JP2000264677A - Glass composition, paste using the same, green sheet, electric insulator, bulkhead for pdp and pdp - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass composition suitable as a material for plasma display panels(PDP), to provide a paste using the same, to provide a green sheet, to provide an electric insulator, to provide a bulkhead for the PDP, and to provide the PDP. SOLUTION: This glass composition comprises 0-40 mol.% of SiO2, 10-60 mol.% of B2O3, 10-50 mol.% of one or more kinds of alkaline earth metal oxides selected from the group consisting of MgO, CaO, SrO and BaO, 5-50 mol.% of one or more kinds of oxides selected from the group consisting of Li2O, Na2O and K2O and 0-10 mol.% of one or more kinds of fluorides selected from the group consisting of BaF2, CaF2, SrF2, MgF2 and AlF3. A mixture comprises the glass composition and one or more ceramic fillers selected from the group consisting of zircon, alumina, titania, cordierite, mullite, β-eucryptite, spodumene, anorthite, celsian, forsterite, and aluminum titanate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a PDP (plas
The present invention relates to a glass composition suitable for a material for a ma display panel, a mixture of the glass composition and a ceramic filler, a paste, a green sheet, an insulator and a partition using the glass composition. .

[0002]

2. Description of the Related Art Conventionally, as a glass composition of this kind,
Lead borosilicate glass, which is a borosilicate glass having a low coefficient of thermal expansion and exhibiting a low softening point by adding PbO (Japanese Patent Laid-Open No. 3-170346). B ₂ O ₃ − with low softening temperature, high ionic discharge impact resistance, and lead-free
_{V 2 O 5 -ZnO-Na 2} O-SiO 2 -Al 2 O 3 -ZrO
Lead-free glass which is a ₂ series glass (Japanese Patent Laid-Open No.
No.). And the relative permittivity of the obtained PDP partition wall is 7 to
10, P ₂ O ₅ − which can reduce the display crosstalk.
_{ZnO-Na 2 O-SnO- (} Li 2 O-Na 2 O-K
_{2 O) - (MgO-CaO} -SrO-BaO) -Al 2 O
₃ based lead-free glass is glass (JP 8-301631
Is known.

[0003]

However, the above-mentioned conventional features
Lead borosilicate glass disclosed in JP-A-3-170346.
Since PbO contains PbO, the specific gravity of glass is large, and PbO
Glass-containing layer in DP (white insulator layer or transparent dielectric
Layers, partition walls, etc.), which is not suitable for weight reduction of panels.
It is. It can also cause environmental pollution,
In this case, the relative dielectric constant is as high as 10 to 12
Leakage to the wiring and the problem that crosstalk is likely to occur in the image
there were. As shown in the above-mentioned conventional Japanese Patent Application Laid-Open No. 48-43007.
Ionic discharge impact resistance low softening temperature lead-free glass
V_TwoO_Five, It is colored brown and the reflectance is low
There was a defect. In addition, the above-mentioned conventional Japanese Patent Application Laid-Open No. 8-30163
In the lead-free glass disclosed in Japanese Patent Publication No. _TwoO_FiveIncluding
Therefore, there is a problem that water resistance is poor. Also, JP-A-8-30
In the plasma display disclosed in Japanese Patent No. 1631,
Since the thermal expansion coefficient of glass is larger than the glass substrate,
To match the coefficient of thermal expansion with the glass substrate,
A large amount of cupfiller must be added, and the structure after firing
The structure becomes porous, the strength decreases, and the discharge characteristics decrease.
There was a title. An object of the present invention is to provide a glass substrate for PDP.
No warpage and crosstalk on PDP images
Glass composition that can improve reflectance without causing
Glass-ceramic mixtures, pastes and powders using the same
Provide lean sheet, insulator, PDP partition and PDP
Is to provide. Another object of the invention is to provide strength and release.
Lower the thermal expansion coefficient without lowering the electrical characteristics
Number can be matched with the PDP glass substrate and
Glass composition and glass composition capable of lowering softening point than glass substrate
Las-ceramic mixture, paste and grease using it
-Provide sheet, insulator, PDP partition and PDP
It is to be.

[0004]

