WO2007029425A1

WO2007029425A1 - Nonlead glass composition

Info

Publication number: WO2007029425A1
Application number: PCT/JP2006/314761
Authority: WO
Inventors: Yoshitaka Mayumi
Original assignee: Nihon Yamamura Glass Co., Ltd.
Priority date: 2005-09-02
Filing date: 2006-07-26
Publication date: 2007-03-15
Also published as: CN101277908A; JP2007063105A

Abstract

A nonlead glass composition that solving the problem of conventional Bi2O3 glass with respect to glass softening point and acid resistance, not only can retain the same level of softening point as that of conventionally employed lead glass but also realizes excellent acid resistance. There is provided a nonlead glass composition comprising, in terms of oxide, 55 to 75 wt.% Bi2O3, 5 to 15 wt.% B2O3, 4 to 12 wt.% SiO2, 3 to 12 wt.% ZnO, 3 to 10 wt.% Al2O3 and 0.1 to 5 wt.% ZrO2.

Description

Specification

Lead-free glass composition

Technical field

[0001] The present invention relates to a lead-free glass composition. More specifically, the present invention relates to a lead-free glass composition used for the formation, adhesion, coating or sealing of electronic components that require acid resistance. More specifically, lead-free glass added to conductor wiring parts such as Ag conductors that require acid resistance over plasma display panels, or lead-free glass used to protect surfaces that require acid resistance of electronic components and elements. Relates to a glass composition.

Background art

[0002] In a display device such as a plasma display panel, for example, a conductor used for wiring is formed by mixing Ag powder with glass powder and sintering the glass, and protecting the surface of the element with glass. It has been usefully used. Conventionally, lead glass has been mainly used as these glasses, but in recent years, products containing lead have a tendency to be avoided from an environmental point of view.

Low melting glass that does not contain lead includes P O ZnO, P O—SnO, and Bi O

2 5 2 5 2 3 Glass is known. However, from the point of mechanical durability, Bi O glass has recently been used.

2 3 Often used.

Patent Document 1: JP 2002-270035 A

Patent Document 2: JP 2000-67750 A

Patent Document 3: Japanese Patent Laid-Open No. 10-231141

Disclosure of the invention

Problems to be solved by the invention

[0003] However, the above-mentioned BiO glass has the same glass soft spot as that of conventional lead glass.

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In the case where the temperature is too high, the acid resistance is poor.

For this reason, when manufacturing a plasma display panel, a conductor wiring is formed on a glass substrate by sintering using a metal powder and the BiO glass powder, and further forming a wiring.

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When forming a partition from a layer laminated on a glass substrate, the partition is formed. When etching is performed using an acid, there has been a problem that the conductor containing the glass is corroded by the etching using the acid.

Patent Document 1 discloses the use of vitreous powder mainly composed of bismuth zinc borosilicate glass, and Patent Document 2 discloses non-crystalline glass or bismuth composed mainly of zinc oxide. It is disclosed to use an amorphous glass mainly composed of a system, and both Patent Documents 1 and 2 aim at improving the stability of the glass and adjusting the glass softening point. However, neither Patent Document 1 or 2 improves the acid resistance of the glass itself.

In Patent Document 3, the bismuth borosilicate glass contains ZnO and AlO.

Although attempts have been made to improve the acid resistance of glass by adjusting the amount, there is a problem that the soft spot rises compared to lead glass, and it also solves the problem of peeling due to acid resistance. Not yet.

[0004] Therefore, the present invention solves the above-mentioned problems in the conventional BiO-based glass and has been used in the past.

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It is an object of the present invention to provide a lead-free glass composition that can have a soft temperature equivalent to that of the conventional lead-based glass and has good acid resistance.

Means for solving the problem

[0005] As a result of intensive studies to solve the above problems, the present inventors have found that Bi O— B O— Si.

2 3 2 3

O—ZnO—Al O—ZrO glass composition in a certain component range.

2 2 3 2

Thus, as a substitute for lead-based glass, the inventors have found that it has a soft temperature equivalent to that of lead-based glass and exhibits good acid resistance, and has completed the present invention.

That is, the lead-free glass composition of the present invention is, in terms of oxide, Bi 2 O: 55 to 75% by weight, B

2 3 2

O: 5 to 15% by weight, SiO: 4 to 12% by weight, ZnO: 3 to 12% by weight, A1 0: 3 to 10% by weight

3 2 2 3

%, ZrO: 0.1 to 5% by weight of the composition is the first feature.

