JP4777814B2 - Multilayer conductive glass lining, multilayer conductive glass lining structure, and multilayer conductive glass lining construction method - Google Patents

Description

  The present invention has corrosion resistance used in the chemical industry, pharmaceutical industry, food industry, etc., and has a non-conductive undercoat glass lining layer, a non-conductive overcoat glass lining layer, a first overcoat conductive A multilayer conductive glass lining comprising at least four glass lining layers of a conductive glass lining layer and an outermost second conductive conductive glass lining layer; a glass lining structure comprising the multilayer conductive glass lining; And a method for constructing a multilayer conductive glass lining.

A glass layer composed of siliceous (SiO ₂ ) and alumina (Al ₂ O ₃ ) is strongly fired and bonded to the metal surface, and of these, it is particularly excellent in acid resistance, alkali resistance, and heat resistance. This is called glass lining (GL). GL used for GL devices and the like is manufactured by baking an undercoat glaze on a metal substrate such as a low-carbon steel plate or a stainless steel plate, and then baking an overcoat glaze with high corrosion resistance.

Since GL material is an insulating material with a surface resistivity of about 1 × 10 ¹³ to 10 ¹⁴ Ω / sq., When a non-aqueous organic solvent is stirred inside the GL device, sometimes high voltage static electricity is charged. However, even when the GL device or the like is grounded, there has been a problem that GL dielectric breakdown can occur due to static electricity.

  As means for solving this problem, it is known that a conductive substance is added to a glass frit and fired to form a conductive GL layer. For example, Patent Document 1 discloses a composition comprising metal fibers having a diameter of 0.01 to 0.5 microns, a length of 0.5 to 1500 microns, and a length / diameter shape ratio of 50 or more to 100 parts by weight of the frit. A conductive GL having a two-layer structure comprising an upper GL layer and an undercoat GL layer, which is characterized by containing ˜0.05 parts by weight and releases the charge in the volume direction (metal substrate direction), is disclosed.

  Also, a GL composition containing a frit, 0.05 to 1.5 parts by weight of ceramic fiber having a diameter of 0.1 to 30 microns, a length of 0.005 to 3 mm, and a length / diameter shape ratio of 50 or more with respect to 100 parts by weight of the frit Patent Document 2 discloses a conductive GL having a two-layer structure comprising an overlying GL layer and a subbing GL layer, which is characterized by being contained and releases a charge in the volume direction.

  In addition, at least three layers of GL including an undercoat GL layer and an overcoat GL layer fired without adding a conductive material to the glass frit, and an overcoat GL layer fired by adding a conductive material to the glass frit. Patent Document 3 discloses a conductive GL that is composed of layers and the upper conductive GL layer is the outermost layer.

Furthermore, Patent Document 4 discloses a GL composition in which acicular conductive antimony-containing tin oxide powder is added to a glass frit as a conductive oxide ceramic.
Japanese Patent Laid-Open No. 11-116273 JP-A-11-189431 Japanese Patent Laid-Open No. 2005-314791 JP 2005-314194 A

  However, in the conductive GL disclosed in Patent Document 1 and Patent Document 2, when a high-voltage electrostatic discharge actually occurs, a high-voltage charge flows through the GL layer to the metal substrate. Therefore, there is a problem that the GL layer is easily broken down. Moreover, since the entire GL layer contains a conductive material, there is a problem in quality control that a no-pinhole confirmation test cannot be performed by a discharge test, and there is a large amount of conductive material used, which is an expensive conductive material. There was also an economic problem that the production cost would be higher when using.

  On the other hand, the conductive GL disclosed in Patent Document 3 is characterized in that the charge is released in the surface direction (the creeping direction), and therefore it is necessary to add a highly conductive noble metal or noble metal compound to the glass frit. is there. However, since noble metals or noble metal compounds are very expensive, there is a problem that if the thickness of the uppermost conductive GL layer is increased in order to improve the durability of the GL, the manufacturing cost increases.

  In addition, in the GL disclosed in Patent Document 4, since the content of antimony-containing tin oxide is low, it is difficult to obtain a sufficient antistatic effect. Moreover, since a conductive substance is added to all layers, it has the same defects as the conductive GL disclosed in Patent Document 1 and Patent Document 2.