According to the first aspect of the present invention, 0 to 40 mol% of SiO ₂ and B ₂
10 to 60 mol% of O _3, 10 to 50 mol% of one or more alkaline earth oxides selected from the group consisting of MgO, CaO, SrO and BaO, Li ₂ O, Na ₂
O, and K ₂ 1 kind or a 5 to 50 mol% of two or more members selected from the group consisting of _{O, BaF 2, CaF 2,} Sr
1 selected from the group consisting of F ₂ , MgF ₂ and AlF ₃
It is composed of a glass composition containing 0 or 10 mol% of a kind or two or more kinds of fluorides. In the glass composition according to the first aspect, when the glass components are mixed within the above ranges, the firing temperature is lowered and the softening point is also lowered. Further, by adding an alkali oxide, the firing temperature and the softening point can be further lowered (600 ° C. or lower). PDP
When the white insulating layer and the partition wall are formed, the glass is softened under the firing conditions of 600 ° C. or lower, and is fused with particles such as a glass substrate for a panel and a filler. In addition, since the glass component does not contain a high-density Pb component, the weight can be reduced and the weight of the panel can be reduced. In addition, since the glass component does not contain P ₂ O ₅ , the water resistance can be improved and the environment can be polluted. Absent. The invention according to claim 2 is characterized in that, as the ceramic filler, zircon, alumina, titania, cordierite, mullite, β-eucryptite, spodumene, ano-
A glass composition comprising one or more ceramic fillers selected from the group consisting of sight, celsian, forsterite, and aluminum titanate, and the glass composition according to claim 1, and a ceramic filler. Consists of a mixture. In the invention according to claim 2, claim 1
By adding and mixing the above ceramic filler to the glass composition described in the above, by adjusting the thermal expansion coefficient, the consistency with the glass substrate is improved, the strength is high,
There is no warpage, the reflectance is improved, and the occurrence of crosstalk in the PDP image can be prevented. According to a third aspect of the present invention, there is provided a glass composition according to the first aspect, or a glass composition according to the second aspect and a ceramic filler.
A paste comprising a mixture of a polymer, a polymer resin, and a solvent. According to a fourth aspect of the present invention, there is provided a green sheet comprising the glass composition according to the first aspect or a mixture of the glass composition according to the second aspect and a ceramic filler, a polymer resin, and a solvent. It is. The invention according to claim 5 is an insulator formed by firing the glass composition according to claim 1 or a mixture of the glass composition according to claim 2 and a ceramic filler. Since the softening point is low, the firing temperature of the insulator can be lowered.
An insulator having high reflectance can be obtained by adding a ceramic filler. The invention according to claim 6 is a partition wall for PDP formed by firing the glass composition according to claim 1 or a mixture of the glass composition according to claim 2 and a ceramic filler. The invention according to claim 7 is the glass composition according to claim 1 or claim 2.
A PDP formed by firing a mixture of the glass composition described above and a ceramic filler.

In the PDP according to the sixth aspect or the PDP according to the seventh aspect, a ceramic green screen containing an organic binder in the glass composition or a mixture of the glass composition and the ceramic filler. By firing the port, the partition wall or PDP is obtained. Alternatively, an organic solvent is added to a glass composition, a ceramic filler and an organic binder, paste-screened, dried, and then fired, and the ceramic green layer is fired to form a PDP partition or PDP. . The sintering temperature at this time is 100 degrees from the softening point of the glass substrate.
Since the temperature is lower than ℃, the glass substrate does not warp. In addition, since the thermal expansion coefficient of the partition wall for PDP or the PDP is substantially the same as the thermal expansion coefficient of the glass substrate, the warpage of the glass substrate can be further controlled. Since the relative permittivity of the partition or PDP is relatively small, about 4 to 7, electric signals do not leak to neighboring wirings, and no crosstalk occurs in an image. Further, since the amount of the ceramic filler component added to the glass component is relatively small, the strength after firing and the discharge characteristics do not decrease.

[0006]

Embodiments of the present invention will be described below in detail. Examples of the glass composition of the present invention include at least one of Mg, Ca, Sr, and Ba as an alkaline earth metal (M) and L, Na, and K as an alkali metal (M '). And alkaline earth metal salts (eg, CaCO ₃ and CaSO ₄ ) and alkaline earth fluorides (eg, MgF ₂ and CaF ₂ )
Powder of boric acid (H ₃ BO ₃ ), SiO ₂ and an alkali metal salt (for example, Li ₂ CO ₃ or Li ₂ SO ₄ ) in terms of oxide and fluoride, MO: 10 to 50 mol%, MF:
0 to 10 mol%, B ₂ O _3: 10~60 mol%, Si
O _2: 0 to 40 mol%, M'O: weighed with 5 to 50 mol% of the specific, volume of each powder - After mixing 0.5 to 6 hours using a like mill, a platinum crucible and the mixed powder Etc., 9
After maintaining at 00 to 1200 ° C. for 1 to 6 hours, the quenched material is pulverized and classified using a sieve having a mesh number of 200 mesh or more to obtain a glass composition. In the above glass composition, the reason why SiO ₂ is limited to the range of 0 to 40 mol% is that if it exceeds 40 mol%, the softening point of the glass increases, and the glass does not soften and fuse even at a firing temperature of 600 ° C. it is further preferred SiO ₂ is 10 to 30 mol%. When B ₂ O ₃ is limited to the range of 10 to 60 mol%, if it is less than 10 mol%, there is a problem that it does not become glass and the softening point is high, and if it exceeds 60 mol%, there is a problem that water resistance is poor. From 20 to 50 mol% of B ₂ O _3.
Is more preferable. The reason why ZnO is limited to the range of 15 to 45 mol% is that if it is less than 15 mol%, there is a problem that the softening point is high, and if it exceeds 45 mol%, there is a problem that the softening point is high. More preferably, it is mol%. The reason why one or two or more kinds of alkaline earth oxides selected from the group consisting of MgO, CaO, SrO and BaO are limited to the range of 10 to 50 mol% is that the softening point is less than 10 mol%. Is too high, and if it exceeds 50 mol%, there is a problem that it does not become glass, and it is more preferable that this oxide is 20 to 40 mol%. Further, the content of one or more alkali oxides selected from the group consisting of Na ₂ O, K ₂ O and Li ₂ O is limited to 5 to 50 mol%,
Below, there is a problem that the softening point is high, and if it exceeds 50 mol%, the coefficient of thermal expansion becomes very high.
It was determined to be 50 mol%. BaF ₂ , CaF ₂ , Sr
1 selected from the group consisting of F ₂ , MgF ₂ and AlF ₃
The reason why the kind or two or more kinds of fluorides are limited to the range of 0 to 10 mol% is that if the amount exceeds 10 mol%, there is a problem that the coefficient of thermal expansion becomes high.
More preferably, it is 10 mol%. Examples of the ceramic filler used in the above-mentioned mixture include zircon, alumina, titania, cordierite, mullite, β-eucryptite, and spodge classified using a sieve having a mesh number of 200 mesh or more. -Obtained by mixing a powder composed of an oxide containing at least one of men, anorthite, celsian, forsterite and aluminum titanate with the above glass composition using a ball mill or the like for 1 to 24 hours. .

