it contains another component, the total of those content becomes like this. Preferably it is 10% or less, More preferably, it is 5% or less.
Examples of such other components include SnO ₂ , ZrO ₂ , TiO ₂ , CeO ₂ , K ₂ O, and CuO as components for adjusting Ts or α, suppressing devitrification, and the like. Furthermore, rare earth oxides such as La ₂ O ₃ other than CeO ₂ , P ₂ O ₅ , MnO, Fe ₂ O ₃ , CoO, 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 and PdO.

Among these, when one or more of SnO ₂ , CeO ₂ and CuO are contained, the total of these contents is preferably 2% or less. If it exceeds 2%, devitrification tends to occur, or Ts becomes too high.
In order to suppress coloring of the partition walls obtained by firing, SnO ₂ may be contained in a range of 2% or less. If it exceeds 2%, Ts may be too high. Preferably it is 0.9% or less.

When it is desired to further improve the water resistance, ZrO ₂ or TiO ₂ may be contained in a total range of 7% or less. If it exceeds 7%, Ts tends to be too high.
Also, the content if it contains ZrO ₂ must be less than 2%. If it exceeds 2%, the glass becomes unstable.
When K ₂ O is contained, the content is preferably 5% or less. If it exceeds 5%, w may be large. The content is more preferably 3.5% or less, particularly preferably less than 1%.

The second glass of the present invention is different from the first glass of the present invention in that the upper limit of the content of B ₂ O ₃ is different, the lower limit of the content of ZnO is different, and the upper limit of the content of Na ₂ O Are different from each other in that (Na ₂ O—Li ₂ O) is 4% or less. Since the description of the other common points of both glasses is the same as that for the first glass of the present invention, it will be omitted, and only the differences will be described below.

B ₂ O ₃ is a component that stabilizes glass and enhances sinterability, and is essential. If it exceeds 32%, the alkali resistance or water resistance will decrease, or the w will increase. Preferably it is 23% or less, More preferably, it is 21% or less.
ZnO is a component that enhances sinterability or solubility and is essential. If it is less than 15%, the sinterability is lowered, and it may be difficult to obtain a dense partition, or the solubility may be lowered. Further, if ZnO is less than 15%, phase separation is likely to occur when MgO is contained, for example, more than 2% or more than 1%.

Na ₂ O is a component that lowers Ts and increases sinterability, and is essential. If it exceeds 15%, α tends to be too large, or the sinterability is lowered. Preferably it is 13% or less, More preferably, it is 9% or less, Most preferably, it is 8% or less.
If (Na ₂ O—Li ₂ O) exceeds 4%, the sinterability decreases. Preferably it is 3% or less.

The third glass of the present invention is a preferred embodiment when it is desired to reduce w.
The third glass of the present invention is the first glass of the present invention, the lower limit of the content of SiO ₂ , the upper and lower limit of the content of B ₂ O ₃ , the upper and lower limit of the content of ZnO, the content of Li ₂ O The upper and lower limits of Na ₂ O, the upper and lower limits of the content of Na ₂ O, and the upper limit of the content of Al ₂ O ₃ , the point that (B ₂ O ₃ + ZnO) is 50% or less, and K ₂ O In the case of containing ZrO ₂ , the content is 5% or less, and the upper limit of the content in the case of containing ZrO ₂ is not explicitly provided. Since the description of the other common points of both glasses is the same as that for the first glass of the present invention, it will be omitted, and only the differences will be described below.

SiO ₂ is a network former and is essential. If it is less than 21%, Ts becomes too low, and it becomes difficult to maintain the shape as a partition when firing, or α becomes too large. Preferably it is 24% or more, more preferably 27% or more, and particularly preferably 30% or more.
B ₂ O ₃ is a component that stabilizes glass and enhances sinterability, and is essential. If it is less than 12%, the sinterability is lowered, and it may be difficult to obtain a dense partition. Preferably it is 13% or more. If it exceeds 35%, the alkali resistance or water resistance will decrease, or w will increase. Preferably it is 32% or less.

ZnO is a component that enhances sinterability or solubility and is essential. If it is less than 15%, the sinterability is lowered, and it may be difficult to obtain a dense partition, or the solubility may be lowered. If ZnO is less than 15%, phase separation tends to occur when MgO is contained, for example, more than 2% or more than 1%. If it exceeds 37%, the alkali resistance or water resistance is lowered, devitrification tends to occur, or the sinterability is lowered. Typically 32% or less.
The sum of B ₂ O ₃ and ZnO is 50% or less. If it exceeds 50%, w may be large. Preferably it is 45% or less.

