KR101212393B1 - Lead-Free Borosilicate Glass Frit and Glass Paste Thereof - Google Patents

Abstract

In order to prevent environmental pollution, there is provided a glass frit for forming an insulating layer containing no PbO in the glass composition forming the insulating layer.

The total glass composition includes _{two or more} of SiO ₂ : 16 to 32 mol%, Al ₂ O ₃ : 4 to 8 mol%, B ₂ O ₃ : 20 to 35 mol%, Li ₂ O + Na ₂ O + K ₂ O 8-14 mol%, MgO + CaO + BaO + SrO is 3-16 mol%, ZnO: 6-33 mol%, Cu ₂ O: 0.01-3 mol%, Ag ₂ O: 0.01-1 mol%, The B ₂ O ₃ An unleaded borosilicate salt-free glass having a composition ratio of ZnO / B ₂ O ₃ = 0.27 to 1.3, wherein the glass frit has an average particle diameter of 1 to 5 µm and a maximum particle diameter of 20 µm or less. An unleaded borosilicate glass frit for forming an insulating layer having an excellent water resistance with a glass transition point of 500 ° C. or less, an average linear expansion coefficient of 65 to 80 × 10 ⁻⁷ / ° C., and a water resistance loss value of 0.1 mg / cm ² or less. .

Lead-free borosilicate, glass frit, glass paste, insulation layer

Description

Lead-Free Borosilicate Glass Frit and Glass Paste Thereof}

1 is a diagram showing an embodiment of the present invention.

2 is a diagram showing an embodiment of the present invention.

3 is a diagram showing an embodiment of the present invention.

4 is a diagram showing an embodiment of the present invention.

5 is a diagram showing an embodiment of the present invention.

It is a figure explaining a water resistance test and an acid resistance test.

7 is a plan view of the test article.

8 is a cross-sectional view of FIG. 7 showing a test article.

<Short description of symbols>

4 Black stripe 5, 6, 7 insulation layer (film)

6 Insulation layer (film) 10 Alumina substrate

11 Resistor 12 Internal Electrode

13 External Electrode 15 Glass Substrate

16 electrodes 17 wiring

Substrate glass of 18 copper foil 20 fluorescent display tube

21 wiring 22 lead

23 electrode 24 phosphor

25 grid 26 transparent electrode

27 windshield 28 filaments

30 back glass substrate 31 front glass substrate

32 address electrode 33 dielectric layer

34, 36, 37 Ribs (Interval) 40 Protective Film (MgO)

41 Dielectric Layer 42 Transparent Electrode

43 bus electrode

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to lead-free borosilicate salt glass frits, and more specifically, to insulating layers of electronic device components such as black stripes of plasma display panels and electronic display panels such as fluorescent display tubes and chip resistors. The present invention relates to a lead-free borosilicate glass frit and a glass paste comprising the glass frit for forming by firing.

Low melting point glass has been used as a composition of the glass which insulates the interlayer of electronic circuits, such as a plasma display panel and a fluorescent display tube. Conventional low melting point glass contains lead as a main component for lowering the melting point, but environmental problems have recently been pointed out for lead-containing glass, and lead-free glass having no problem in working environment and waste disposal is required. As a glass corresponding to such a problem, P ₂ O ₅ , Al ₂ O ₃ , SnO ₂ , ZnO, etc. which contain sealing and coating of a plasma display panel, a fluorescent display tube, and the like at a firing temperature of 600 ° C. or lower are mainly contained. A phosphate-based lead-free low melting glass has been proposed (Patent Document 1).

[Patent Document 1] Japanese Patent Application Laid-Open No. 2001-180972

This invention provides the glass frit for insulating layer formation which does not contain PbO in the glass composition which forms an insulating layer, in order to prevent the environmental pollution at the time of disposal, and can plate at the temperature of 590 degreeC or less, and averages The linear expansion coefficient is 65-80x10 <^-7> / degreeC, and it is providing the glass frit for insulating layer formation in which the crack did not generate | occur | produce in an insulating layer after plating.