The paste of the present invention is characterized in that the above-mentioned glass composition or a mixture of the glass composition and the ceramic filler is mixed with a polymer resin such as ethyl cellulose or an acrylic resin and α-terpion. And a solvent such as butyl carbitol acetate is added, and the mixture can be sufficiently kneaded with a triple roll. In the embodiment of the present invention, the mixing ratio of each component of the paste described above is 30 to 70% by weight of the glass composition and the ceramic filler, 15 to 3% by weight of the organic binder, and 55 to 27% by weight of the solvent. %. The solvent must be an organic solvent having relatively low volatility at room temperature, and examples thereof include terpineol, butyl carbitol acetate, and ether. By configuring the paste in this manner, a paste having a predetermined viscosity can be obtained. By blending the paste in this manner, a paste having a viscosity of 1000 to 500,000 cps can be obtained, and when a partition is formed, dripping of the partition formed on the substrate is suppressed and the partition is formed. Form accurately. The paste has a viscosity of 5,000 to 50.
10,000 cps is preferred, and 10,000 to 300,
000 cps is more preferred.

The green sheet of the present invention is generally prepared by a press molding method using a powder of the above-mentioned glass composition or a mixture of the glass composition and a ceramic filler, It can be obtained by adding the same organic binder and organic solvent and molding the mixture by a doctor blade method, an extrusion molding method, an injection molding method or the like.

The insulator of the present invention is usually obtained by sintering a green body obtained by a screen printing method using the above paste or sintering the above green sheet.

A partition wall (ceramic rib) for a PDP as an embodiment of the present invention is formed by firing the above glass composition. A method of forming the ceramic rib according to the first embodiment will be described with reference to FIGS. First, the edge 12a of the blade 12 having the comb teeth 12b is brought into contact with the surface of the glass substrate 10 with respect to the ceramic paste film 11 formed by applying the ceramic paste on the surface of the glass substrate 10. Then, the ceramic capillary rib 13 is formed on the surface of the glass substrate 10 by moving the blade 12 or the glass substrate 10 in a predetermined direction. The ceramic paste contains the above-mentioned glass composition, ceramic filler material, organic binder and solvent, and the ceramic capillary is a glass powder (glass component).
And ceramic filler powder (ceramic filler component)
A state in which most of the organic binder and the solvent remain after the paste containing the organic binder (the binder component) and the solvent is applied.

The ceramic filler powder is preferably not more than 60% by volume based on the volume of the glass powder. When the ceramic filler powder exceeds 60% by volume, rib 1
This is because 3 becomes porous and is not preferred. The particle diameters of the glass powder and the ceramic filler powder are each 0.1.
It is preferably from 30 to 30 μm. The reason why the particle size of the glass powder and the ceramic filler powder is limited to the range of 0.1 to 30 μm is that when the particle size is less than 0.1 μm, the particles tend to agglomerate and the handling becomes troublesome. This is because a desired rib 13 cannot be formed during the movement.

The mixing ratio of each component of the paste is preferably 30 to 70% by weight of the glass powder and the ceramic filler powder, 3 to 15% by weight of the organic binder, and 27 to 55% by weight of the solvent. It is necessary that the solvent be an organic solvent having relatively low volatility at room temperature.
Butyl carbitol, acetate or ether. By configuring the paste in this manner, a paste having a predetermined viscosity can be obtained, and the ceramic capillary rib 13 formed on the glass substrate 10 can be obtained.
By firing while suppressing drooling, the ceramic ribs can be accurately formed.

The paste is applied to the surface of the glass substrate 10 by a screen printing method, a dip method or a doctor blur method.
This is done by existing means such as the C-law. As shown in FIG. 1, a plurality of comb teeth 12b are formed at equal intervals and in the same direction on a blade 12 which comes into contact with the surface of a glass substrate 10 on which a paste film 11 is formed. The blade 12 is made of a metal, ceramic, plastic or the like which is not dissolved in the paste reacted with the paste. In particular, from the viewpoint of dimensional accuracy and durability, ceramic or Fe, N
i, Co-based alloys are preferred. The spacing between the respective comb teeth 12b is formed in accordance with the sectional shape of the ceramic capillary rib 13 formed by the blade 12.

The formation of the ceramic capillary rib 13 by the blade 12 constructed as described above is performed by the following method.
The glass substrate 10 is fixed while the edge 12a is in contact with the surface of the glass substrate 10 on which the paste film 11 is formed, and the blade 12 is moved in a certain direction as shown by a solid line arrow in FIG. Alternatively, the fixing is performed by fixing the blade 12 and moving the glass substrate 10 in a certain direction as shown by a broken line arrow in FIG.

The portion corresponding to the comb teeth 12b of the paste blade 12 applied to the surface of the glass substrate 10 by this movement is moved to the gap between the comb teeth 12b or is swept away. Page located in the gap between 12b
Only the strike remains on the glass substrate 10 and the glass substrate 1
A ceramic capillary rib 13 is formed on the zero surface.
If the depth of the grooves of the comb teeth is larger than the thickness of the paste film 11, the paste swept out when the blade 12 moves on the glass substrate 10 in a certain direction enters the grooves and pastes. The ceramic capillary rib 13 having a height equal to or greater than the thickness of the film 11 can be formed.