Li ₂ O is a component that lowers Ts and increases sinterability, and is essential. If it is less than 1%, the sinterability decreases. Preferably it is 3% or more. If it exceeds 25%, α may be too large. Preferably it is 20% or less.
Na ₂ O is not essential, but may be contained up to 21% in order to reduce Ts and increase sinterability. If it exceeds 21%, α will be too large, or the sinterability will deteriorate. Preferably it is 15% or less. When Na ₂ O is contained, its content is preferably 1% or more.
Al ₂ O ₃ has an effect of stabilizing the glass, increasing the chemical durability, or reducing the α, and is essential. If it exceeds 25%, Ts increases and the sinterability decreases, or the glass becomes unstable. Preferably it is 15% or less.

Third glass of the present invention is its content when they contain K _{2 O} is less than 5%. If it exceeds 5%, w may be large. The content is preferably 3.5% or less, more preferably less than 1%.
The third glass of the present invention may contain ZrO _2, the content in that case is preferably 2% or less. If it exceeds 2%, the glass may become unstable.

When it is desired to reduce Ts or ε, the glass of the present invention is, for example, SiO ₂ 30-50%, B ₂ O ₃ 13-21%, ZnO 14-32%, Li ₂ O 6-16%, Na ₂ O 2. _{~8%, Al 2 O 3 1~5} %, MgO + CaO + SrO + a BaO 0%, and preferably contains no _Bi 2 _{O 3.}

For example, when it is desired to obtain a partition wall having a cross-sectional shape in which the upper end of the trapezoid is rounded, the glass of the present invention includes, for example, SiO ₂ 25-40%, ZnO 14-32%, Li ₂ O + Na ₂ O + Bi _{2. O 3 11~22%, Al 2 O} 3 5 super ~15%, MgO + CaO + SrO + BaO 0~10%, it is preferable that _{SiO 2 + Al 2 O 3 25~55} %.
_{Alternatively, SiO 2 25~40%, B 2} O 3 15~23%, ZnO 14~32%, Li 2 O 6~14%, Na 2 O 3~13%, Al 2 O 3 5~15%, MgO + CaO + SrO + BaO 0-10%, SiO ₂ + Al ₂ O ₃ 30-55%, Li ₂ O + Na ₂ O 11-22%, (Na ₂ O—Li ₂ O) ≦ 4%, [(B ₂ O ₃ + ZnO) —Al ₂ O ₃ ] ≧ 24%, Bi ₂ O ₃ is not contained, and when SnO ₂ is contained, the content is 2% or less.
When it is desired to increase electrical insulation, the glass of the present invention is, for example, SiO ₂ 24-45%, Li ₂ O + Na ₂ O 4-15%, Bi ₂ O ₃ 0.1-9%, SiO ₂ + Al ₂ O ₃ 25 It is preferably ˜55%.

  As described above, the glass of the present invention is used for manufacturing a partition wall formation substrate (back substrate) such as a PDP. For example, a glass paste containing the glass powder of the present invention is applied on a glass substrate on which an address data electrode and a dielectric layer as an insulating coating layer are formed, and then a predetermined pattern is applied by sandblasting or the like. An unsintered partition wall is formed, and then fired to obtain a partition wall-forming substrate using the unsintered partition wall as a partition wall.

The raw materials were prepared and mixed so as to have the composition indicated by mol% in the columns of SiO ₂ to BaO, SiO ₂ to SnO ₂ or SiO ₂ to CeO _{2 in the} table. This was heated to 1250 to 1350 ° C. using a platinum crucible and dissolved for 60 minutes. The molten glass was then poured into a stainless steel roller and flaked. The obtained flaky glass was dry-pulverized with an alumina ball mill for 20 hours to obtain glass powder having an average particle diameter of 2 to 4 μm. Incidentally, showing the _{[(B 2 O 3 + ZnO} ) -Al 2 O 3] in the column of "B + Zn-Al" in tables.
Examples 1 to 10, 16 to 22, and 28 to 41 are the first, second, and third glasses of the present invention, Examples 12 to 15 are the third glass of the present invention, and Examples 11, 23 to 27 are comparative examples. is there. Examples 26 and 27 were not vitrified.

The softening point Ts (unit: ° C) of the obtained glass powder was measured by differential thermal analysis (DTA) at a heating rate of 10 ° C / min.
Furthermore, 2 g of glass powder was press-molded with a stainless steel mold having a diameter of 13 mm, fired at 560 ° C. for 30 minutes, and the sinterability was visually evaluated (（: extremely good, ○: good, ×: poor). Although this evaluation was performed at 560 ° C., the firing for forming the partition walls is often performed at a temperature higher than 560 ° C. In such higher-temperature firing, there is a possibility that it can be used even if it is evaluated as defective in this evaluation, that is, the evaluation result of defective in this evaluation immediately denies applicability to partition wall formation. is not.
The molten glass is poured into a stainless steel mold and subjected to a heat treatment to remove the strain. Then, the molten glass is processed into a cylindrical shape having a length of 20 mm and a diameter of 5 mm, and an average linear expansion coefficient α (unit: 50 to 350 ° C.). 10 ⁻⁷ / ° C.). These results are shown in the table.