In the present invention (claim 1), the glass composition is in terms of mol

SiO ₂ : 16-32 mol%,

Al ₂ O ₃ : 4-8 mol%,

B ₂ O ₃ : 20-35 mol%,

At least two or more of Li ₂ O + Na ₂ O + K ₂ O, the total of which is 8-14 mol%,

At least 3 mol% or more of BaO among MgO + CaO + BaO + SrO, and the sum of one or more of these is 3-16 mol%,

ZnO: 6-33 mol%,

Cu ₂ O: 0.01-3 mol%,

Ag ₂ O: 0.01 to 1 mol%,

And the composition ratio of the B ₂ O ₃ and _{ZnO, ZnO / B 2 O 3} = 0.27 ~ 1.3 the lead-free borosilicate glass as a basic composition,

The glass of the said composition is a glass frit whose average particle diameter is 1-5 micrometers, and whose maximum particle diameter is 20 micrometers or less, and whose glass transition point is 500 degrees C or less, and the average linear expansion coefficient is 65-80x10 <^-7> / degreeC, water resistance ( Lead-free borosilicate glass frit for forming an insulating layer by firing, characterized by excellent water resistance, having a performance of 0.1 mg / cm ² or less as a water resistant value under conditions exposed to pure water at 80 ° C. for 24 hours. to be.

In addition, the present invention (Claim 2) is formed by firing an insulating layer comprising an inorganic oxide, an organic solvent of at least one of the lead-free borosilicate glass frit, the inorganic pigment and the inorganic filler as described in (Claim 1). It is a glass paste for that.

In the present invention (Claim 3), the glass paste for forming the insulating layer according to (Claim 2) by firing is a black inorganic pigment whose inorganic pigment is Cu-Cr or Cu-Cr-Mn. It is characterized by being used for a display panel or an electronic display panel.

Specifically, the inorganic pigment is a black inorganic pigment of Cu-Cr or Cu-Cr-Mn type, or the inorganic filler is SiO ₂ And a low-expansion double oxide containing Al ₂ O ₃ , for example β-lithia spiteum or kojilite (cordierite), and at least one of these inorganic oxides and an organic binder and an organic solvent. It is a glass paste containing a vehicle made up.

Best Mode for Carrying Out the invention

The lead-free borosilicate glass frit of the present invention is a glass paste in which at least one inorganic oxide and an organic solvent of an inorganic pigment and an inorganic filler are mixed and coated and plated, thereby being used for electronic display panels such as black stripes of plasma display panels and fluorescent display tubes. The insulating layer of an electronic device component, such as an insulating layer and a chip resistor, is formed.

As electronic substrate components, such as a plasma display panel, an electronic display panel, and a chip resistor which plate an insulating layer, soda-lime plate glass is generally used as the board | substrate. By the way, the borosilicate-based glass frit according to the present invention is supposed to be plated with soda-lime glass, which is a general plate glass. The lead-free borosilicate glass frit is obtained by allowing the plate to be plated with a plate glass or the like at a temperature of 590 ° C. or less, considering the thermal expansion coefficient of 87 to 91 × 10 ⁷ / ° C. When it applies and bakes as a paste, it is a thing which a crack does not generate | occur | produce in the insulating layer formed by baking. In addition, aluminosilicate-based glass having a softening temperature of about 870 ° C. and a distortion point of about 570 ° C. can be plated at a temperature of 590 ° C. or less, and cracks are formed in the insulating layer formed by firing. It does not happen.

First, the glass composition of the lead-free borosilicate glass frit of the present invention will be described.

SiO ₂ is a network former, and is effective in stabilizing glass. When the content is less than 16 mol%, the stabilization effect of the glass is not sufficient, and when it exceeds 32 mol%, the softening point becomes too high. Therefore, the content of SiO ₂ is 16 ~ 32mol%, preferably 17 ~ 30mol%, and most preferably 18 ~ 25mol%.

Al ₂ O ₃ has an effect of stabilizing the glass and has an effect of increasing chemical durability. If the content is less than 4 mol%, the effect is not sufficient, the adhesiveness with the glass substrate is bad, and the durability is also poor. When it exceeds 8 mol%, the softening temperature becomes high and it is difficult to calcinate below 590 ° C. Further, Al ₂ O ₃ is more effective in water resistance than one quarter of the SiO ₂ content. Therefore, the content of Al ₂ O ₃ is 4 ~ 8mol%, preferably 4.5 ~ 7.0mol%.

B ₂ O ₃ has the effect of stabilizing the glass and increasing fluidity. If the content is less than 20 mol%, the effect is not sufficient, and the linear expansion coefficient is increased. If it exceeds 35 mol%, the effect on the stabilization and fluidity of the glass is insignificant, and the water resistance is lowered. Therefore, the content of B ₂ O ₃ is 20 ~ 35mol%, preferably 22 ~ 32mol%, and most preferably 25 ~ 30mol%.