The thus formed ceramic capillary rib 13 is then dried and dried.
And then heated for binder removal and subsequently fired to form the ceramic rib 14 shown in FIG.

FIGS. 3 and 4 show a ceramic rib (PDP partition) according to a second embodiment of the present invention. 3 and 4, the same reference numerals as those in FIGS. 1 and 2 indicate the same parts.
In this embodiment, as shown in FIG.
Paste film 1 formed by applying the above paste on the surface
1, the blade 12a having the comb teeth 12b is floated from the surface of the glass substrate 10 at a predetermined height.
By moving the glass 12 or the glass substrate 10 in a certain direction, the ceramic capillary layer 2 is formed on the surface of the glass substrate 10.
1 are formed, and the ceramic capillary layer 21 and the ceramic capillary rib 23 are dried to form a ceramic green layer and a ceramic green rib, and further heated for binder removal, and subsequently fired. Insulating layer 2 formed on a glass substrate 10 shown in FIG.
2 and a ceramic rib 2 formed on the insulating layer 22.
It becomes 4.

Further, as a third embodiment of the present invention,
The following method is available (see FIG. 5). (1) First, a solid film is formed on a substrate such as glass by a screen printing method using the paste described above. (2) The printed substrate is heated at a temperature of 100 to 200 ° C. After drying for 10 to 30 minutes, pre-sintering is performed at a temperature of 300 to 400 ° C. for 0.5 to 3 hours. (3) Using a laminator on the surface of the pre-sintered film,
After laminating photosensitive dry fill resist (DFR),
Place a film mask on the DFR, center wavelength 254nm
(4) Then, a concentration of 0.1 was applied to the exposed substrate.
A 5% aqueous solution of Na ₂ CO ₃ is sprayed to remove unexposed portions, and development is performed. (5) The developed DFR-patterned substrate is
Sand blasting using a grinding stone such as alumina powder,
(6) Finally, baking is performed at a temperature of 500 to 600 ° C. for 0.1 to 2 hours to form a printed film in a portion where the DFR is not formed.

The PDP (an example of forming a back plate in an AC type plasma display panel) of the present invention is as follows: (1) First, a conductive paste such as Ag is screen-printed on a substrate such as glass. After forming a pattern having a width of 50 to 200 μm, drying at a temperature of 100 to 200 ° C. for 10 to 30 minutes, and baking at a temperature of 500 to 600 ° C. for 0.1 to 1 hour, (2) forming an address electrode . A screen printing method is performed on the substrate on which the address electrodes are formed using the glass paste obtained by the above-described method to form a solid film. (3) The printed substrate is heated at a temperature of 100 to 150 ° C. for 1 hour.
After drying for 0 to 30 minutes, baking is performed at a temperature of 500 to 600 ° C. for 0.5 to 3 hours to form a white insulating layer. (4) A screen printing method is performed on the substrate on which the white insulating layer is formed by using the glass paste obtained by the above-described method to form a solid film. (5) The printed substrate is heated at a temperature of 100 to 200 ° C. for 1 hour.
After drying for 0 to 30 minutes, calcination is performed at a temperature of 300 to 400 ° C for 0.5 to 3 hours. (6) After laminating a photosensitive dry film resist (DFR) on the surface of the calcined film using a laminator,
Place a film mask on the DFR, center wavelength 254nm
Is exposed to ultraviolet light. (7) The exposed substrate is sprayed with an aqueous solution of Na ₂ O ₃ having a concentration of 0.1 to 5% to remove unexposed portions and to perform development. (8) The developed DFR-patterned substrate is subjected to sand blasting using abrasive grains such as alumina powder to obtain D
A portion of the print film where no FR is formed is removed. (9) The substrate is heated at a temperature of 500-600 ° C. for 0.1-2.
Baking is performed for a time to form partition walls. (10) Using a paste made of a phosphor powder that emits red, green, or blue light by ultraviolet light in the partition walls, each is formed by drop-in printing by a screen printing method.

[0020]

Hereinafter, examples of the present invention will be described in detail together with comparative examples. EXAMPLE 1 Glass powder (glass containing the a SiO ₂ 20 mol%, the B ₂ O ₃ and 30 mol% of BaO and 20 mol% 25 mol% and Li ₂ O and the MgF ₂ 5 mole% 70% by weight) and 20% by weight of β-eucryptite powder having an average particle size of 5.0 μm as a ceramic filler, and both were sufficiently mixed. More specifically as a raw material of the glass powder, H ₃ BO ₃ as a B ₂ O _3, Zn
O is mixed as it is, BaCO ₃ as BaO, Li ₂ CO ₃ as Li ₂ O, and MgF ₂ as they are, respectively, so as to become predetermined components. And solidified and then pulverized (average particle size: 3 to 5 μm). The mixed powder, ethyl cellulose as an organic binder, and α-terpineol as a solvent were blended at a weight ratio of 50/5/45, and kneaded sufficiently to obtain a paste. The paste thus obtained was used as Example 1. In addition, the glass powders of the following Examples 2 to 29 and Comparative Examples 1 to 8 were also made of SiO 2 similarly to the above.
In addition to the _2, H ₃ BO ₃ as a B ₂ O _3, ZnO intact,
BaO, SrO, CaO, M which are alkaline earth oxides
BaO ₃ , SrCO ₃ , CaCO _3, M as gO, and Na ₂ O, K ₂ O or Li ₂ O which are alkali oxides
_{gCO 3, NaCO 3, K 2} CO 3 or Li ₂ CO _3,, MgF ₂ is _{fluoride, CaF 2, SrF 2, MgF} 2 or AlF ₃ is to be the composition shown directly to respective Tables 1 and 2 And melted in the air at 1100 ° C. for 30 minutes, poured out into a platinum dish, solidified and then pulverized (average particle size: 3 to 5 μm).

