JPH11228178A - Glass composition, insulating material using the same, partition for fpd and insulating layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve reflectivety without causing the warp of a glass substrate for FPD and generating crosstalk on an image of FPD. SOLUTION: As glass components in a glass composition, 2-45 mol.% B2 O3 , 15-45 mol.% ZnO, 1.5-40 mol.% one or more kinds of oxides selected from a group composed of BaO, SrO, CaO and MgO and 10-30 mol.% one or more kinds of fluorides selected from a group composed of BaF2 , CaF2 , SrF2 , MgF2 , and AlF3 are contained. And an insulating body (partition of FPD, insulating layer for FPD) is obtained by firing a mixture containing the glass composition and one or more kinds of ceramic fillers selected from a group composed of zircon, alumina, silica, mullite, β-eucryptite, cordierite, β-spodumene and forsterite.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a PDP (plasma d
isplay panel: plasma display panel), PAL
The present invention relates to a glass composition suitable for a partition and an insulating layer for an FPD (flat panel display) such as C (plasma addressed liquid crystal display) and an insulator using the same.

[0002]

2. Description of the Related Art Conventionally, a glass composition of this type has a glass powder content of 70 to 95% by weight and a refractory filler of 5 to 3%.
Japanese Patent Application Laid-Open No. 3-170346 discloses that the heat-resistant pigment contains 0 to 10% by weight. In this glass composition, the glass component has a PbO content of 55 to 65% by weight,
5% by weight of ZnO, 0 wt% of B ₂ O _3, 15~
25 wt% SiO _2, 0.5 to 5 wt% Al ₂ O _3,
0.5 to 15% by weight of (SnO ₂ + TiO ₂ );
10% by weight of (MgO + CaO + SrO + BaO),
0.1 to 2% by weight of CeO _2, 0.1~5% by weight of La ₂
Consists of O ₃ . However, in the above conventional glass composition,
Since the glass composition contains the Pb component, the density of the glass composition increases, and when this glass composition is used as a partition wall on a glass substrate of PDP, it causes a problem that the weight of the glass substrate increases and causes environmental pollution. There was a problem. When the weight of the glass substrate increases, the glass substrate is likely to be warped during firing of the glass substrate, that is, the glass substrate is point-supported at several points from below in order to prevent uneven heating in the firing process of the glass substrate. However, there is a problem that if the glass substrate is heavy, warpage is likely to occur due to its own weight. Further, in the above conventional glass composition, since the relative dielectric constant of the partition is relatively large at about 10 to 12, electric signals leak to neighboring wirings,
There is a problem that crosstalk easily occurs in an image. Furthermore, in the above-mentioned conventional glass composition, there is a problem that metal Pb precipitates during use as a PDP partition or an insulating layer (under a reduced-pressure plasma atmosphere), and the discharge characteristics deteriorate.

As a glass containing no Pb component, an ion discharge impact resistant low softening temperature glass (JP-A-48-4300)
7) and a plasma display panel (JP-A-8-301)
631) is disclosed. JP-A-48-4300
The resistant ion discharge damage, low softening temperature glasses shown in 7 JP, 30-43 wt% of boric anhydride (B ₂ O _3), 18
To 33% by weight of vanadium pentoxide (V ₂ O _5), 17~2
The main component is ₂ % by weight of zinc oxide (ZnO) and 8 to 12% by weight of sodium oxide (Na2O), and 6% by weight
Or less of silicic acid (SiO ₂ ), 5% by weight or less of alumina (A
l ₂ O ₃ ), 4% by weight or less of zirconium oxide (Zr
O ₂ ). In this ion discharge shock resistant low softening temperature glass,
Since it has substantially the same coefficient of thermal expansion as a generally used window glass plate and a lower softening temperature than the window glass plate, it is uniformly fused to the window glass without causing cracks or the like. In addition, since it does not contain any heavy metal oxide such as lead oxide (PbO) or bismuth oxide (Bi ₂ O ₃ ), which is liable to undergo a change such as dissociation due to the impact of the discharge of gas ions or the like, it is used as a coating glass for PDP glass substrates. Even when used for a portion that is subjected to gas ion discharge shock for a long time, gas ion discharge characteristics are not affected at all, and deterioration such as blackening of the coating and change in transparency does not occur.