Li ₂ O, Na ₂ O, and K ₂ O contain at least two or more of these three kinds, and the total is 8 to 14 mol%. This has the effect of lowering the softening temperature of the glass, and increasing the fluidity of Li ₂ O, Na ₂ O and K ₂ O. If the sum total is less than 8 mol%, the effect will not be acquired sufficiently. That is, the effect of lowering the softening temperature of the glass was not sufficient, and the yield point became 550 ° C. or more. Moreover, the viscosity of glass also becomes large and fluidity | liquidity falls. If the content exceeds 14 mol%, adverse effects such as lowering of chemical durability, lowering of electrical insulation, and excessive expansion coefficient may occur. Therefore, the total of Li ₂ O + Na ₂ O + K ₂ O is 8 to 14 mol%, preferably Preferably it is 9-12.5 mol%.

In addition, it was not sufficient to include at least two or more of three kinds of Li ₂ O, Na ₂ O, and K ₂ O in one kind of the effect of lowering the softening temperature of the glass and the effect of increasing the fluidity. The lead-free borosilicate glass frit of the present invention could not have its glass transition point below 500 ° C.

Three kinds of Li ₂ O, Na ₂ O, K ₂ O are, but total 8 ~ 14mol% as described above, Examples of the proportion of each, Li ₂ O is 4 parts, Na ₂ O is 6 parts, K ₂ O is Two parts are very preferred.

MgO, CaO, BaO and SrO are effective for stabilizing glass. When the sum total is less than 3 mol%, the devitrification of glass tends to occur, the crystallization at the time of baking cannot be suppressed, and when it exceeds 16 mol%, a softening temperature will become high and baking will become difficult. Moreover, when it exceeds 16 mol%, an average linear expansion coefficient will increase more than 80x10 <^-7> / degreeC, and when a film is formed into a film on a glass substrate, a crack generate | occur | produced and the coating film which has sufficient insulation effect was not obtained.

In addition, although the sum total of MgO + CaO + BaO + SrO is 3-16 mol%, since at least BaO suppresses the devitrification of glass, it is excellent in suppressing crystallization at the time of baking, and content of BaO is 3 mol% or more. It is.

ZnO is effective in stabilizing glass, lowering the softening temperature, and suppressing devitrification. If the content is less than 6 mol%, the effect is not sufficient, and if it exceeds 33 mol%, the crystallization becomes easy and a stable glass cannot be obtained, so the content is 6 to 33 mol%, preferably 10 to 28 mol%.

As the composition having the same composition as the borosilicate glass not containing Pb of the present invention, Cu ₂ O: 0.01 to 3 mol%, preferably 0.1 to _2.5 mol% and Ag ₂ O: 0.01 to 1 mol%, preferably 0.05 to 0.5 By containing mol%, it could plate on plate glass at the temperature of 590 degreeC or less, and the average linear expansion coefficient could be 65-80x10 <^-7> / degreeC at 40-300 degreeC.

In addition, copper oxide, silver oxide, but is limited to that amount as Cu ₂ O, Ag ₂ O, which, which will contain dissolved copper to the compound, the compound as a raw material, which may be the state of CuO, AgCO _3.

In the conventional low melting glass frit, lead is contained as a main component for the low melting point. Moreover, bismuth and phosphoric acid are contained as a main component as not using lead.

In the present invention, a borosilicate glass containing boric acid or silicic acid without containing lead and containing no bismuth or phosphoric acid, and containing CuO or Ag ₂ O to form an insulating film at or below 590 ° C. It is intended to have sufficient low melting performance and to form a dense and smooth film.

By the _{ZnO / B 2 O 3 = 0.27} ~ 1.3, it is possible to lower the crystallization rate. Specifically, the crystallization ratio can be 20% or less. Lead-free borosilicate glass frits that do not contain PbO are susceptible to crystallization. However, in the insulating coating obtained by firing with a glass paste containing a high glass powder having a crystallization ratio of 20% or more, the surface of the insulating coating does not smooth out unevenness. It may also cause a short circuit of the insulation coating. So lowering the crystallization rate. Preferably, ZnO / B ₂ O ₃ = 0.3 to 1.1. If the ZnO / B ₂ O ₃ of less than 0.27 will decrease the water resistance. The decrease in water resistance causes the absorbency of the glass in the fine grinding process for obtaining the fine particles, and causes the deterioration of the properties of the glass frit.