Example 2 The glass powder was Mg of Example 1.
A paste was formed in the same manner as in Example 1 except that SrF ₂ was contained in an amount of 5 mol% instead of F ₂ . This paste was designated as Example 2.

Example 3 The glass powder was Mg of Example 1.
A paste was formed in the same manner as in Example 1 except that CaF ₂ was contained in an amount of 5 mol% instead of F ₂ . This paste was designated as Example 3.

Example 4 The glass powder was Mg of Example 1.
A paste was formed in the same manner as in Example 1, except that 5 mol% of AlF ₃ was used instead of F ₂ . This paste was used as Example 4.

Example 5 A glass powder containing SiO ₂
As in Example 1 except that 5 mol%, B ₂ O ₃ was 25 mol%, BaO was 40 mol%, Li ₂ O was 15 mol% and CaF ₂ was 5 mol%. To form a paste. This paste was designated as Example 5.

[0025] [Example 6] glass powder, the SiO ₂ 1
And 5 mol%, B and the ₂ O ₃ 45 mol%, 30 mol% of BaO and CaF ₂ a except that it contains a 10 mol%, Bae in the same manner as in Example 1 - was formed strike. This paste was used as Example 6.

[0026] [Example 7] glass powder, the SiO ₂ 1
As in Example 1, except that 5 mol%, 15 mol% of B ₂ O ₃ , 15 mol% of BaO, 45 mol% of Na ₂ O and 10 mol% of CaF ₂ were contained. A paste was formed. This paste was used as Example 7.

[0027] [Example 8] glass powder, a SiO ₂ 2
Same as Example 1 except that it contains 5 mol%, 20 mol% of B ₂ O ₃ , 25 mol% of BaO, 20 mol% of K ₂ O, and 10 mol% of CaF _2. To form a paste. This paste was used as Example 8.

[0028] Example 9 glass powder, a SiO ₂ 2
As in Example 1 except that 0 mol%, 30 mol% of B ₂ O ₃ , 25 mol% of BaO, 15 mol% of Li ₂ O and 10 mol% of CaF ₂ were contained. To form a paste. This paste was used as Example 9.

Example 10 The glass powder was composed of 40 mol% of SiO ₂ , 15 mol% of B ₂ O ₃ , 25 mol% of SrO, 15 mol% of Li ₂ O and 5 mol of CaF _2. %, And a paste was formed in the same manner as in Example 1. This paste was used as Example 10.

Example 11 A paste was formed in the same manner as in Example 9 except that the glass powder contained 25 mol% of MgO instead of BaO of Example 9. This paste was used as Example 11.

Example 12 20 mol% of SiO ₂
Glass powder containing B and a ₂ O ₃ 30 mol%, and 10 mol% 10 mol% and SrO to BaO, and 10 mol% of CaO, and 1 mol% of Li ₂ O, and the CaF ₂ 10 mol% 6
0% by weight was prepared, and 40% by weight of alumina powder having an average particle size of 4.5 μm was prepared as a ceramic filler powder, and both were sufficiently mixed. Except for the above, a paste was formed in the same manner as in Example 1. This paste was used as Example 12.

Example 13 The content of SiO ₂ was 10 mol%,
B ₂ and O ₃ of 55 mol%, 5 mol% and SrO a BaO 5
Mole%, with the exception of the 10 mol% of MgO, and 10 mol% of Na ₂ O, that has been prepared 60 wt% of glass powder containing an a BaF ₂ 5 mole%, in the same manner as in Example 12 Bae -Formed a strike. This paste was used as Example 13.

Example 14 The content of SiO ₂ was 20 mol%,
B ₂ and O ₃ of 40 mol%, 5 mol% and SrO a BaO 5
Mol%, 10 mol% of CaO and 5 mol% of MgO
A paste was formed in the same manner as in Example 12, except that 60% by weight of a glass powder containing 5 mol% of K ₂ O and 10 mol% of SrF ₂ was prepared. This paste was used as Example 14.

Example 15 20 mol% of SiO ₂
B and ₂ O ₃ 30 mol%, and 10 mol% 10 mol% and the CaO and BaO, and 10 mol% of MgO, the Na ₂ O 10
A paste was formed in the same manner as in Example 12, except that 60% by weight of a glass powder containing 10 mol% of AlF ₃ and 10 mol% of AlF ₃ was prepared. This paste was used as Example 15.

Example 16 20 mol% of SiO ₂
30 mol% of B ₂ O ₃ , 15 mol% of CaO and MgO
60 mol% of a glass powder containing 9 mol%, 20 mol% of K ₂ O, 2 mol% of BaF ₂ , 2 mol% of CaF ₂ and 2 mol% of AlF _3. Except for this, a paste was formed in the same manner as in Example 12. This paste was used as Example 16.

Example 17: 20 mol% of SiO ₂
B and ₂ O ₃ 30 mol%, and 5 mol% of SrO, and 10 mol% of CaO, and 5 mol% of MgO, and 10 mol% of Li ₂ O, and the SrF ₂ 5 mole%, MgF ₂ A paste was formed in the same manner as in Example 12, except that 60% by weight of a glass powder containing 5 mol% was prepared. This paste was used as Example 17.