On the other hand, in the plasma display disclosed in Japanese Patent Application Laid-Open No. Hei 8-301631, a partition is formed between each pixel of the display between glass substrates facing each other,
The partition is characterized by being made of a fired product of a glass ceramic composition comprising a glass powder composed of P ₂ O ₅ glass and a low expansion ceramic powder. In this plasma display panel, the glass ceramic composition contains 20 to 7
0% by weight of glass powder and 30 to 80% by weight of low expansion ceramic powder, wherein the glass powder is 25 to 35 mol%
Of P ₂ O _5, 0~50 mol% of ZnO, 0 to 70 mol% of SnO, 0 to 10 mol% of Li ₂ O, 0 to 10 mol% of Na ₂ O, of 0 mole% K ₂ O, from 0 to 20 _{mol% (Li 2 O + Na 2} O + K 2 O), 0~10 mol% of Mg
O, 0-10 mol% CaO, 0-10 mol% Sr
O, 0-10 mol% BaO, 0-20 mol% (Mg
O + CaO + SrO + BaO), 0 to 10 mol% of B ₂
O ₃ , consisting of 0-10 mol% Al ₂ O ₃ . In the plasma display panel thus configured, the relative dielectric constant of the partition is between 7 and 10, and crosstalk in display can be reduced as compared with the partition containing Pb. In addition, since the partition walls do not contain a Pb component, the density is small and a large PD
Ideal for P. Furthermore, since the coefficient of thermal expansion matches that of a normal PDP glass substrate, there is no warpage when a partition is formed on the PDP glass substrate, and no cracks are formed in the overcoat of the base, and the glass substrate Is also difficult to crack.

[0005]

The above-mentioned conventional Japanese Patent Application Laid-Open No. Sho 48
JP-A-43007 discloses a glass having a low softening temperature resistant to ionic discharge impact, which contains V ₂ O ₅ , so that it was colored brown and had a problem that the reflectance was lowered. Further, the conventional plasma display disclosed in Japanese Patent Application Laid-Open No. H8-301631 has a problem that water resistance is poor because it contains P ₂ O ₅ . In the conventional plasma display disclosed in Japanese Patent Application Laid-Open No. H8-301631, the glass has a large thermal expansion coefficient with respect to the glass substrate, so that a large amount of ceramic filler is added to match the thermal expansion coefficient with the glass substrate. Therefore, there is a problem that the structure after firing becomes porous, the strength is reduced, and the discharge characteristics are also reduced.

SUMMARY OF THE INVENTION An object of the present invention is to provide a glass composition, an insulator using the same, which can improve the reflectance without causing warpage in the glass substrate of the FPD and without causing crosstalk in the image of the FPD. An object of the present invention is to provide an FPD partition and an insulating layer. Another object of the present invention is to reduce the thermal expansion coefficient and reduce the thermal expansion coefficient to FPD without reducing the strength and discharge characteristics.
It is an object of the present invention to provide a glass composition, an insulator, an FPD partition wall, and an insulating layer using the same, which can be matched with a glass substrate and have a softening point lower than that of the glass substrate.

[0007]

The invention according to claim 1 is
As glass component, and B ₂ O ₃ 20 to 45 mol%, ZnO
15 to 45 mol%, BaO, SrO, CaO and Mg
One or more oxides 1 selected from the group consisting of O
5 to 40 mol%, BaF ₂ , CaF ₂ , SrF ₂ , Mg
It is one or the glass composition comprising 10 to 30 mol% more of fluoride selected from the group consisting of F _2, and AlF _3. 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, since the glass component does not contain a high-density Pb component, the weight can be reduced and the environment is not polluted.

[0008] The invention according to claim 2 is a method according to claim 2, wherein B ₂ O ₃ 20 to 45
Mol%, ZnO 15 to 45 mol%, BaO, Sr
One or two or more oxides selected from the group consisting of O, CaO and MgO, 15 to 40 mol%, and BaF ₂ , Ca
A glass composition comprising 10 to 30 mol% of one or more fluorides selected from the group consisting of F ₂ , SrF ₂ , MgF ₂ and AlF ₃ ; zircon, alumina, silica, mullite, β-U An insulator obtained by firing a mixture containing one or more ceramic fillers selected from the group consisting of krypite, cordierite, β-spodumene, and forsterite. In the insulator according to the second aspect, since the softening point of the glass is low, the firing temperature of the insulator can be lowered. Further, since V ₂ O ₅ is not contained in the glass component, a white insulator having high reflectance can be obtained.

According to a third aspect of the present invention, there is provided an FPD partition wall formed of the insulator according to the second aspect. According to a fourth aspect of the present invention, there is provided a semiconductor device comprising:
This is a PD insulating layer. The FPD according to claim 3
The partition for FPD or the insulating layer for FPD according to claim 4,
By firing ceramic green ribs or ceramic green sheets containing an organic binder in a mixture of the glass composition and the ceramic filler, the ribs or sheets become partition walls or insulating layers. Or a glass composition,
An organic solvent is added to the ceramic filler and the organic binder to form a paste, and the ceramic capillary rib or the ceramic capillary layer is dried and fired by a screen printing method or the like, whereby the ceramic capillary rib or the ceramic capillary layer becomes a partition wall or an insulating layer. Since the firing temperature at this time is lower than the softening point of the glass substrate by 100 ° C. or more, the glass substrate does not warp. Further, since the coefficient of thermal expansion of the partition or the insulating layer is substantially the same as the coefficient of thermal expansion of the glass substrate, warpage of the glass substrate can be further suppressed. Since the relative permittivity of the partition or the insulating layer is relatively small, about 4 to 7, electric signals do not leak to neighboring wirings, and no crosstalk occurs in an image. Furthermore, 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. The above-mentioned ceramic capillary refers to a state where most of the organic binder and the solvent remain after the paste containing the glass composition, the ceramic filler, the organic binder, and the solvent is applied.