The glass frit of the present invention has a glass composition in terms of mol in terms of SiO ₂ : 16-32 mol%, Al ₂ O ₃ : 4-8 mol%, B ₂ O ₃ : 20-35 mol%, Li ₂ O ₃ and Na ₂ O and It contains at least two or more of K ₂ O, the total amount is 8 to 14 mol%, at least 3 mol% of MgO, CaO, BaO and SrO and at least 3 mol%, and the total of at least one kind is 3 to 16 mol%, ZnO: 6 to 33 mol%, Cu ₂ O: 0.2 to 3 mol%, Ag ₂ O: 0.01 to 1 mol% as a basic composition, and the composition ratio of B ₂ O ₃ and ZnO is ZnO / B ₂ O ₃ = 0.27 to 1.3 Lead-free borosilicate glass frit.

The glass frit of the composition of the present invention is a finely powdered powder having an average particle diameter of 1 to 5 µm and a maximum particle diameter of 20 µm or less, which is easy to melt and easy to paste into glass, and is suitable for coating and firing. As a result, a better insulating film can be obtained. However, when the glass is pulverized into fine powder, the surface area becomes large, so that the property of easily adsorbing moisture in the air is generally obtained. However, the glass frit of the present invention has a water resistance of 80 by adjusting to such a particle size. It was possible to make it excellent in water resistance which has the performance of 0.1 mg / cm <^2> or less as a water resistant loss value on the conditions exposed to pure water of 24 degreeC for 24 hours. The insulating film obtained by sintering has properties such as deterioration of the performance of the insulating film due to its performance of 0.1 mg / cm ² or less as a water resistant value under conditions of 24 hours exposure to pure water at 80 ° C. There is no change.

In addition, the glass frit of this invention has a glass transition point of 500 degrees C or less. In order to form a dense insulating coating at 590 ° C. or less on the device component and the glass substrate, the glass used as the coating material is required to have a glass transition point of 500 ° C. or less. As the glass frit of the present invention is finely powdered by adjusting the composition and particle size as described above, the glass transition point is 500 ° C or less, specifically, 450 ° C to 500 ° C.

When coating and baking a glass paste, when the baking temperature is high, the electrical characteristics of an electric circuit on a glass substrate will deteriorate, or a glass substrate will deform | transform, and it is necessary to bake at the baking temperature below 590 degreeC.

In addition, the glass frit of the present invention has an average linear expansion coefficient of 65 to 80 × 10 ⁻⁷ / ° C. In general, soda-lime-based glass is used for substrates such as plasma display panels, electronic display panels such as fluorescent display tubes, and chip resistors. And assuming that the insulating layer can be plated on a glass substrate of soda lime system, the glass frit of the present invention has the same composition as described above, so that the average linear expansion coefficient is 65 to 80 × 10 at 40 to 300 ° C. ^{It was -7} / ° C.

Generally, the linear expansion coefficient of the glass of soda lime system is 87-91x10 <^-7> / degreeC, and considering that, it is preferable that the average linear expansion coefficient is 65-80x10 <^-7> / ^degreeC . Since this is small in difference with the average linear expansion coefficient of the glass frit of this invention, when apply | coating and baking as a glass paste, a crack does not arise in the insulating layer formed by baking.

In other words, the insulating layer may deteriorate the insulation performance due to cracks, so that cracks do not occur.

In addition, when the insulating layer can be plated on the glass substrate, the glass substrate should not be deformed at the plating temperature. Glass substrate of soda lime system is softening temperature 730-740 degreeC, distortion point 495-505 degreeC, and when assuming that an insulating layer can be plated on the glass substrate of soda lime system, a glass substrate will deform | transform at plating temperature. In order to prevent this from happening, and in order not to deteriorate the electrical characteristics of an electric circuit, the glass transition point needs to be 500 degrees C or less, and the glass frit of this invention can meet such a request.

The glass frit of the present invention contains a vehicle made of at least one inorganic oxide and an inorganic filler, an organic binder and an organic solvent to form a glass paste, which is coated and baked to form an insulating layer. As the inorganic pigment, black inorganic pigment is used, and it is Cu-Cr type (for example, an oxide mainly composed of CuO, Cr ₂ O ₃ ) or Cu-Cr-Mn type, and the inorganic filler is SiO _2. And a low-expansion double oxide containing Al ₂ O ₃ , for example β-litia spodumene or kojilite. Black inorganic pigments and inorganic fillers are useful for suppressing transmittance.