Example 18 20 mol% of SiO ₂
30 mol% of B ₂ O ₃ , 30 mol% of CaO, Li ₂
10 mol% of O, 5 mol% of MgF ₂ and 5 mol of AlF ₃
A paste was formed in the same manner as in Example 12, except that 60% by weight of a glass powder containing 5% by mole was prepared.
This paste was used as Example 18.

Example 19 20 mol% of SiO ₂
30 mol% of B ₂ O ₃ , 25 mol% of CaO and Na ₂
O and 16 mol%, and a BaF ₂ 3 mol%, the MgF ₂ 3
Glass powder containing 6 mol% and 3 mol% of AlF _3.
A paste was formed in the same manner as in Example 12, except that 0% by weight was prepared. This paste was used as Example 19.

Example 20 30 mol% of SiO ₂
25 mol% of B ₂ O ₃ , 15 mol% of SrO and K ₂ O
60 mol% of a glass powder containing 15 mol%, 6 mol% of Li ₂ O, 3 mol% of CaF ₂ , 3 mol% of SrF ₂ and 3 mol% of MgF _2. Except for this, a paste was formed in the same manner as in Example 12. This paste was used as Example 20.

Example 21 24 mol% of SiO ₂
36 mol% of B ₂ O ₃ , 20 mol% of BaO and Li ₂
O, 5 mol%, Na ₂ O, 5 mol%, and CaF ₂
And 50% by weight of a titania powder having an average particle size of 3.2 μm was prepared as a ceramic filler powder, and both were sufficiently mixed. Except for the above, a paste was formed in the same manner as in Example 1. This paste was used as Example 21.

[Example 22] 24% by mole of SiO ₂
36 mol% of B ₂ O ₃ , 20 mol% of BaO and Li ₂
O, 5 mol%, Na ₂ O, 5 mol%, and CaF ₂
Glass powder containing 70% by weight was prepared, and 45% by weight of zircon powder having an average particle diameter of 1.2 μm was prepared as a ceramic filler powder, and both were sufficiently mixed. Except for the above, a paste was formed in the same manner as in Example 1. This paste was used as Example 22.

Example 23: 24 mol% of SiO ₂
36 mol% of B ₂ O ₃ , 20 mol% of BaO and Li ₂
O, 5 mol%, Na ₂ O, 5 mol%, and CaF ₂
80% by weight of a glass powder containing 0.1% by mole and 35% by weight of a mullite powder having an average particle diameter of 4.3 μm as a ceramic filler powder, and both were sufficiently mixed. Except for the above, a paste was formed in the same manner as in Example 1. This paste was used as Example 23.

[Example 24] 24 mol% of SiO ₂
36 mol% of B ₂ O ₃ , 10 mol% of BaO and Li ₂
70% by weight of glass powder containing 20 mol% of O and 10 mol% of CaF ₂ was prepared, and 45% by weight of spodumene powder having an average particle size of 3.7 μm was prepared as a ceramic filler powder. Mix well. Except for the above, a paste was formed in the same manner as in Example 1. This paste was designated as Example 24.

Example 25 24 mol% of SiO ₂
46 mol% of B ₂ O ₃ , 20 mol% of BaO and CaF
80% by weight of a glass powder containing 10 mol% of ₂ and a ceramic filler powder having an average particle size of 6.7 μm
Was prepared in an amount of 25% by weight, and both were sufficiently mixed. Except for the above, the same procedure as in Example 1 was carried out.
A strike was formed. This paste was designated as Example 25.

Example 26 24 mol% of SiO ₂
36 mol% of B ₂ O ₃ , 25 mol% of BaO and K ₂ O
80% by weight of a glass powder containing 5 mol% of CaF ₂ and 10 mol% of CaF ₂ , and 30% by weight of a forsterite powder having an average particle size of 4.9 μm as a ceramic filler powder. Mixed. Except for the above, a paste was formed in the same manner as in Example 1. This paste was designated as Example 26.

Example 27 25% by mole of SiO ₂
30 mol% of B ₂ O ₃ , 30 mol% of BaO and Na ₂
75% by weight of glass powder containing 5 mol% of O and 10 mol% of CaF ₂ was prepared, and 30% by weight of anosite powder having an average particle size of 2.9 μa as a ceramic filler powder.
Prepared and mixed well. Other than the above, Example 1
A paste was formed in the same manner as described above. This paste was designated as Example 27.

Example 28 25 mol% of SiO ₂
30 mol% of B ₂ O ₃ , 20 mol% of BaO and K ₂ O
5 mol%, Li ₂ O 10 mol%, and CaF ₂ 10 mol%.
% By weight of glass powder, and 20% by weight of celsian powder having an average particle diameter of 4.3 μm as a ceramic filler powder, and both were sufficiently mixed. Except for the above, a paste was formed in the same manner as in Example 1.
This paste was designated as Example 28.

Example 29 25 mol% of SiO ₂
15 mol% of B ₂ O ₃ , 50 mol% of BaO and CaF
70% by weight of a glass powder containing 10 mol% of ₂ as a ceramic filler powder having an average particle size of 3.2 μm
Of aluminum titanate powder was prepared at 45% by weight, and both were sufficiently mixed. Except for the above, a paste was formed in the same manner as in Example 1. This paste was used as Example 29.