[0010]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A first embodiment of the present invention will be described in detail with reference to the drawings. The insulator of the present invention is formed by firing a mixture containing a glass composition and a ceramic filler. As the glass composition, B ₂
20 to 45 mol% of O ₃ and 15 to 45 mol% of ZnO
And 15 to 40 mol% of one or more oxides selected from the group consisting of BaO, SrO, CaO and MgO.
And BaF ₂ , CaF ₂ , SrF ₂ , MgF ₂ and AlF ₃
And 10 to 30 mol% of one or more fluorides selected from the group consisting of

The reason why B ₂ O ₃ is limited to the range of 20 to 45 mol% is that if it is less than 20 mol%, it does not become glass and has a high softening point, and if it exceeds 45 mol%, it has a problem of poor water resistance. is because there, more preferably B ₂ O ₃ is 25 to 40 mol%. In addition, ZnO is 15 to 45 mol%
The reason 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, and ZnO is 20 to 40 mol%. More preferred.

Also, one or more oxides selected from the group consisting of BaO, SrO, CaO and
The reason why the content is limited to the range of ４０40 mol% is that if it is less than 15 mol%, there is a problem that the softening point is high, and if it exceeds 40 mol%, there is a problem that it does not become glass. Is more preferable. Furthermore, Ba
One or two or more fluorides selected from the group consisting of F ₂ , CaF ₂ , SrF ₂ , MgF ₂ and AlF ₃ are mixed with 10 to 3
The reason why the content is limited to the range of 0 mol% is that if it is less than 10 mol%, there is a problem that the softening point is high, and if it exceeds 30 mol%, there is a problem that it does not become glass.
More preferably, it is 2 to 25 mol%.

The ceramic filler includes one or more ceramics selected from the group consisting of zircon, alumina, silica, mullite, β eucryptite, cordierite, β spodumene and forsterite. The reason why the ceramic filler component is mixed with the glass component is, for example, a PDP using the above glass component.
This is because when the partition walls are formed on a glass substrate, the thermal expansion coefficients of the partition walls and the glass substrate are matched.

In this embodiment, ceramic ribs (PDP partition walls) are formed by firing the mixture. A method for forming the ceramic rib will be described with reference to FIG. 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 paste film 11 formed by applying the paste containing the glass composition and the ceramic filler to the surface of the glass substrate 10. 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 certain direction. The paste includes the glass composition, a ceramic filler, an organic binder, and a solvent.

It is preferable that the content of the ceramic filler is 60% by volume or less based on the volume of the glass composition. This is because if the amount of the ceramic filler exceeds 60% by volume, the ribs 13 become porous, which is not preferable. The glass composition and the ceramic filler each have a particle size of 0.1.
Preferably, the powder is 1 to 30 μm. The reason why the particle diameter of the glass composition and the ceramic filler is limited to the range of 0.1 to 30 μm is that when the particle diameter is less than 0.1 μm, it is likely to be agglomerated and the handling thereof becomes troublesome. This is because the ribs 13 cannot be formed.

The mixing ratio of each component of the paste is preferably 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 a relatively small volatility at normal temperature, and terpineol,
Butyl carbitol, acetate, ether and the like. By configuring the paste in this way, a paste having a predetermined viscosity can be obtained, and the ceramic ribs 13 formed on the glass substrate 10 can be formed while suppressing the dripping of the ceramic capillary ribs 13 and firing the ceramic ribs accurately. be able to.

The paste is applied to the surface of the glass substrate 10 by an existing means such as a screen printing method, a dip method or a doctor blade method. Blade 12 contacting the surface of glass substrate 10 on which paste film 11 is formed
Are formed with a plurality of comb teeth 12b at equal intervals and in the same direction. The blade 12 is made of a metal, ceramic, plastic, or the like that does not react with the paste or is dissolved in the paste. In particular, from the viewpoint of dimensional accuracy and durability, ceramic or an alloy based on Fe, Ni, or Co is preferable. The gap between the respective comb teeth 12b is formed by the ceramic capillary rib 1 formed by the blade 12.
3 is formed corresponding to the cross-sectional shape.