  Furthermore, when a noble metal or noble metal compound powder is added to the glass frit and baked, the GL layer becomes a dark color close to black. For this reason, there has been a demand for a conductive glass lining structure that is easier to inspect the inside of the structure with a brighter color.

  Therefore, the present invention maintains the conductivity of the GL surface while suppressing the manufacturing cost, and the hue of the conductive GL layer so that the inside can be observed more easily than a GL structure that holds a black or amber GL layer. It is an object to provide a multi-layered conductive GL and a structure made of GL that retain the above. Moreover, it aims at providing the construction method of such a multilayer electroconductive GL.

  The present invention relates to a conductive GL comprising at least an undercoat GL layer and an overcoat GL layer having no conductivity, and at least two types of overcoat GL layers containing different conductive substances. Further, the present invention relates to a GL device constituted by the multilayer conductive GL, a GL structure such as a GL container, and a construction method thereof.

Specifically, the present invention
An undercoat normal GL layer fired without adding a conductive material to a glass frit on a metal substrate;
An overlying normal GL layer fired without adding a conductive material to the glass frit;
A first overlying conductive GL layer fired by adding a first conductive material to a glass frit;
A multilayer conductive film comprising at least four GL layers including a second overlying conductive GL layer obtained by adding a second conductive material different from the first conductive material to a glass frit and firing the glass frit. It relates to sex GL (Claim 1).

The present invention also provides:
A subbing normal GL layer fired without adding a conductive material to the glass frit;
An overlying normal GL layer fired without adding a conductive material to the glass frit;
A first overlying conductive GL layer fired by adding a first conductive material to a glass frit;
At least four GL layers including a second overlying conductive GL layer obtained by adding a second conductive material different from the first conductive material to the glass frit and firing are applied on the metal substrate. It is related with the construction method of multilayer electroconductive GL (Claim 9).

  The first conductive material is preferably an indium compound, an antimony compound, a noble metal, or a noble metal compound, and the second conductive material is titanium oxide coated with antimony-containing tin oxide, tin oxide, or antimony-containing oxide. It is preferably any one of barium sulfate coated with tin, phosphorus-containing tin oxide, or barium sulfate coated with tin oxide (claims 2 and 10).

  The indium compound is preferably indium oxide or tin oxide-containing indium oxide, the antimony compound is preferably antimony oxide, or antimony oxide-containing tin oxide, and the noble metal or noble metal compound is platinum, silver, It is preferably either ruthenium dioxide or iridium dioxide (claims 3 and 11).

  In particular, the first conductive material is preferably ruthenium dioxide, and the second conductive material is preferably titanium oxide or tin oxide coated with antimony-containing tin oxide (claims 4 and 12).

  In this case, the amount of ruthenium dioxide added to the glass frit is 2 to 15% by weight, and the amount of titanium oxide coated with antimony-containing tin oxide to the glass frit is 6 to 30% by weight. (Claims 5 and 13).

  Further, the amount of ruthenium dioxide added to the glass frit is preferably 2% by weight to 15% by weight, and the amount of tin oxide added to the glass frit is preferably 10% by weight to 20% by weight. ).

  The thickness of the second overlying conductive GL layer on the surface layer side is preferably larger than the thickness of the first overlying conductive GL layer on the lower layer side (Claims 7 and 15).

  Moreover, this invention relates to the structure made from multilayer conductive GL comprised from the multilayer conductive GL of any one of Claims 1 thru | or 7. (Claim 8).

  The average particle diameter of the first conductive material added to the glass frit is preferably 0.2 μm or less (claim 16).

  In the multilayer conductive GL of the present invention, the conductive GL layer containing different conductive substances is made into a multilayer, so that combinations of conductive substances according to the application are possible, and antistatic performance and durability can be improved. it can.