2

In addition, the lead-free glass composition of the present invention is, in terms of oxide, Bi O: 65 to 72% by weight, B 2 O

2 3 2 3

: 10-15% by weight, SiO: 5-10% by weight, ∑110: 3-6% by weight, 8 10: 3-8% by weight,

2 2 3

The second feature is that the composition contains ZrO: 0.5 to 3% by weight.

2

In addition to the first or second feature, the lead-free glass composition of the present invention precipitates garnite (ZnAl 2 O 3) or zircon (ZrSiO 2) crystals when fired at 600 ° C. or lower. Is the third feature.

The lead-free glass composition of the present invention is added to the metal powder as a conductor that requires acid resistance in addition to any of the first to third features described above, and is sintered together. The fourth feature is that it is a glass powder as an agent.

Further, the lead-free glass composition of the present invention is, in addition to any of the first to fourth features described above, a glass powder for adding a metal electrode formed on a glass substrate of a plasma display panel. As a feature of

The lead-free glass composition of the present invention has a sixth feature that it is used as a glass for coating an electronic component surface in addition to any of the first to third features.

The invention's effect

[0006] According to the lead-free glass composition of claim 1, Bi O: 55 to 75 layers in terms of oxide

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Amount%, 0: 5-15% by weight, SiO: 4-12% by weight, ZnO: 3-12% by weight, A1 0: 3

2 3 2 2 3

10wt ^_0/0, ZrO: since a composition containing 1-5 wt% 0.,

2

It has been used in the past and does not adversely affect the environment due to the use of lead-based glass, and it has a soft temperature characteristic equivalent to that of lead-based glass as a glass, more specifically, a soft spot of 530 ° C or lower. It is possible to provide a glass material having characteristics that are maintained and have very good acid resistance. Therefore, as a glass material used for various components, parts, and devices such as plasma display panels that are exposed to acid in the manufacturing process and other usage conditions, it is possible to withstand an acidic atmosphere that is lead-free.

[0007] In addition, according to the lead-free glass composition of claim 2, the glass composition is converted into an oxide, Bi

O: 65 to 72% by weight, B O: 10 to 15% by weight, SiO: 5 to 10% by weight, ∑ 110: 3 to 6%

2 3 2 3 2

The amount ^_0/0, Al O: ^3~8 wt ^_0/0, ZrO: since a composition containing from 0.5 to 3 wt%,

2 3 2

The same effects as those of the lead-free glass composition according to claim 1 can be obtained. Furthermore, it is possible to secure a soft saddle point of 520 ° C. or lower and more reliably have good acid resistance.

[0008] In addition, according to the lead-free glass composition according to claim 3, garnite (ZnAl 2 O 3) when fired at 600 ° C or less in view of the effect of the structure according to claim 1 or 2. Or Jill

By precipitating crystals of 2 4con (ZrSiO), The acid resistance of the glass can be sufficiently improved.

[0009] Further, according to the lead-free glass composition according to claim 4, in addition to the effect of the structure according to any one of claims 1 to 3, the metal powder is formed to form a conductor that requires acid resistance. By being a glass powder as a sintering aid that is added and sintered together,

The sintered conductor of the metal powder mixed with the lead-free glass composition of the present invention can exhibit preferable acid corrosion resistance as a part of the apparatus, member, and component.

[0010] According to the lead-free glass composition according to claim 5, the metal electrode configured on the glass substrate of the plasma display panel in consideration of the effect of the configuration according to any one of claims 1 to 4. By adding glass powder for

The metal electrode formed by adding this glass powder is adapted to the glass substrate, and at the time of manufacturing the plasma display panel in the manufacturing process, etching using an acidic solution is performed during the manufacturing process. However, it is possible to prevent the metal electrode from being easily damaged by corrosion.

[0011] According to the lead-free glass composition according to claim 6, in addition to the effect of the structure according to any one of claims 1 to 3, the lead-free glass composition is acidic by being used as a glass for coating an electronic component surface. In the atmosphere, it is possible to exert a durable component protecting effect. BEST MODE FOR CARRYING OUT THE INVENTION

[0012] The lead-free glass composition of the present invention constitutes electrodes and electric wires laminated on a glass substrate of a plasma display panel, other glass substrates, and ceramic substrates. Mainly used as added glass powder. In addition, it can be used as glass for coating the surface of an electronic component that covers the surface of an electronic component that requires acid resistance, other glass members, glass components, and glass devices.