The formation of the ceramic capillary rib 13 by the blade 12 configured as described above is performed by
The glass substrate 10 is fixed while the edge 12a of the glass substrate 10 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. The fixing is performed by moving the glass substrate 10 in a fixed direction as shown by a broken arrow in FIG. By this movement, the comb teeth 12b of the blade 12 of the paste applied to the surface of the glass substrate 10
Is moved or swept into the gap between the comb teeth 12b, and only the paste located in the gap between the comb teeth 12b remains on the glass substrate 10 and the ceramic capillary rib 13 Is formed. If the depth of the groove of the comb tooth is larger than the thickness of the paste film 11, the paste swept out when moving the blade 12 or the glass substrate 10 enters the groove and has a height greater than the thickness of the paste film 11. The ceramic capillary rib 13 can be formed.

The thus formed ceramic capillary rib 13 is then dried into a ceramic green rib (not shown), heated for binder removal, and subsequently fired to obtain the ceramic green rib shown in FIG. It becomes the rib 14. The firing temperature at this time is lower than 600 ° C., which is 100 ° below the softening point (735 ° C.) of the glass substrate 10 when soda-lime glass is used as the glass substrate.
° C or lower (the softening point of glass is
This is the temperature minus 0 ° C. ), The glass substrate 10 does not soften, and the glass substrate 10 does not warp. The thermal expansion coefficient of the ceramic rib 14 is 65 to 87 × 10 ^-7 /
C. and the thermal expansion coefficient of the glass substrate 10 (85 × 10 ⁻⁷ /
° C), and the glass composition does not contain a high-density Pb component, so that the weight of the glass composition can be reduced. Therefore, the warpage of the glass substrate 10 can be further suppressed.

Further, since V ₂ O ₅ is not contained in the glass component,
The ceramic ribs 14 having high white reflectance can be obtained, and the relative permittivity of the ceramic ribs 14 is relatively small, about 4 to 7, so that electric signals do not leak to neighboring wirings, and the image does not cross the image. No talk occurs. Furthermore, since the amount of the ceramic filler added to the glass composition is relatively small, the strength and discharge characteristics of the fired ceramic rib 14 do not decrease.

FIGS. 3 and 4 show 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, the glass substrate 1
0, the edge 12a of the blade 12 having the comb teeth 12b is floated at a predetermined height from the surface of the glass substrate 10 with respect to the paste film 11 formed by applying the paste on the surface of the glass substrate 10. Is moved in a certain direction, whereby a ceramic capillary layer 21 is formed on the surface of the glass substrate 10, and a ceramic capillary rib 23 is formed on the ceramic capillary layer 21 (FIG. 3). 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 are further heated for binder removal and subsequently fired, so that the ceramic capillary layer 21 and the ceramic capillary rib 23 are fired on the glass substrate 10 shown in FIG. Insulating layer 2 formed
2 and a ceramic rib 2 formed on the insulating layer 22.
It becomes 4.

As shown in FIG. 5, the ceramic ribs 24 may be formed on the glass substrate 30 by a thick film printing method. In this method, the glass substrate 3
The paste is aligned with a predetermined pattern on the surface of No. 0 by a thick-film printing method, applied repeatedly, and dried to form a paste film 31. This step is repeated a number of times to form the paste film 31 at a predetermined height and then firing, whereby the ceramic ribs 34 are formed on the glass substrate 30 at predetermined intervals.

As shown in FIG. 6, the ceramic ribs 44 may be formed on the glass substrate 30 by a sand blast method. In this method, the paste is applied to the entire surface of the glass substrate 30 by a thick film method,
After drying, or by laminating a ceramic green tape made from the paste, a pattern forming layer 41 having a predetermined height is formed, and then the pattern forming layer 41 is covered with a photosensitive film 42, and further, The film 42 is covered with a mask 43 and exposed and developed to form a resist pattern 46 having a predetermined pattern. Next, sandblasting is performed from above the resist layer 46 to remove the portion that becomes the cell 47, so that the pattern forming layer 41 becomes a ceramic green rib 48.
Becomes Further, by firing after removing the resist layer 46 using a release agent or the like, the ceramic ribs 44 are formed on the glass substrate 30 at predetermined intervals. Furthermore, in the first and second embodiments, the PDP partition and the PDP insulating layer are formed by the insulator of the present invention, but the PALC partition and the PALC insulating layer may be formed.