  In addition, the multilayer conductive GL of the present invention includes a noble metal or a noble metal compound that has high conductivity but is expensive, or an indium compound or antimony compound that has high conductivity but has poor corrosion resistance. Antistatic effect, durability and manufacturing cost by constructing the second overlying conductive GL layer containing an inexpensive conductive material on the first overlying conductive GL layer contained as a material) All of them are excellent.

  In addition, the multilayer conductive GL of the present invention is made of GL by using a conductive material (second conductive material) having a light color for the second overlying conductive GL layer as the outermost layer. It has a feature not found in the conventional conductive GL that it is easy to visually check the inside of the structure.

  Furthermore, the multilayer conductive GL of the present invention can be inspected for the occurrence of pinholes by a discharge test if a primary inspection is performed before the first overlying conductive GL layer is formed. It is also possible to improve the quality of management.

  Embodiments of the present invention will be described below with reference to the drawings as appropriate. The present invention is not limited to these.

  A cross-sectional view of the multilayer conductive GL of the present invention is shown in FIG. The multi-layer conductive GL of the present invention has an undercoat GL layer that does not contain a conductive material (undercoat normal GL layer) and an overcoat GL layer that does not contain a conductive material (overcoat normal GL layer) on a metal substrate. ), An indium compound, an antimony compound, a noble metal or a noble metal compound added to a glass frit and fired as a first conductive material, and an antimony-containing tin oxide as a second conductive material Second over-conductive film fired by adding any of titanium oxide coated with tin, tin oxide, phosphorus-containing tin oxide, tin oxide-coated barium sulfate, antimony-containing tin oxide coated barium sulfate to a glass frit At least four glass lining layers of the sex GL layer are provided in this order.

  The first conductive material preferably has high conductivity. Furthermore, the first overlying conductive GL layer added with the second conductive material is formed on the first overlaid conductive GL layer added with the first conductive material. The conductive substance may have low corrosion resistance against acids and alkalis. Further, the first overlying conductive GL layer may have any color.

  On the other hand, it is preferable that the second overlying conductive GL layer to which the second conductive material is added has high corrosion resistance. Moreover, since it is a GL layer constructed on the surface layer, the color is preferably light. Furthermore, the multilayer conductive GL of the present invention has a structure that uses the first overlying conductive GL layer and the second overlying conductive GL layer to release the charged charges in the creeping direction. The conductivity of the overlying conductive GL layer may be lower than that of the first conductive glass lining layer.

  The overlying normal GL layer, the first overlying conductive GL layer, or the second overlying conductive GL layer is one layer in the example of FIG. 1, but may be two or more layers.

  Since the outermost layer of the multilayer conductive GL of the present invention is a conductive GL layer, it is possible to release the charge in the surface direction (creeping direction) as in the case of the conductive GL disclosed in Patent Document 3. Here, in the field | area where the apparatus which constructed the electrically conductive glass lining of this invention is used, in addition to favorable antistatic performance, it is calculated | required that a discharge breakdown voltage is high.

  Even if the GL layer is prevented from being charged by imparting electrical conductivity to the GL layer (antistatic), the insulating contents continue to rub against each other by stirring, etc. inside the device, and charging is always generated. For this reason, when the charge of the contents increases, even if GL is conductive, a discharge occurs and the glass is broken.

  In the multi-layer conductive GL of the present invention, both the above-described both are provided in order to release the electric charges in the surface (creeping) direction and hold a normal GL layer having high insulation between the metal substrate and the conductive GL layer. The performance can be satisfied.

  In the conductive GL disclosed in Patent Document 3, in order to obtain a high antistatic effect, a noble metal or a noble metal compound is used as a conductive substance, so that the outermost layer is used to improve the durability and wear resistance of the GL. Increasing the thickness of the overlying conductive GL layer increases the manufacturing cost. For this reason, in order to reduce the manufacturing cost, the overlying conductive GL layer has to be applied thinner than the overlying normal GL applied to the lower layer, and the GL structure at the beginning of manufacture is prevented from being charged. While the effect was very high, it was difficult to construct thickly for long life.