The glass paste which specified the composition etc. in this invention mixes finely powdered glass frit, an inorganic heat-resistant pigment, and an inorganic filler, and then knead | mixes with a vehicle and forms a glass paste. The glass paste containing the frit of the specific glass etc. of this invention etc. are apply | coated to the predetermined | prescribed site | part on a component or a glass substrate by the screen-printing method, and after fully drying at 120 degreeC, it bakes at 590 degreeC or less. As said vehicle, what consists of resin and an organic solvent, and what melt | dissolved ethyl cellulose which is resin powder in butyl carbitol acetate or terpineol which is a solvent is used.

The glass frit of the present invention is mixed with a black inorganic pigment of Cu-Cr or Cu-Cr-Mn system as an inorganic pigment, mixed with an inorganic filler if necessary, and then kneaded with a vehicle to contain glass paste. The black stripe of the plasma display panel is used. The glass paste of this invention is apply | coated to the predetermined | prescribed site | part of a plasma display panel by the screen printing method, and after drying enough at 120 degreeC, it forms by baking at 590 degreeC or less. As a vehicle, what melt | dissolved ethyl cellulose which is resin powder in butyl carbitol acetate or terpineol which is a solvent is used.

According to the glass paste containing the glass frit of the present invention, a dense coating is formed by the composition, particle size adjustment, lowering the crystallization ratio, and the like of the specific glass in the present invention. It is reliable as an insulating layer of electronic display panels, such as a display tube.

Glass frit of the present invention is a raw material, silica, alumina, boric anhydride, boric acid, potassium nitrate, lithium carbonate, magnesium oxide, barium carbonate, calcium carbonate, galvanized, copper compound or silver compound in mol conversion percentage, SiO ₂ : 16 to 32 mol%, Al ₂ O ₃ : 4 to 8 mol%, B ₂ O ₃ : 20 to 35 mol%, Li ₂ O and at least two or more of Na ₂ O and K ₂ O are included, and the sum thereof 8-14 mol%, MgO, CaO, BaO and SrO contain at least 3 mol% of BaO, the total of at least one of them is 3-16 mol%, ZnO: 6-33 mol%, Cu ₂ O: 0.2-3 mol%, Ag ₂ O: 0.01 ~ 1mol% to the formulation so that the lead-free borosilicate glass as a basic composition, and melted.

Melting is performed in an atmospheric atmosphere using a platinum crucible. Friting is obtained by finely powdering a glass obtained by outflow onto an iron plate or by input into water and drying by a ball mill.

Specifically, it is vitrified for 20 minutes at 1240-1260 degreeC in a platinum crucible, and is rapidly air cooled. Grinding frit pulverizes a glass, and adjusts particle size to an average particle diameter of 1-5 micrometers, and to a maximum particle diameter of 20 micrometers or less.

In addition, the glass paste containing the glass frit of this invention,

40-50% by weight of glass frit of the present invention

Black Inorganic Pigment 15 ~ 25% by weight

Inorganic filler 0-5 wt%

3 ~ 5% by weight of resin

30-35% by weight of organic solvent

For example, 45% by weight of the glass frit, 20% by weight of black inorganic pigment, 2.5% by weight of inorganic filler, 3% by weight of ethyl cellulose, 29.5% by weight of butyl carbitol acetate or terpineol.

1-5, the Example of the insulating layer formed using the lead-free borosilicate glass frit of this invention is shown.

1-3 show the case where the lead-free borosilicate glass frit of this invention is used as a black stripe of a plasma display panel. FIG. 1 is a perspective view of a plasma display panel in which the front glass substrate 31 and the back glass substrate 30 are separated. 2 and 3 illustrate the front glass substrate 31 and the rear glass substrate 30 bonded together, and FIG. 2 is a cross-sectional view taken along line AA of FIG. 1 and FIG. 3 is a cross-sectional view taken along line BB of FIG. It is called.

1 to 3, the address electrode 32 is disposed on the back glass substrate 30 and is covered with the dielectric layer 33. Ribs (spacings) 34 are formed in the longitudinal direction of FIG. 1, and ribs (spacings) 36, 37 are formed in the transverse direction of FIG. 1. Phosphors R, G, and B are formed between the ribs (intervals) 34 and 36, 37.

The transparent glass 42, the black stripe 4, the bus electrode 43, the dielectric layer 41, and the protective film (MgO) 40 are formed on the front glass substrate 31.

The black stripe 4 of the front glass substrate 31 is polymerized to the ribs (intervals) 36 and 37 of the back glass substrate 30.

The front glass substrate 31 and the rear glass substrate 30 are bonded to each other, and then the gas is filled with a gas such as Ne-Xe after the vacuum is hermetically sealed.