[0024]

Next, examples of the present invention will be described in detail together with comparative examples. And the <Example 1> B ₂ O ₃ 30 mol%, and 20 mol% of ZnO, and 30 mol% of BaO, glass powder (glass composition) of 70 wt% prepared containing and an MgF ₂ 20 mol% Then, 30% by weight of zircon powder having an average particle diameter of 4.3 μm was prepared as a ceramic filler, and both were sufficiently mixed. Specifically, the above glass powder is H ₃ B as B ₂ O _3.
O ₃ and ZnO are used as they are, and BaCO ₃ and Mg are used as BaO.
F ₂ was mixed as it was to obtain the prescribed components, dissolved in air at 1100 ° C. for 30 minutes, poured out into a platinum dish, solidified and pulverized (average particle size of 3 to 5 μm).
m) obtained. This mixed powder, ethyl cellulose as an organic binder, and α-terpineol as a solvent were mixed in a weight ratio of 5%.
The mixture was blended at a ratio of 0/10/40 and kneaded sufficiently to obtain a paste. The paste thus obtained was used in Example 1
And In addition, the following Examples 2 to 29 and Comparative Examples 1 to 8
Glass powder may, H ₃ BO ₃ as above as B ₂ O _3,
BaO, SrO, and Ca are oxides as they are.
BaCO ₃ , SrCO ₃ , CaCO ₃ as O or MgO
Or MgCO ₃ , fluorides of MgF ₂ , CaF ₂ , S
rF ₂ , MgF _2, or AlF ₃ are mixed as they are so as to have predetermined components.
It was melted for 0 minutes, poured out into a platinum dish, solidified and then pulverized (average particle size: 3 to 5 μm) to obtain.

Example 2 The glass powder was Mg of Example 1.
A paste was formed in the same manner as in Example 1, except that 20 mol% of SrF ₂ was used instead of F ₂ . This paste was used as Example 2. Example 3 A paste was formed in the same manner as in Example 1 except that the glass powder contained 20 mol% of CaF ₂ instead of MgF ₂ of Example 1. This paste was used in Example 3
And Example 4 A paste was formed in the same manner as in Example 1 except that the glass powder contained 20 mol% of AlF ₃ instead of MgF ₂ of Example 1. This paste was used in Example 4
And Example 5 A glass powder containing 30 mol% of B ₂ O ₃ and Zn
A paste was formed in the same manner as in Example 1, except that 20 mol% of O, 40 mol% of BaO, and 10 mol% of CaF ₂ were contained. This paste was used as Example 5.

Example 6 The glass powder contained 45 mol% of B ₂ O ₃ , 15 mol% of ZnO and 20 mol% of BaO.
And a paste was formed in the same manner as in Example 1 except that CaF ₂ was contained in an amount of 20 mol%. This paste was used as Example 6. Example 7 A glass powder containing 30 mol% of B ₂ O ₃ and Zn
And 45 mol% of O, and except a 15 mol% of BaO, to include and the CaF ₂ 10 mol%, to form a paste in the same manner as in Example 1. This paste was used as Example 7. Example 8 A glass powder containing 20 mol% of B ₂ O ₃ and Zn
And 35 mol% of O, and except a 15 mol% of BaO, to include and the CaF ₂ 30 mol%, to form a paste in the same manner as in Example 1. This paste was used as Example 8.

Example 9 The glass powder was composed of 30 mol% of B ₂ O ₃ , 20 mol% of ZnO and 30 mol% of CaO.
And a paste was formed in the same manner as in Example 1 except that CaF ₂ was contained in an amount of 20 mol%. This paste was used as Example 9. Example 10 A paste was formed in the same manner as in Example 9, except that the glass powder contained 30 mol% of SrO instead of CaO of Example 9. This paste was used in Example 10
And Example 11 A paste was formed in the same manner as in Example 9 except that the glass powder contained 30 mol% of MgO instead of CaO of Example 9. This paste was used in Example 11
And

Example 12 30 mol% of B ₂ O ₃ and Z
and 20 mol% nO, and 10 mol% of BaO, and 10 mol% of SrO, and 10 mol% of CaO, a CaF ₂ 20
% By weight of glass powder was prepared, and 40% by weight of alumina 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 12. Example 13 30 mol% of B ₂ O ₃ , 20 mol% of ZnO, 5 mol% of BaO, 5 mol% of SrO, M
Example 1 Except that 60% by weight of a glass powder containing 20 mol% of gO and 20 mol% of BaF ₂ was prepared.
A paste was formed in the same manner as in No. 2. This paste was used as Example 13.

Example 14 30 mol% of B ₂ O ₃ and Z
A glass powder containing 20 mol% of nO, 10 mol% of BaO, 5 mol% of SrO, 10 mol% of CaO, 10 mol% of MgO, and 20 mol% of SrF ₂ is used as a glass powder.
A paste was formed in the same manner as in Example 12, except that the weight% was prepared. This paste was used as Example 14. Example 15 30 mol% of B ₂ O ₃ , 20 mol% of ZnO, 10 mol% of BaO, and 10 mol% of CaO
And 10 mol% of MgO and 10 mol% of CaF ₂ ,
60% by weight of glass powder containing 10 mol% of AlF ₃
A paste was formed in the same manner as in Example 12, except that the paste was prepared. This paste was used as Example 15.