  However, the multi-layer conductive GL of the present invention has a low conductivity but is slightly inferior to the first overlying conductive GL layer (high conductive GL layer) to which a highly conductive substance is added. A second overlying conductive GL layer using a material is applied to form a multilayer conductive GL layer. For this reason, it is possible to improve the corrosion resistance of the GL while maintaining the antistatic effect on the GL surface and suppressing the manufacturing cost, thereby extending the life.

  That is, by laminating an expensive and highly conductive first overlying conductive GL layer and a second inexpensive overlying conductive GL layer that is moderately conductive, a high antistatic effect and a long It is possible to achieve both life extension.

  The second overlying conductive GL layer, which is the outermost layer, is preferably constructed thicker than the first overlying conductive GL layer. This is because if the outermost layer is thin, it is not possible to sufficiently extend the life.

  The second overcoat GL layer, which is the outermost layer, is not particularly limited as long as the color of the conductive glass lining is light when the conductive material is added to the glass frit and baked. In the color system, the hue is red (R), yellow (Y), green (G), purple (P), yellow-red (YR), yellow-green (GY), blue-green (BG), blue-violet (PB), red In the case of purple (PR), it is preferable to select a conductive substance having a brightness of 7 to 9.5. Moreover, when the hue is blue (B) in the Munsell color system, it is preferable to select a conductive substance having a lightness of 6 to 9.5 and a saturation of 0 to 6. This is to facilitate observation of the inside of the GL structure while maintaining the conductive performance.

As a conductive substance (first conductive substance) added to the glass frit of the first overlying conductive GL layer, a noble metal or a noble metal compound is preferable. These are because of high conductivity. When ruthenium oxide or iridium oxide (IrO ₂ ) is added as the noble metal compound, the addition amount is preferably 2 wt% or more and 15 wt% or less. If it is less than 2% by weight, the antistatic performance is low, and if it exceeds 15% by weight, the antistatic performance does not change and only the construction cost increases.

  Moreover, an indium compound or an antimony compound can also be used as a conductive substance (first conductive substance) added to the glass frit of the first conductive GL layer. The amount added to the glass frit is preferably 11% by weight to 25% by weight when using tin oxide-containing indium oxide (ITO), and 15% by weight to 30% by weight when using antimony-containing tin oxide (ATO). .

  As the noble metal, Ru, Rh, Pd, Ag, Os, Ir, Pt or Au can be used, and one or more of these may be used. Moreover, these alloys may be sufficient. In addition, when using silver (Ag), it is preferable that the addition amount to a glass frit shall be 30 to 70 weight%.

The noble metal compound is preferably a noble metal oxide from the viewpoint of corrosion resistance, and more preferably ruthenium dioxide (RuO ₂ ) from the viewpoint of improving the conductivity by forming a composite oxide after firing. When ruthenium dioxide is used as the conductive material, the firing temperature of the overlying highly conductive GL layer must be 880 ° C. or lower.

  On the other hand, the conductive material (second conductive material) added to the glass frit of the second overlying conductive GL layer is titanium oxide coated with antimony-containing tin oxide, tin oxide, phosphorus-containing tin oxide or tin oxide. Are preferably barium sulfate coated with antimony and tin oxide coated with antimony-containing tin oxide, and one or more of these may be used. This is because they are inexpensive and the color tone of the glass frit after firing is light.

  The second conductive material is titanium oxide coated with antimony-containing tin oxide because it has a light glass color tone when added to a glass frit and fires the GL layer, and has good conductivity and corrosion resistance. Or tin oxide is particularly preferable.

  When the second conductive material is titanium oxide coated with tin oxide, the amount added to the glass frit is preferably 6% by weight or more, and 15% by weight or more from the viewpoint of ensuring conductivity. Is more preferable. On the other hand, if the amount added is too large, the glass frit does not become glassy after firing, and therefore it is preferably less than 30% by weight and more preferably less than 25% by weight.

  When the second conductive material is tin oxide, the amount added to the glass frit is preferably 10% by weight or more, and preferably 20% by weight or less. Normally, when only tin oxide is used alone as a conductive material, good conductivity cannot be obtained even if tin oxide is added to a glass frit of 20% by weight or more. Thus, even a conductive material that has low conductivity and cannot be used alone can be used.