As the glass frit and the inorganic pigment of the present invention, a glass paste obtained by mixing a Cu-Cr-based or Cu-Cr-Mn-based black inorganic pigment and kneading a kneader into a glass paste, as shown in the black stripe 4 of FIG. It apply | coats to 31 by screen printing method, and after drying enough, it forms by baking at 580 degreeC.

Fig. 4 shows the case where the lead-free borosilicate glass frit of the present invention is used as the insulating layer of the fluorescent display tube.

As shown in FIG. 4, the fluorescent display tube includes a wiring 21 formed on the substrate glass 20, a lead 22, an insulating layer (film) 6, an electrode 23, a phosphor 24, and a grid ( 25), the filament 28, the transparent electrode 26, and the windshield 27. As the insulating layer (film) 6, a glass paste obtained by mixing a black inorganic pigment of Cu-Cr or Cu-Cr-Mn system as a glass frit and an inorganic pigment of the present invention and kneading with a vehicle is used as the substrate glass 20. After apply | coating on the wiring 21 formed in the inside and performing sufficient drying, it is baked and formed at 580 degreeC.

Fig. 5 shows a case where the lead-free borosilicate glass frit of the present invention is used as the insulating layer of the chip resistor.

As shown in FIG. 5, the chip resistor consists of a resistor 11, an internal electrode 12, an external electrode 13, and an insulating layer (film) 5 on the alumina substrate 10. As the insulating layer (film) 5, the glass frit kneaded with the glass frit of the present invention is applied to the resistor 11 formed on the substrate 10, and after being sufficiently dried, it is baked and formed at 590 ° C or lower. will be.

The glass frit which specified the composition of this invention etc. specifies that the water resistance is excellent in water resistance which has the performance of 0.1 mg / cm <^2> or less as a water resistant value on the conditions of 24-hour exposure to 80 degreeC pure water.

About this water resistance, a water resistance test and an acid test are demonstrated. It is shown in the flowchart of FIG. The glass is powdered glass frit powdered and has an average particle diameter of 1 to 5 µm and a maximum particle size of 20 µm or less. The glass frit is subjected to a water resistance test and an acid resistance test in the state of sintering the glass frit, and exhibits its water resistance performance. will be.

As shown in the flowchart of Fig. 6, the glass frit is put in a plaster mold and sintered in a lump form. Subsequently, it processes to cylinder shape, and sets it as the sample of diameter 5mm x length 20mm. In the water resistance test, cylindrical glass samples having a diameter of 5 mm x 20 mm are placed in 50 ml of pure water in a poly container with a lid. This was hold | maintained for 24 hours in the thermostat set to 80 degreeC. It was taken out and the weight loss amount was computed. The amount of weight reduction per specific surface area of the columnar glass sample was calculated. This was made into the water weight loss value which shows water resistance.

In the acid resistance test, a cylindrical glass sample having a diameter of 5 mm x 20 mm was placed in 50 ml of a 1 N sulfuric acid solution in a poly container with a lid. This was kept for 24 hours in a thermostat set at 50 ° C. It was taken out and the weight loss amount was computed. The amount of weight reduction per specific surface area of the columnar glass sample was calculated. This shows acid resistance. And it evaluates comparatively about each glass sample.

In the present invention, the water resistance is specified to be excellent in water resistance such as having a performance of 0.1 mg / cm ² or less as a water resistance loss value under conditions of 24 hours exposure to pure water at 80 ° C. This shows that the lead-free borosilicate glass frit specifying the composition of the present invention is superior in long-term reliability, and is inferior to the frit of conventional lead oxide-containing glass, and is suitable for insulating layers and chip resistors of electronic display panels. It is useful for forming insulating layers of electronic device components.

Example

About this invention, Examples 1-5 and Comparative Examples 1-3 are shown in Table 1, 2.

In Tables 1 and 2, the composition is mol%, the glass transition point is ° C, the yield point is ° C, and the linear expansion coefficient α is in the range of 40 to 300 ° C at 10 ^-7 / ° C and the water resistance is 24Hr x 80 ° C. Mass loss (mg / cm ² ). That is, the chemical composition of Tables 1 and 2 is about 100% in total, but it is due to other components such as impurities.

Tables 1 and 2 show the chemical composition of the lead-free borosilicate glass frit and its properties. Glass frit has an average particle diameter of 1 to 5 µm and is powdered to a maximum particle diameter of 20 µm or less. Examples 1-5 are in the range of the specific composition in this invention.