Example 16 30 mol% of B ₂ O ₃ and Z
and 20 mol% nO, and 15 mol% of CaO, and 15 mole% of MgO, and a BaF ₂ 5 mole%, a CaF ₂ and 10 mol%, the AlF ₃ glass powder containing a 5 mol% 60
A paste was formed in the same manner as in Example 12, except that the weight% was prepared. This paste was used as Example 16. Example 17 30 mol% of B ₂ O ₃ , 20 mol% of ZnO, 5 mol% of SrO, 20 mol% of CaO,
MgO 5 mol%, SrF ₂ 10 mol%, MgF ₂
Was prepared in the same manner as in Example 12, except that 60% by weight of a glass powder containing 10 mol% of was prepared. This paste was used as Example 17.

Example 18 30 mol% of B ₂ O ₃ and Z
20 mol% of nO, 30 mol% of CaO, and CaF ₂
Was prepared in the same manner as in Example 12, except that 60% by weight of a glass powder containing 10 mol%, 5 mol% of MgF ₂ and 5 mol% of AlF ₃ was prepared. This paste was used as Example 18. <Example 19> B ₂ and O ₃ of 30 mol%, and 20 mol% of ZnO, and 30 mol% of BaO, BaF ₂ and 10 mole%
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 MgF ₂ and 5 mol% of AlF ₃ was prepared. This paste was used as Example 15.

Example 20 30 mol% of B ₂ O ₃ and Z
20 mol% of nO, 30 mol% of SrO, and CaF ₂
, 5 mol% of SrF ₂ , 5 mol% of MgF ₂ , and 60 mol% of a glass powder containing 5 mol% of AlF ₃ in the same manner as in Example 12. To form a paste. This paste was used as Example 20. And 36 mol% <Example 21> B ₂ O _3, and 24 mol% of ZnO, and 30 mol% of BaO, and CaF ₂ 10 mol%
Was prepared, and 50% by weight of an alumina 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> 36 mol% of B ₂ O ₃ and Z
24 mol% of nO, 30 mol% of BaO, and CaF ₂
And 70% by weight of a glass powder containing 10 mol%
30% by weight of zircon 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 Example 22. <Example 23> B ₂ and O ₃ of 36 mol%, and 24 mol% of ZnO, and 30 mol% of BaO, and CaF ₂ 10 mol%
And 80% by weight of a glass powder containing silica powder having a mean particle size of 2.0 μm as a ceramic filler powder.
0% by weight 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 Example 23.

<Example 24> 36 mol% of B ₂ O ₃ and Z
24 mol% of nO, 20 mol% of BaO, and CaF ₂
And 70% by weight of a glass powder containing 20 mol% of
30% by weight of mullite 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 designated as Example 24. <Example 25> B ₂ and O ₃ of 36 mol%, and 24 mol% of ZnO, and 20 mol% of BaO, and CaF ₂ 20 mol%
Was prepared by 80% by weight, and 20% by weight of β-eucryptite powder having an average particle size of 2.6 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 25.

Example 26 36% by mole of B ₂ O ₃ and Z
24 mol% of nO, 20 mol% of BaO, and CaF ₂
And 80% by weight of a glass powder containing 20 mol% of
20% by weight of cordierite powder having an average particle size of 4.9 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 26. <Example 27> B and the ₂ O ₃ 30 mol%, and 25 mol% of ZnO, and 30 mol% of BaO, and CaF ₂ 30 mol%
Was prepared, and forsterite powder having an average particle size of 2.9 μm was prepared as a ceramic filler powder at 25% 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 27.

Example 28 30 mol% of B ₂ O ₃ and Z
25 mol% of nO, 30 mol% of BaO, and CaF ₂
And 60% by weight of glass powder containing
A 40% by weight zircon 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 Example 28. And the <Example 29> B ₂ O ₃ 30 mol%, and 25 mol% of ZnO, and 30 mol% of BaO, and CaF ₂ 30 mol%
Was prepared, and 70% by weight of an alumina 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 29.

Comparative Example 1 20 mol% of B ₂ O ₃ and Zn
A glass powder containing 20 mol% of O, 45 mol% of BaO, and 15 mol% of CaF ₂ was prepared. No ceramic filler powder was used. Example 1 other than the above
A paste was formed in the same manner as described above. This paste was used as Comparative Example 1. Comparative Example 2 70% by weight of a glass powder containing 35 mol% of B ₂ O ₃ , 45 mol% of ZnO, 10 mol% of BaO, and 10 mol% of CaF ₂ was prepared. Zircon powder having an average particle size of 4.3 μm
0% by weight 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 2.