  In the GL example shown in FIG. 1, the thickness of the second overlying conductive GL layer is preferably 0.1 mm or more and 0.6 mm or less. If the thickness is less than 0.1 mm, the conductivity is high, but the construction cost is high, and the effect of protecting the overlying highly conductive GL layer is low, which is insufficient to improve the corrosion resistance. Accordingly, it is usually necessary to reduce the thickness of the GL layer, so that the discharge breakdown voltage performance is degraded.

  Furthermore, since the overall thickness of the GL is determined from its workability, if the second overlying conductive GL layer is made too thick, the first overlying conductive GL layer, usually the overlying GL, is adjusted accordingly. It is necessary to reduce the thickness of the layer and the subbing normal GL layer, and as a result, the discharge breakdown voltage may be reduced.

  Also, from the viewpoint of facilitating observation of the inside of the GL tank or the like, the thickness of the second overlying conductive GL layer is preferably 0.1 mm or more. This is because if the thickness is less than 0.1 mm, the first overlying conductive GL layer can be seen through, making it difficult to observe the inside of the tank.

  As described above, the hue of the second overlying conductive GL layer is not particularly limited as long as it is a light color, but in the Munsell color system, the hue is red (R), yellow (Y), green (G), In the case of purple (P), yellow-red (YR), yellow-green (GY), blue-green (BG), blue-purple (PB), and red-purple (PR), the lightness is preferably 7 to 9.5, and the hue is blue In the case of (B), it is preferable that the lightness is 6 to 9.5 and the saturation is 0 to 6. The color tone of the GL layer can be measured using a commercially available color difference meter.

(Slip production)
Table 1 shows the composition of the glass frit used in the production of the light-colored conductive GL having the four-layer structure. The glass frit that can be used for the production of the undercoat GL layer and the overcoat GL layer of the multilayer conductive GL of the present invention is not limited to Table 1, and any commonly used one can be used. is there. Addition of ruthenium dioxide as the first conductive material and titanium oxide coated with antimony-containing tin oxide as the second conductive material (ATO-TiO ₂ , Ishihara Sangyo ET-300W) did.

  After the glass frit (and the conductive material) was put into a pot mill, water was further added and the frit was pulverized until it was ready for glazing. After pulverization, the particle size distribution of the glass particles is measured using a Nikkiso Microtrack Series 9200 FRA, and the average particle size of the glass particles (50% of the weight cumulative particle size distribution) is 20 to 40 μm. It was confirmed. If the particle size distribution is within the above range, the slip is completed.

  The average particle diameter of the glass particles in the slip is preferably 1 to 100 μm, particularly 10 to 60 μm from the viewpoint of slip spraying work and GL quality after firing.

  In order to evenly disperse the conductive material in the second overlying conductive GL layer and to smooth the surface of the second overlying conductive GL layer, a conductive material (first material mixed with the glass frit) is used. The second conductive material) is preferably in the form of a fine powder. Specifically, the average particle diameter (50% diameter of the weight cumulative particle size distribution) of the conductive powder material is preferably 0.2 μm or less.

In addition, the specific surface area of the second conductive substance in powder form is 5 m ² / g or more, preferably 10 m ² / g or more, more preferably 20 m ² / g or more. Further, by smoothing the surface of the second overlying conductive GL layer, adhesion of the processed material to the surface of the second overlying conductive GL layer can be reduced. The surface of the second overlying conductive GL layer 3 preferably has an average roughness (Ra) of about 0.05 to 0.09 μm.

In applications where surface smoothness is not a problem, the second conductive material may be in the form of fibers or needles.
(Glazing and firing on metal substrates)
As the metal substrate, a commonly used metal substrate such as low carbon steel or stainless steel can be used. Here, a square mild steel having a side of 100 mm was used. In addition, the slip of the undercoat GL layer and the overcoat GL layer was applied on the metal base material in order by a well-known method of using a spray and fired.

  First, a subbing normal GL layer was applied to a metal substrate with a thickness of 0.2 mm using a spray and fired at 920 ° C.