The lead-free borosilicate glass frit of Examples 1 to 5 had a glass transition point of 500 ° C. or lower, a low yield point, a linear expansion coefficient α of 65 to 80 × 10 ⁻⁷ / ° C., and a water resistance of 0.1 mg / cm ² or less. It was excellent as a glass frit for forming the black stripe of a plasma display panel, the insulating layer of an electronic display panel, and the insulating layer of an electronic display component by baking.

Comparative Example 1 is 2.0 mol% of Li ₂ O and 5.0 mol% of Na ₂ O, and 7.0 mol% of the specific Li ₂ O + Na ₂ O + K ₂ O in the present invention outside the range of 8 to 14 mol%. . This yield point is more than _{550 ℃, Li 2 O, Na} 2 O, was not an effect of lowering the softening temperature of the glass by the K ₂ O is sufficient.

In Comparative Example 2, BaO is 14.5 mol% and SrO is 8.5 mol%, and the specific MgO + CaO + BaO + SrO is 23.0 mol% outside the range of 3 to 16 mol% in the present invention. The coefficient of linear expansion α is 89.2 × 10 ⁻⁷ / ° C., which exceeds the upper limit of 80 × 10 ⁻⁷ / ° C. of the specific expansion coefficient (65 to 80 × 10 ⁻⁷ / ° C.) in the present invention, and is plated on the glass substrate. When the film was formed, cracks occurred, and a coating film having a sufficient insulating effect could not be obtained.

In Comparative Example 3, B ₂ O ₃ is 36 mol%, the specific B ₂ O ₃ in the present invention is out of the range of 20 to 35 mol%, and ZnO / B ₂ O ₃ is 0.18, and ZnO / B specific in the present invention. ₂ O ₃ = 0.27 to 1.3. This is water resistance (mass loss 0.88 mg / cm ² ), indicating that the water resistance deteriorates when the ratio of ZnO / B ₂ O ₃ is less than 0.27.

Table 1 :

Example 1 Example 2 Example 3 Example 4 Example 5 SiO ₂ 18.5 30.0 21.0 19.0 19.0 Al ₂ O ₃ 4.5 5.5 6.0 6.0 6.0 B ₂ O ₃ 28.0 34.0 28.0 28.0 27.0 Li ₂ O 1.0 12.0 4.0 4.0 4.0 Na ₂ O 6.5 2.0 7.0 9.0 8.0 K ₂ O 2.0 MgO 6.5 1.0 1.0 CaO 3.5 2.5 2.5 BaO 3.0 3.0 3.0 3.0 3.0 SrO 3.0 ZnO 22.0 10.0 28.0 27.5 31.5 Cu ₂ O 2.3 0.4 0.4 0.1 0.4 Ag ₂ O 0.1 0.1 0.1 0.1 0.1 ZnO / B ₂ O ₃ 0.78 0.29 1.00 0.98 1.16 Glass transition point
Yielding point
Coefficient of linear expansion α
Water resistance 486.5
528.9
79.5
0.05 490.9
532.2
75.6
0.09 491.5
529.6
74.6
0.07 478.6
513.6
76.3
0.01 473.3
521.2
72.4
0.06

Table 2 :

Comparative Example 1 Comparative Example 2 Comparative Example 3 SiO ₂ 21.0 23.0 30.0 Al ₂ O ₃ 3.0 3.0 5.0 B ₂ O ₃ 30.0 27.0 36.0 Li ₂ O 2.0 10.0 12.5 Na ₂ O 5.0 2.0 1.5 K ₂ O MgO CaO 7.0 BaO 4.0 14.5 5.0 SrO 2.0 8.5 3.0 ZnO 22.5 7.5 6.5 Cu ₂ O 1.8 2.3 0.4 Ag ₂ O 0.1 0.1 0.1 ZnO / B ₂ O ₃ 0.75 0.27 0.18 Glass transition point
Yielding point
Coefficient of linear expansion α
Water resistance 510.2
561.4
69.1
0.07 451.8
492.6
89.2
1.54 490.9
532.1
75.6
0.88

In addition, the present invention will be described. Melting was melted in an atmospheric atmosphere using a platinum crucible. It carried out for 20 minutes at about 100 g of glass batch and 1240 degreeC.

Friting is obtained by ball-milling the glass obtained by the outflow to an iron plate, the input into water, and drying by a ball mill, and the particle size was adjusted to an average particle diameter of 1-5 micrometers, and 20 micrometers or less.