Further, in the present invention, “substantially free of Pb” means that no raw material containing lead such as PbO is used, and the raw materials of each component constituting the glass, the inorganic filler, etc. It does not exclude the case where lead as an impurity contained in is mixed.

[0013] The composition range of the lead-free glass composition according to the present invention will be described.

Bi 2 O is an essential component for forming a glass network and melting the glass.

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The component range is 55 to 75% by weight. Less than 55% by weight of glass has low melting On the other hand, when it exceeds 75% by weight, the acid resistance of the glass is lowered and becomes insufficient.

BiO is preferably 65 to 72% by weight. By making such a content range,

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Acid resistance can be improved without increasing the soft spot of the glass.

Bi O is more preferably 66 to 69% by weight.

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[0014] B 2 O forms a glass network and improves stability when the glass melts

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Is an essential ingredient.

The component range is 5 to 15% by weight. If it is less than 5% by weight, the glass becomes unstable. On the other hand, if it exceeds 15% by weight, the acid resistance of the glass decreases, which is not preferable.

B 2 O is preferably 10 to 15% by weight. By setting this content range,

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The acid resistance can be improved without increasing the soft saddle point of the lath.

B 2 O is more preferably 10 to 13% by weight.

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[0015] SiO forms a glass network to improve the acid resistance and stability of the glass when melted.

2

Is an essential ingredient.

The component range is 4 to 12% by weight. If it is less than 4% by weight, the acid resistance of the glass and the stability at the time of melting are lowered and become insufficient. On the other hand, if it exceeds 12% by weight, the glass tends to be devitrified.

SiO is preferably 5 to 10% by weight. By making such a content range,

2

The acid resistance can be improved without increasing the soft soft spot.

More preferably, SiO is 6 to 9% by weight.

2

[0016] ZnO is an essential component for melting the glass at a low temperature.

The component range is 3 to 12% by weight. If it is less than 3% by weight, the glass will not be sufficiently melted. On the other hand, if it exceeds 12% by weight, the acid resistance of the glass will decrease and become insufficient.

ZnO is preferably 3 to 6% by weight. By setting the content to such a range, the acid resistance can be improved without increasing the soft soft spot of glass.

[0017] Al 2 O is an essential component for improving the acid resistance of glass.

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The component range is 3 to: L0% by weight. If it is less than 3% by weight, the acid resistance of the glass It drops and becomes insufficient. On the other hand, if it exceeds 10% by weight, it tends to devitrify when the glass melts.

. Further, the binder performance as a sintering aid is lowered.

Al 2 O is preferably 3 to 8% by weight. By setting the content to such a range,

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The acid resistance can be improved without deteriorating the binder performance as a binder.

[0018] ZrO is an essential component for improving acid resistance.

2

The component range is 0.1 to 5% by weight. If it is less than 1% by weight, it will not be effective in improving the acid resistance of the glass. On the other hand, if it exceeds 5% by weight, it tends to devitrify when the glass melts. Further, the binder performance as a sintering aid is lowered.

ZrO is preferably 0.5 to 3% by weight. By making such a content range,

2

Acid resistance can be improved without deteriorating the binder performance as a sintering aid.

Regarding the firing of the glass composition of the present invention, garnite (ZnAl 2 O 3) or

2 4 Rucon (ZrSiO 2) crystals tend to precipitate and the acid resistance tends to improve immediately.

Four

In general, when glass contains a large amount of ZnO, the acid resistance tends to deteriorate. However, in the case of the present invention, the reason why the acid resistance is improved is as follows: Bi 2 O, B 2 O, SiO, ZnO,

2 3 2 3 2

By including Al O and ZrO in an appropriate range, (1) the glass softens during the heating process and becomes an adhesive.

2 3 2

(2) Decreasing the acid resistance of the glass phase As a result of a decrease in ZnO in the glass network due to part of the ZnO changing to crystals, etc. It is estimated that the acid resistance of the glass has improved.

[0020] In addition to the above components, BaO, SrO, CaO, MgO, FeO, CuO, CoO, TiO, etc. are used for the purpose of improving the stability during glass melting and adjusting the softening point and crystal precipitation of the glass. S

2 3 2 nO, CeO, Ln 2 O (lanthanoid), etc. may be added up to 2% by weight in total.

2 2 2 3

[0021] The lead-free glass composition of the present invention is dry pulverized as glass, the particle size is adjusted by the conditions of wet pulverization using an aqueous solvent or an organic solvent solvent, and the average particle size is 0.5 to 2 111. The maximum particle size is 10 μm or less.