Next, for comparison, an example in which the amount of any component is out of the range of the present invention will be described below as a comparative example. Comparative Example 1 20 mol% of SiO ₂ , 20 mol% of B ₂ O ₃ , 45 mol% of CaO, and 15 mol% of CaF ₂
An attempt was made to produce a glass powder containing

Comparative Example 2 35 mol% of SiO ₂ and B ₂
47 mol% of O ₃ , 8 mol% of SrO, and 1 mol of CaF ₂
70% by weight of a glass powder containing 0% by mole and 30% by weight of a zircon powder having an average particle diameter of 4.3 μm as a ceramic filler powder were sufficiently mixed. Except for the above, a paste was formed in the same manner as in Example 1.
This paste was used as Comparative Example 2.

Comparative Example 3 10 mol% of SiO ₂ and B ₂
40 mol% of O ₃ , 5 mol% of MgO and ₂ mol of Li ₂ O
70% by weight of a glass powder containing 5 mol% and 20 mol% of CaF ₂ was prepared, and 10% by weight of β-eucryptite powder having an average particle diameter of 4.3 μm was prepared as a ceramic filler powder. Was mixed. Except for the above, a paste was formed in the same manner as in Example 1. This paste was used as Comparative Example 3.

Comparative Example 4 40 mol% of SiO ₂ and B ₂
A glass powder containing 30 mol% of O ₃ , 20 mol% of BaO, 4 mol% of Na ₂ O, and 6 mol% of MgF ₂ was prepared in an amount of 70% by weight, and the average particle size was determined as a ceramic filler powder. 20% by weight of 4.3 μm β-spodumene powder was prepared, and both were sufficiently mixed. Except for the above, a paste was formed in the same manner as in Example 1. This paste was used as Comparative Example 4.

Comparative Example 5 25 mol% of SiO ₂ and B ₂
O ₃ is 10 mol%, BaO is 40 mol%, and K ₂ O is 5 mol%.
An attempt was made to prepare a glass powder containing 20 mol% of SrF ₂ and 20 mol% of SrF ₂ , but it could not be vitrified.

Comparative Example 6 25 mol% of SiO ₂ and B ₂
50 mol% of O ₃ , 5 mol% of BaO and 8 mol of Li ₂ O
70% by weight of a glass powder containing mol% and 12% by mol of CaF ₂ was prepared, and 20% by weight of an alumina powder having an average particle diameter of 4.3 μm was prepared as a ceramic filler powder, and both were sufficiently mixed. Except for the above, a paste was formed in the same manner as in Example 1. This paste was used as Comparative Example 6.

Comparative Example 7 10 mol% of SiO ₂ and B ₂
45 mol% of O ₃ , 20 mol% of BaO and 5 mol of K ₂ O
Mole%, and 6 mol% of Na ₂ O, the Li ₂ O 4 mol%
And 70% by weight of a glass powder containing AlF ₃ and 10 mol% of AlF _3, and 10% by weight of a zircon powder having an average particle diameter of 4.3 μm as a ceramic filler powder, and both were sufficiently mixed. Except for the above, a paste was formed in the same manner as in Example 1. This paste was used as Comparative Example 7.

Comparative Example 8 25 mol% of SiO ₂ and B ₂
An attempt was made to produce a glass powder containing 25 mol% of O ₃ , 15 mol% of BaO, and 35 mol% of CaF ₂ .
Could not be vitrified.

[Comparative Tests and Evaluations] The pastes of Examples 1 to 29 and Comparative Examples 2 to 4 and 6 to 7 were each 2 inches in length and width.
Print on a glass substrate in a pattern of 5mm x 25mm,
After drying at 150 ° C. for 10 minutes, firing at various firing temperatures,
The firing temperature at which the adhesion to the glass substrate was good and the lowest was determined as the firing temperature of the paste of the glass composition and ceramic filler. The paste was poured into a cavity of 5 mm × 5 mm × 20 mm, fired at the firing temperature, and the thermal expansion coefficient of the glass plate formed after firing (× 1
0 ⁻⁷ / ° C.) and reflectance (%) were measured. The reflectance was measured by measuring the reflectance of a glass / ceramic film fired on a glass substrate to visible light (380 to 800 nm). Tables 1 to 3 show these results.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

As is clear from Tables 1 to 3, Example 1
In Comparative Examples 2 to 4, Comparative Examples 6 and 7, the firing temperature was as high as 600 ° C. or higher, whereas in Comparative Examples 1, 5, and 8, the firing temperature was lower than 600 ° C. Vitrification could not be performed with the glass component.

In Examples 1 to 29, the coefficient of thermal expansion was (80 to 89) × 10 ⁻⁷ / ° C., whereas in Comparative Examples 2 to 4, and Comparative Examples 6 and 7, the coefficient of thermal expansion was (91-
105) × 10 ⁻⁷ / ° C. The thermal expansion coefficients of Examples 1 to 29 were substantially the same as the thermal expansion coefficient of the glass substrate (soda-lime glass) of PDP (85 × 10 ⁻⁷ / ° C.).
Further, in Examples 1 to 29, the reflectance is 74 to 81%, whereas in Comparative Examples 2 to 4 and 6 to 7, the reflectance is 58 to 69%.
Met.