  Next, glazing by spraying and baking at 850 ° C. were repeated a plurality of times in order to construct a 0.7 mm upper normal GL layer on the lower normal GL layer. In the multilayer conductive GL of the present invention, it is desirable that the thickness of the undercoat normal GL layer + the overcoat normal GL layer is 0.4 mm to 1.0 mm.

  Here, the non-conductive GL is a non-pinhole confirmation in which a brush or needle-like electrode to which a high voltage of direct current or alternating current is applied is applied to the test sample, and the presence or absence of pinholes in the GL layer is inspected by concentration of short circuit or discharge. The quality control of the product was able to be performed by the test. However, in the conventional all-layer conductive GL, both the overcoat GL layer and the undercoat GL layer contain a conductive material. Therefore, after glazing and firing the GL layer, non-pinhole property confirmation by discharge is performed. The test could not check for the presence of pinholes. For this reason, the non-pinhole property is confirmed by inspection with the naked eye, and it can be said that it is impossible to actually inspect the entire surface of the GL layer by visual inspection or the like, which is a big problem in quality control. It was.

  On the other hand, in the multi-layer conductive GL of the present invention, the undercoat normal GL layer and the overcoat normal GL layer do not contain a conductive material, so that the undercoat normal GL layer and the overcoat normal GL layer are coated on a metal substrate. Even after firing, the presence or absence of pinholes can be inspected by a non-pinhole property confirmation test by applying a high voltage by direct current or alternating current. Thus, before the first overlying conductive GL layer and the second overlying conductive GL layer are glazed and fired, the occurrence of pinholes is checked as a primary inspection of the product (work-in-process). In the unlikely event that pinholes exist in the first overlying conductive GL layer and the second overlying conductive GL layer of the final product, the metal substrate and the second overlying conductive material Since there is an underlayer normal GL layer and an overlayer normal GL layer without a pinhole between the GL layer, the second uppermost conductive layer GL which is the outermost layer and the first upper conductive layer which is the lower layer. Corrosion / elution of the metal substrate can be effectively prevented by erosion from the pinholes present in the conductive GL layer.

  Next, on the overlying normal GL layer, the first overlying conductive GL layer was applied with a spray with a thickness of 0.1 mm to 0.2 mm and baked at 850 ° C. A second overlying conductive GL layer was applied thereon with a spray having a thickness of 0.1 mm to 0.6 mm, and baked at 830 ° C. to form two conductive GL layers.

[Example]
After applying up to the normal GL layer by the above construction method, a slip with 4 to 6% by weight of ruthenium dioxide (RuO ₂ ) added to the glass frit as a conductive material (first conductive material) is 0.1 mm thick And baked at 850 ° C., and applied the first overlying conductive GL layer (black).

On top of that, a slip of 25% by weight of ATO-TiO ₂ added to a glass frit as a conductive material (second conductive material) was applied using a spray with a thickness of 0.3 mm by the above construction method. Firing was performed at 0 ° C., and a second overlying conductive GL layer was applied.

  A GL (a square with a side of 100 mm) provided with four GL layers thus produced was used as an example of the present invention. In addition, the thickness of the undercoat normal GL layer was 0.2 mm, the thickness of the normal overcoat GL layer was 0.6 mm, and the total thickness of the GL layer was 1.2 mm.

[Comparative Example 1]
On the same metal substrate as in the example, without adding a conductive substance to the glass frit, two layers of a subbing normal GL layer 0.2 mm and a subbing normal GL layer 1.0 mm were applied by the above-mentioned construction method and had no conductivity. Usually, GL (a square with a side of 100 mm) was used as Comparative Example 1 of the present invention.

[Comparative Example 2]
A conductive GL produced in the same manner as in the example, except that the first overlying conductive GL layer was not applied and the second overlying conductive GL layer was 0.3 mm, Comparative Example 2 of the present invention. It was.

[Comparative Example 3]
In order to make the entire GL layer conductive GL, 25% by weight of ATO-TiO ₂ as a conductive material is added to the glass frit for subbing, and the subbing GL layer is constructed with a thickness of 0.2 mm. As a conductive material, 25% by weight of ATO-TiO ₂ was added to the glass frit for coating, and an overcoat GL layer was applied with a thickness of 1.0 mm. The conductive GL produced in this manner was used as Comparative Example 3 of the present invention.