This glass frit is mixed with a vehicle which is a mixture of a black pigment, an inorganic filler, an ethyl cellulose resin, a terpineol or a butyl carbitol solvent (for example, 50 parts of glass frit, 22 parts of black pigment, 3 parts of inorganic filler, A stirrer and three rolls of zirconia were used in the ratio of 40 parts of vehicles), and it was set as the glass paste.

Using this glass paste, as shown in the plan view of FIG. 7 and the cross-sectional view of FIG. 8 as test articles, the electrode 16 and the wiring 17 are provided on the glass substrate 15, and the insulating layer is formed on the wiring 17. (7) was covered. And the copper foil 18 was provided on the insulating layer 7, the electrode 16 was connected with the conducting wire 19, and the withstand voltage test was done.

As a test article, the glass frit of the composition shown to Examples 1-5 and Comparative Examples 1 and 2 was kneaded with an inorganic pigment and a vehicle, it was made into a glass paste, it was apply | coated on the wiring 17, and sufficient drying was performed, The thing which baked at 580 degreeC and formed the insulating layer 7 was produced, respectively.

The withstand voltage test of the insulating layer 7 made the thickness of the insulating layer 7 of each test object 10 micrometers. The copper foil 18 was provided on the insulating layer 7, and the electrode 16 was connected by the conducting wire 19. As shown in FIG. Here, while voltage was applied between the copper foil 18 and the electrode 16, the voltage at which the insulation ruptured was measured while raising the voltage. As a result, Example 1 was 600V, Example 2 was 530V, Example 3 was 700V, Example 4 was 530V, and Example 5 was 530V. On the other hand, the thing of the comparative example 1 was 100V and the thing of the comparative example 2 was 300V.

This invention is excellent as a glass paste for forming insulating layers, such as an electronic component by baking, can plate at the temperature below 590 degreeC, and has an average linear expansion coefficient of 65-80x10 <^-7> / ^degreeC , After plating, an insulating layer can be formed so that a crack will not generate | occur | produce in an insulating layer, and the insulating layer with high breakdown voltage can be formed.

According to the lead-free borosilicate glass frit for forming the insulating layer of the present invention by firing, since it does not contain lead, there is no problem of environmental pollution, and the average coefficient of linear expansion at a glass transition point of 500 ° C. or lower and 40 to 300 ° C. Is 65 to 80 × 10 ⁷ / ° C., and when the water resistance is exposed to pure water at 80 ° C. for 24 hours, the water loss value is 0.1 mg / cm ² or less, which is excellent in water resistance and cracks in the insulating layer after firing. This does not occur and is excellent as a glass frit and a glass paste for forming an insulating layer of an electronic device component such as a black stripe of a plasma display panel, an electronic display panel such as a fluorescent display tube, or an electronic device component such as a chip resistor.

Claims (3)

The glass composition is in mol conversion percentage, SiO ₂ : 16-32 mol%, Al ₂ O ₃ : 4-8 mol%, B ₂ O ₃ : 20-35 mol%, At least two or more of Li ₂ O + Na ₂ O + K ₂ O, the total of which is 8-14 mol%, At least 3 mol% or more of BaO among MgO + CaO + BaO + SrO, and the sum of one or more of these is 3-16 mol%, ZnO: 6-33 mol%, Cu ₂ O: 0.01-3 mol%, Ag ₂ O: 0.01 to 1 mol%, The composition ratio of the B ₂ O ₃ and _{ZnO, ZnO / B 2 O 3} = 0.27 ~ 1.3, Lead-free borosilicate glass with The glass of the said composition is a glass frit whose average particle diameter is 1-5 micrometers, and whose maximum particle diameter is 20 micrometers or less, and whose glass transition point is 500 degrees C or less, and the average linear expansion coefficient is 65-80x10 <^-7> / degreeC, water resistance performance. Lead-free borosilicate for forming an insulating layer by firing, which is excellent in water resistance having a performance of 0.1 mg / cm ² or less as a water resistance loss value under conditions exposed to pure water at 80 ° C. for 24 hours. 염) Salt glass frit. A glass paste for forming an insulating layer by firing, comprising an inorganic oxide and an organic solvent of at least one of lead-free borosilicate glass frits, inorganic pigments and inorganic fillers according to claim 1. 3. The method of claim 2, The said inorganic pigment is a black inorganic pigment of Cu-Cr system or Cu-Cr-Mn system, and is used for a plasma display panel or an electronic display panel, The glass paste for forming an insulating layer by baking.

Images