If the average particle size is less than 0.5 m, the specific surface area of the glass powder increases, which makes foaming difficult to design. If the average grain size exceeds 2 m and the maximum grain size force S 10 m, fine patterning of wiring becomes difficult.

Preferably, the average particle size is 0.5 to 1. O ^ m, and the maximum particle size is 4 / zm or less. It is more preferable that the average particle size is 0.5 to 0.7 / ζ πι and the maximum particle size is 3 m or less. The obtained glass powder is mixed with a single substance or a metal powder for constituting a conductor, for example, Ag powder. Then, after printing or dispensing with a dispenser, firing is performed in a temperature range of 550 to 600 ° C. which is generally used in the manufacture of plasma display panels.

Example

Hereinafter, the present invention will be further described with reference to examples. However, the present invention is not limited to these examples.

(Examples 1 to 5 and Comparative Examples 1 to 5)

The raw materials were prepared and mixed for Examples 1 to 5 so as to have the component composition shown in Table 1, and placed in a platinum crucible and melted at 1200-1300 ° C for 2 hours. A lux body was produced. Separately, the molten glass was quenched to obtain glass flakes. Furthermore, glass flakes and ion-exchanged water were put in a pot mill, and wet pulverization was performed until the average particle size became 0.8 to 0.9 μm, followed by drying with hot air to produce a glass powder.

Similarly, glass powders were produced for Comparative Examples 1 to 5 so as to have the component compositions shown in Table 2.

[0023] For each example and comparative example, the glass load soft spot Td (° C) and acid resistance were measured. Moreover, about the Example, the identification of the deposit was performed.

The average particle diameter of glass powder, glass load softening point Td, and acid resistance were measured using the following methods.

(1) Average particle size of glass powder

The value of D in the volume distribution mode was determined using a laser scattering particle size distribution analyzer.

50

(2) Glass load soft spot Td (° C)

After melting at 1200 to 1300 ° C. for 2 hours, the glass barta body obtained by pouring into a mold was cut out to about 5 × 5 × 15 mm to prepare a test piece. Using a TMA measuring device, a glass load softening point Td (.C) was obtained with the yield point of the thermal expansion curve obtained when the temperature was raised from room temperature at 10 ° C. Zmim.

(3) Acid resistance The obtained glass powder was formed into a diameter of 20 mm by a dry press, sintered at 600 ° C., cut into 10 × 1 OX 3 mm, and a test piece was prepared. This specimen was immersed in a 10% aqueous nitric acid solution at 45 ° C. for 60 seconds, and the erosion rate (μm / mim) was measured from the weight loss and the bulk density.

[table 1]

[Table 2]

From Tables 1 and 2, it can be seen that the lead-free glass of Examples 1 to 5 has a soft spot equivalent to that of the lead-based glass of Comparative Example 1 and also exhibits excellent acid resistance.

In particular, the lead-free glass of Examples 4 and 5 has relatively low BiO, so it is excellent in cost.

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Yes.

Compared to the lead-free glass of the examples, the lead-free glasses of Comparative Examples 2 to 5 have a soft spot as low as that of lead-based glass, but are inferior in acid resistance.

Claims

The scope of the claims

[1] Oxide conversion

Bi O: 55 to 75% by weight

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B O: 5 to 15% by weight

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SiO: 4 to 12% by weight

2

ZnO: 3-12% by weight

Al O: 3 to 10% by weight

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ZrO: 0.1-5% by weight

2

The lead-free glass composition characterized by the above-mentioned.

[2] Oxide conversion

Bi O: 65-72% by weight

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B O: 10-15% by weight

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SiO: 5 to 10% by weight

2

ZnO: 3-6% by weight

Al O: 3 to 8% by weight

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ZrO: 0.5 to 3% by weight

2

The lead-free glass composition characterized by the above-mentioned.

[3] Garnite (ZnAl 2 O 3) or zircon (ZrSiO 2) crystals when fired at 600 ° C or lower

The lead-free glass composition according to claim 1, wherein 2 4 4 is precipitated.

[4] The glass powder according to any one of claims 1 to 3, which is a glass powder as a sintering aid that is added to a metal powder as a conductor that requires acid resistance and sintered together. Lead-free glass composition.

[5] The lead-free glass composition according to any one of [1] to [4], wherein the lead-free glass composition is a glass powder for adding a metal electrode formed on a glass substrate of a plasma display panel.

[6] The lead-free glass composition according to any one of [1] to [3], which is used as a glass for coating an electronic component surface.