Comparative Example 3 40 mol% of B ₂ O ₃ and Zn
70% by weight of glass powder containing 10 mol% of O, 30 mol% of BaO, and 20 mol% of CaF ₂ is prepared, and 30% by weight of zircon powder having an average particle diameter of 4.3 μm is prepared as a ceramic filler powder. Then, 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 3. Comparative Example 4 70% by weight of a glass powder containing 25 mol% of B ₂ O ₃ , 50 mol% of ZnO, 35 mol% of BaO, and 10 mol% of CaF ₂ was prepared. Zircon powder having an average particle size of 4.3 μm
0% by weight 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 15 mol% of B ₂ O ₃ and Zn
A glass powder containing 25 mol% of O, 40 mol% of BaO, and 20 mol% of CaF ₂ was prepared. No ceramic filler powder was used. Example 1 other than the above
A paste was formed in the same manner as described above. This paste was used as Comparative Example 5. Comparative Example 6 70% by weight of a glass powder containing 50 mol% of B ₂ O ₃ , 25 mol% of ZnO, 15 mol% of BaO, and 10 mol% of CaF ₂ was prepared. Zircon powder having an average particle size of 4.3 μm
0% by weight 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 6.

<Comparative Example 7> 45 mol% of B ₂ O ₃ and Zn
70% by weight of a glass powder containing 25 mol% of O, 22 mol% of BaO, and 8 mol% of CaF ₂ , and 30% by weight of zircon powder having an average particle diameter of 4.3 μm as a ceramic filler powder Then, 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 A glass powder containing 25 mol% of B ₂ O ₃ , 25 mol% of ZnO, 16 mol% of BaO, and 34 mol% of CaF ₂ was prepared. No ceramic filler powder was used. Except for the above, a paste was formed in the same manner as in Example 1. This paste was used as Comparative Example 8.

<Comparative Test and Evaluation> The pastes of Examples 1 to 29 and Comparative Examples 1 to 8 were each 25 mm in length and width.
Print on a glass substrate in a pattern of 25mm, 150 ℃
, And then fired at various firing temperatures. The lowest firing temperature with good adhesion to the glass substrate was taken as the firing temperature of the paste of the glass composition and ceramic filler (glass / ceramic). In addition, the reflectance is measured by the visible light (380) of the glass / ceramic film fired on the glass substrate.
８００800 nm). 5mm x 5m
Pour the above paste into a cavity of mx 20 mm,
The glass was fired at the above firing temperature, and the coefficient of thermal expansion of the glass plate formed after firing was measured. Tables 1 to 3 show these results.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

As is clear from Tables 1 to 3, Example 1
In Comparative Examples 2 to 4 and Comparative Examples 6 and 7, the firing temperature was lower than 600 ° C.
The temperature was as high as 00 ° C. or higher, and in Comparative Examples 1, 5, and 8, vitrification could not be performed with a predetermined glass component. Examples 1 to
29, the thermal expansion coefficient was (65-88) × 10 ⁻⁷ / ° C., whereas in Comparative Examples 2 to 4, Comparative Examples 6 and 7,
The coefficient of thermal expansion was (77 to 83) × 10 ⁻⁷ / ° C. The thermal expansion coefficients of Examples 1 to 29 were substantially the same as the thermal expansion coefficient (85 × 10 ⁻⁷ / ° C.) of the PDP glass substrate (soda-lime glass). Further, in Comparative Examples 2 to 4 and Comparative Examples 6 and 7, the reflectance was 72 to 78%, whereas Example 1 was used.
-29, the reflectance was 71-90%, which was not different from that of the comparative example, but almost all of them exhibited a reflectance of 78% or more.

[0046]

As described above, according to the present invention, according to the present invention, as the glass component of the glass composition, B and ₂ O ₃ 20 to 45 mol%, and ZnO15~45 mol%, BaO, SrO, C
15 to 40 mol% of one or more oxides selected from the group consisting of aO and MgO, and BaF ₂ , CaF ₂ , S
1 selected from the group consisting of rF ₂ , MgF ₂ and AlF ₃
Since it contains 10 to 30 mol% of a kind or two or more kinds of fluorides, the softening point is lowered and the firing temperature is also lowered. Further, since the glass component does not include a Pb component having a large density,
The weight can be reduced, the environment is not polluted, and the discharge characteristics do not deteriorate during use.

The above glass composition and one or more ceramic fillers selected from the group consisting of zircon, alumina, silica, mullite, β eucryptite, cordierite, β spodumene and forsterite are also included. If the insulator is formed by firing the mixture, an insulator having a low firing temperature can be obtained because the softening point of glass is low. Further, since V ₂ O ₅ is not contained in the glass component, a white insulator having high reflectance can be obtained.