[0063]

As described above, according to the present invention, as the glass components of the glass composition, SiO ₂ 0 to 40 mol%, B ₂ O ₃ 10 to 60 mol%, BaO, SrO, C
one or two selected from the group consisting of aO and MgO
10-50 mol% of oxides of at least one species, BaF ₂ , Ca
One or more fluorides selected from the group consisting of F ₂ , SrF ₂ , MgF ₂ and AlF ₃ are selected from the group consisting of 0 to 10 mol% and Na ₂ O, K ₂ O, and Li ₂ O. Since the composition contains 5 to 50 mol% of one or more alkali oxides, the softening point is lowered and the firing temperature is also lowered. Further, since the glass component does not contain a high-density Pb component, the weight can be reduced, the environment is not polluted, and the discharge characteristics do not deteriorate during use. And 1 selected from the group consisting of the above glass composition and zircon, alumina, titania, mullite, β-eucryptite, cordierite, spodumene, anorthite, celsian, forsterite, aluminum titanate and the like. Seed or two or more ceramic fillers
When a paste containing a mixture of the above is used and the paste is fired to form an insulator, an insulator having a low firing temperature can be obtained because the softening point of glass is low. Further, by adding a ceramic filler, a white insulator having a high reflectance can be obtained. Further, when the insulator is applied to a partition for FPD or an insulator layer for FPD, the firing temperature of the glass composition becomes lower than the softening point of the glass substrate by 100 ° C. or more, and the coefficient of thermal expansion of the partition or the insulating layer becomes glass. Since the thermal expansion coefficient is substantially the same as the substrate, the glass substrate does not warp or the like. The electric signal does not leak to the neighboring wiring, and no crosstalk occurs in the image. Further, since the amount of the ceramic filler component added to the glass component is relatively small, the strength after firing is high.

[Brief description of the drawings]

FIG. 1 is a schematic perspective view showing a state of forming a ceramic capillary rib according to a first embodiment of the present invention.

FIG. 2 is a cross-sectional view showing a ceramic rib obtained by drying, heating, and firing the ceramic capillary rib in the cross section along the line AA in FIG. 1;

FIG. 3 is a schematic perspective view corresponding to FIG. 1 and showing a state of forming a rib with a ceramic capillary layer according to a second embodiment of the present invention.

4 is a cross-sectional view corresponding to FIG. 2 showing a ceramic rib with an insulating layer obtained by drying, heating, and firing the rib with the ceramic capillary layer in a cross section taken along line BB of FIG. 3;

FIG. 5 is a schematic cross-sectional view showing the formation of a PDP partition wall in the present invention in the order of steps.

[Explanation of symbols]

 10, 30 Glass substrate 11 Ceramic paste film 12 Blade 12a Blade 12 edge 12b Comb teeth 13, 23, 24 Ceramic capillary rib 14, 25 Ceramic rib (partition) 21 Ceramic capillary layer 22 Insulating layer 41 Pattern Green forming layer 42 photosensitive film 43 mask 44 partition wall 46 resist layer 47 cell 48 green partition wall

 ──────────────────────────────────────────────────の Continuing from the front page (72) Inventor Shiro Kuromitsu 1-297 Kitabukuro-cho, Omiya-shi, Saitama F-term in Mitsubishi Materials Research Laboratory 4G030 AA02 AA07 AA08 AA16 AA17 AA36 AA37 BA12 GA14 GA17 GA23 HA04 HA09 HA16 HA18 HA25 PA22 4G062 AA08 AA09 AA15 BB05 BB08 CC10 DA01 DA02 DA03 DA04 DA05 DB01 DC04 DC05 DC06 DD01 DE01 DF01 EA01 EA10 EB01 EC01 ED01 ED02 ED03 FA ED04 ED05 EE01 EE02 EE03 EF04 EG04 FC01 FD01 FE01 FF01 FG01 FH01 FJ01 FK01 FL01 GA01 GA10 GB01 GC01 GD01 GE01 GE02 GE03 HH01 HH03 HH05 HH07 HH09 HH11 HH13 HH15 HH17 HH20 JJ01 JJ03 JJ05 JJ07 JJ10 KK13 PP03 NN03 PP03 GD07 GF18 KA10 KA11 KA14 KA17 KB02 KB03 KB19 KB28 MA10 MA17 MA20 MA23

Claims (7)

[Claims] 1. A glass component comprising 0 to 40 mol% of SiO ₂ , 10 to 60 mol% of B ₂ O ₃ , MgO, CaO, S
10-50 mol% of one or more alkaline earth oxides selected from the group consisting of rO and BaO, and Li ₂
One or more selected from the group consisting of O, Na ₂ O, and K ₂ O, 5 to 50 mol%, and BaF ₂ , CaF ₂ ,
SrF _2, MgF ₂ and one selected from the group consisting of AlF ₃ or glass composition characterized by containing a 0 to 10 mol% of two or more of fluoride. 2. A ceramic filler material comprising zircon,
Alumina, titania, cordierite, mullite, β
-Eucryptite, spodumene, anorthite,
A glass composition and a ceramic filler comprising at least one ceramic filler selected from the group consisting of celsian, forsterite, and aluminum titanate, and the glass composition according to claim 1. Mixture with things. 3. A paste comprising the glass composition according to claim 1 or a mixture of the glass composition according to claim 2 and a ceramic filler, a polymer resin and a solvent. . 4. A glass comprising a glass composition according to claim 1 or a mixture of the glass composition according to claim 2 and a ceramic filler, a polymer resin and a solvent. -G. 5. An insulator formed by firing the glass composition according to claim 1 or a mixture of the glass composition according to claim 2 and a ceramic filler. 6. A partition wall for a PDP formed by firing the glass composition according to claim 1 or a mixture of the glass composition according to claim 2 and a ceramic filler. 7. A PDP comprising the glass composition according to claim 1 or the glass composition according to claim 2 and a ceramic filler.