[Comparative Example 4]
To make the entire GL layer conductive GL, add 4 to 6% by weight of ruthenium dioxide as a conductive material to the glass frit for subbing, and apply the subbing GL layer to a thickness of 0.2 mm. The glass frit for use was added with 4 to 6% by weight of ruthenium dioxide as a conductive material, and an overcoat GL layer was applied to a thickness of 1.0 mm. The conductive GL produced in this manner was used as Comparative Example 4 of the present invention.

[Comparative Example 5]
On the same metal substrate as in the example, two layers of a subbing normal GL layer 0.2 mm and a subbing normal GL layer 0.9 mm were applied without adding a conductive substance to the glass frit. Further, 4 to 6% by weight of ruthenium dioxide as a conductive material was added to the glass frit, and an overcoat GL layer was applied to a thickness of 0.1 mm. The conductive GL thus produced was used as Comparative Example 5 of the present invention.

  With respect to the six types of GL samples of Examples and Comparative Examples 1 to 5, the charged voltage and the high voltage pulse breakdown voltage were measured.

(Battery voltage confirmation test)
The metal base portion of the GL was grounded, and further grounded from the end of the GL layer through the cross section. After holding this GL sample in an atmosphere with a humidity of 10% or less for 12 hours or more, the needle electrode is placed 1.5 cm away from the GL surface in that atmosphere, and in this state, 15 kV is applied to the needle electrode to cause corona discharge. The GL sample was charged for 30 seconds, and the charged voltage (V) immediately after application for 30 seconds was measured. Further, the time until the measured charged voltage was halved (charged voltage half time: second) was measured.

(Destructive testing using high voltage pulses)
A destructive test using a high voltage pulse was performed assuming that electrostatic discharge was generated. That is, a positive or negative high voltage pulse (pulse half-time of about 20 μsec) adjusted to an arbitrary voltage value is applied to the GL samples of Examples and Comparative Examples 1 to 5, and the GL layer is a base metal in the depth direction. It was confirmed whether it was penetrated to (metal substrate) and destroyed, and the applied pulse voltage at which the destruction occurred was grasped.

  Table 2 shows the results of the charged voltage test and the destructive test, and the measured results of the charged voltage half time.

  As a result of the charged voltage test, the GL samples of Comparative Examples 1 to 3 had a very high charged voltage and were easily charged. On the other hand, the GL sample of the example was 52.5 kV even when a voltage was applied. It was a GL that was only charged and difficult to charge. Further, as for the high voltage pulse breakdown voltage, in Comparative Example 1 and Comparative Example 3, a pinhole was generated on the GL surface when about 30 kV was applied, and dielectric breakdown occurred.

  Further, it was confirmed that the half-life of the charged voltage was less likely to charge the GL sample of the example and the charged charge was more likely to escape than the GL sample of Comparative Example 1.

  Note that the GL sample of Comparative Example 3 has a significantly shorter half-life than that of the Example, which is considered to be due to the high initial voltage.

  In Comparative Example 2, the high voltage pulse breakdown voltage was higher than that in Comparative Example 1 and Comparative Example 3, but a tendency was found that the charged voltage was high and it was easily charged.

  In Comparative Example 4, it was confirmed that the GL had the lowest charged voltage and was difficult to be charged. However, in the high voltage pulse breakdown test, a pinhole was generated on the GL surface at the lowest voltage, and dielectric breakdown occurred.

  In Comparative Example 5, the charged voltage was low, and the high voltage pulse breakdown test showed a high value.

  On the other hand, when the GL sample of the example was discharged with the same high voltage pulse of 30.0 kV as the GL sample of Comparative Example 1, only a discharge trace remained on the GL surface, and no dielectric breakdown occurred. The voltage at which dielectric breakdown occurs was 10 kV or more higher than that of the GL sample of Comparative Example 2 in which the conductive GL layer was a single layer.