The above-mentioned insulator may be used as an FPD partition or FPD.
When applied to the insulating layer for, the firing temperature of the glass composition is 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 substantially the same as the coefficient of thermal expansion of the glass substrate. The glass substrate does not warp. In addition, since the relative permittivity of the partition or the insulating layer is relatively small, about 4 to 7, electric signals do not leak to neighboring wirings, and no crosstalk occurs in an image.
Furthermore, 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 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 perspective view corresponding to FIG. 1 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 a ceramic capillary layer in a cross section taken along line BB of FIG. 3;

FIG. 5 is a sectional view showing the formation of a ceramic rib according to a third embodiment of the present invention in the order of steps.

FIG. 6 is a sectional view showing the formation of a ceramic rib according to a fourth embodiment of the present invention in the order of steps.

[Explanation of symbols]

 10, 30 Glass substrate 14, 24, 34, 44 Ceramic rib (partition) 22 Insulating layer

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 1, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

4. The insulator according to claim 2, or the insulator according to claim 3.
Partition for FPD formed by the paste of (1).

5. The insulator according to claim 2, or the insulator according to claim 3.
Insulating layer for FPD formed by the paste of (1).

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

According to a third aspect of the present invention, there is provided a gas monitor according to the second aspect.
Dissolve organic binder in glass composition and ceramic filler
A paste for insulator prepared by mixing with a medium. The invention according to claim 4 is the insulator or claim according to claim 2.
3 is a partition wall for FPD formed by the paste according to 3 . The invention according to claim 5 provides the insulator according to claim 2 or
An FPD insulating layer formed by the paste according to claim 3 . In the partition for FPD according to claim 4 or the insulating layer for FPD according to claim 5 , a ceramic green rib or a ceramic green sheet containing an organic binder in a mixture of the glass composition and the ceramic filler is fired. By doing so, the rib or sheet becomes a partition or an insulating layer. Alternatively, by adding an organic solvent to a glass composition, a ceramic filler and an organic binder, forming a paste, drying the ceramic capillary rib or the ceramic capillary layer by screen printing or the like, and firing the ceramic capillary rib or the ceramic capillary layer, the partition walls or Becomes an insulating layer. Since the firing temperature at this time is lower than the softening point of the glass substrate by 100 ° C. or more, the glass substrate does not warp. Further, since the coefficient of thermal expansion of the partition or the insulating layer is substantially the same as the coefficient of thermal expansion of the glass substrate, warpage of the glass substrate can be further suppressed. Since the relative permittivity of the partition wall or the insulating layer is relatively small as about 4 to 7, electric signals do not leak to neighboring wirings.
No crosstalk occurs in the image. Furthermore, 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.
The above-mentioned ceramic capillary refers to a state where most of the organic binder and the solvent remain after the paste containing the glass composition, the ceramic filler, the organic binder, and the solvent is applied.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction contents]

The above insulator, organic binder and solvent are
Partition walls for FPD or F by the paste prepared by mixing
Form an insulating layer for PD or replace the insulator with FPD
When applied to the partition wall or the insulating layer for FPD, the firing temperature of the glass composition is lower than the softening point of the glass substrate by 100 ° C. or more, and the thermal expansion coefficient of the partition wall or the insulating layer is approximately equal to the thermal expansion coefficient of the glass substrate. Since they are the same, the glass substrate does not warp or the like. In addition, since the relative permittivity of the partition or the insulating layer is relatively small, about 4 to 7, electric signals do not leak to neighboring wirings, and no crosstalk occurs in an image. Furthermore, since the amount of the ceramic filler component added to the glass component is relatively small, the strength after firing is high.

Claims (4)

[Claims] 1. A glass component comprising 20 to 45 mol% of B ₂ O _3, 15 to 45 mol% of ZnO, BaO, SrO,
15 to 40 mol% of one or more oxides selected from the group consisting of CaO and MgO, and BaF ₂ , CaF ₂ ,
SrF _2, 1 kind selected from the group consisting of MgF ₂ and AlF ₃ or glass composition comprising 10 to 30 mol% of two or more of fluoride. _{2. 20 to} 45 mol% of B ₂ O _{3 and} ZnO 15
~ 45 mol% and one or more oxides 15 or more selected from the group consisting of BaO, SrO, CaO and MgO.
A glass composition comprising 40 mol% and 10 to 30 mol% of one or more fluorides selected from the group consisting of BaF ₂ , CaF ₂ , SrF ₂ , MgF ₂ and AlF ₃ ; An insulator obtained by firing a mixture containing one or more ceramic fillers selected from the group consisting of alumina, silica, mullite, β-eucryptite, cordierite, β-spodumene, and forsterite. 3. An FPD partition formed by the insulator according to claim 2. 4. An insulating layer for an FPD formed by the insulator according to claim 2.