Further, for some examples, ε, specific resistance ρ (unit: Ω · cm) at 100 ° C., w (unit: 10 ⁻¹⁰ A), and partition wall cross-sectional shape were measured or observed.
ε: The glass powder was remelted and formed into a plate shape, processed to 50 mm × 50 mm × 3 mm, aluminum was vapor-deposited on both sides to form electrodes, and the relative dielectric constant at 20 ° C. was measured using an LCR meter.
Using the sample used for the measurement of log ρ: ε, the specific resistance at 100 ° C. was measured according to ASTM D57. The table shows the common logarithm. log ρ is preferably 5 or more.

w: A glass paste was prepared by kneading 16 g of a vehicle prepared by dissolving 12 g of ethyl cellulose in 88 g of terpineol at 80 ° C. over 2 hours, 30 g of glass powder, and 4 g of silica filler using a mortar and three rolls. Using this glass paste, w was measured as described above.
Partition cross-sectional shape: Using the same glass paste used for the measurement of w, the partition cross-sectional shape was observed as described above. The upper end of the trapezoidal cross section is rounded, ◎, the one that is almost straight from one end of the upper side to the other, ○, the upper side and the side are slightly sharp at the upper end What was made was set as △, and what formed a remarkable acute angle was set as x.

Furthermore, as a comparative example, the mol% display composition is SiO ₂ 25.5%, B ₂ O ₃ 22.8%, ZnO 13.7%, Li ₂ O 7.1%, Na ₂ O 10.3%, Al _{When the} raw materials were prepared and dissolved so that 2O ₃ 10.6%, MgO 3.9%, TiO ₂ 2.5%, BaO 3.7%, the obtained glass was phase-separated. .

It can be used to form a PDP partition wall.

Claims (12)

SiO ₂ 24-50%, B ₂ O ₃ 13-23%, ZnO 10-32%, Li ₂ O 3-20%, Na ₂ O 1-9%, Al ₂ Consisting essentially of O ₃ 1-15%, MgO + CaO + SrO + BaO 0-20%, Bi ₂ O ₃ 0-9%, and [(B ₂ O ₃ + ZnO) —Al ₂ O ₃ ] being 24 mol% or more, When ZrO ₂ is contained, the content thereof is 2 mol% or less, and the partition wall forming glass contains neither PbO nor F. SiO ₂ 24-50%, B ₂ O ₃ 13-32%, ZnO 15-32%, Li ₂ O 3-20%, Na ₂ O 1-15%, Al ₂ It consists essentially of O ₃ 1-15%, MgO + CaO + SrO + BaO 0-20%, Bi ₂ O ₃ 0-9%, [(B ₂ O ₃ + ZnO) —Al ₂ O ₃ ] being 24 mol% or more, (Na ₂ O—Li ₂ O) is 4 mol% or less, and when ZrO ₂ is contained, the content is 2 mol% or less, and the partition wall forming glass contains neither PbO nor F. The glass for barrier rib formation according to claim 1 or 2, wherein (B ₂ O ₃ + ZnO) is 50 mol% or less. In mole% based on the following _{oxides, SiO 2 21~50%, B 2} O 3 12~35%, ZnO 15~37%, Li 2 O 1~25%, Na 2 O 0~21%, Al 2 It consists essentially of O ₃ 1-25%, MgO + CaO + SrO + BaO 0-20%, Bi ₂ O ₃ 0-9%, and (B ₂ O ₃ + ZnO) is 50 mol% or less, [(B ₂ O ₃ + ZnO) − When Al ₂ O ₃ ] is 24 mol% or more and K ₂ O is contained, the content is 5 mol% or less, and the partition wall forming glass contains neither PbO nor F. The glass for barrier rib formation according to claim 1 or 4, wherein (Na ₂ O-Li ₂ O) is 4 mol% or less. B ₂ O ₃ is 21 mol% or less partition wall forming glass according to any one of claims 1 to 5,.   The glass for forming a partition wall according to any one of claims 1 to 6, wherein MgO is 0 to 8 mol%, CaO is 0 to 8 mol%, SrO is 0 to 8 mol%, and BaO is 0 to 8 mol%. _{(Li 2 O + Na 2 O} + Bi 2 O 3) is 11 mol% or more in the partition wall forming glass according to any one of claims 1 to 7. Partition wall forming glass according to any one of claims 1 to 8 containing no Bi ₂ O _3.   The glass for forming a partition wall according to any one of claims 1 to 9, which has a softening point of 615 ° C or lower. The partition-forming glass according to any one of claims 1 to 10, which has an average linear expansion coefficient at 50 to 350 ° C of 65 × 10 ^{-7 to} 95 × 10 ^-7 / ° C. The plasma display panel which has a partition formed using the glass for partition formation in any one of Claims 1-11.