  As described above, the GL sample of the example is not only difficult to be charged because the conductive GL layer has a multilayer structure of the first overlying conductive GL layer and the second overlying highly conductive GL layer. In the unlikely event that a high voltage pulse occurs, it was confirmed that the dielectric breakdown was difficult and the performance was equivalent to that of the GL sample of Comparative Example 5.

  Further, in the GL sample of Comparative Example 5, the thickness of the conductive GL layer is 0.1 mm, whereas the GL sample of the Example is 0.4 mm. Therefore, the corrosion resistance of the conductive GL layer compared to Comparative Example 5 ( Life) can be extended.

  In addition, about the GL sample of the comparative example 5, although it is possible to change the thickness of an electroconductive GL layer to 0.4 mm, since a noble metal is utilized as an electroconductive substance, manufacturing cost will become high. In the GL sample of the example, since the conductive material added to the second conductive GL layer as the surface layer is inexpensive, the thickness of the conductive GL layer can be increased while suppressing the manufacturing cost. As a result, the lifetime of the conductive GL layer can be extended.

  Next, the photograph which image | photographed each GL sample surface is shown in FIG. Comparative Example 1 had a dark blue color, and Comparative Examples 4 and 5 had a black surface. For this reason, the GL samples of Comparative Example 1, Comparative Example 4 and Comparative Example 5 become dark when the GL structure is created, and it is difficult to check the cleanability and the GL layer damage status. It became.

  On the other hand, since Example 1, Comparative Example 2 and Comparative Example 3 have a light surface, when the GL structure is created, the inside of the structure is bright and the cleaning property is confirmed and the GL layer is inspected for damage. It became easy to do.

  As described above, the multi-layer conductive GL of the present invention, like the conductive GL disclosed in Patent Document 3, is not easily charged and hardly causes dielectric breakdown, and also has a light surface. When used in a GL structure, the interior is easily observed visually. Also, if lines or numbers are constructed using a glass frit with a highly conductive material such as ruthenium dioxide on the GL surface, a scale may be provided inside the GL structure without affecting the antistatic effect. It is possible and convenient for checking the volume of the contents.

  In addition, the multilayer conductive GL of the present invention can improve the durability and wear resistance of the GL while suppressing the manufacturing cost if the outermost conductive GL layer of the outermost layer is thickly applied. . In addition, when the outermost second conductive GL layer is worn and thinned, the black color of the first upper conductive GL layer, which is the lower layer, becomes visible, so it is predicted that the expiration date has approached. You can also In this case, it is also possible to regenerate the multilayer conductive GL by applying the first conductive GL layer again.

  Thus, the multilayer conductive GL of the present invention can be used for GL production of a product with high economic efficiency and safety by being applied to a GL structure such as a GL device or a GL container.

It is sectional drawing of an example of the multilayer electroconductive GL of this invention. It is the photograph which image | photographed the GL sample surface of the Example of this invention and Comparative Examples 1-5.

Claims (16)

A subbing normal glass lining layer fired without adding a conductive material to a glass frit on a metal substrate,
An overlying normal glass lining layer fired without adding a conductive material to the glass frit, a first overlying conductive glass lining layer fired with the first conductive material added to the glass frit, and
A glass frit is provided with at least four glass lining layers including a second overlying conductive glass lining layer that is fired by adding a second conductive material different from the first conductive material to the glass frit. Multi-layer conductive glass lining. The first conductive material is an indium compound, an antimony compound, a noble metal or a noble metal compound;
The second conductive material is any one of titanium oxide coated with antimony-containing tin oxide, tin oxide, barium sulfate coated with antimony-containing tin oxide, phosphorus-containing tin oxide, or barium sulfate coated with tin oxide. 2. The multilayer conductive glass lining according to 1.   The indium compound is indium oxide or tin oxide-containing indium oxide, the antimony compound is antimony oxide, or antimony oxide-containing tin oxide, and the noble metal or noble metal compound is any one of platinum, silver, ruthenium dioxide, or iridium dioxide. The multilayer conductive glass lining according to claim 2.   The multilayer conductive material according to any one of claims 1 to 3, wherein the first conductive material is ruthenium dioxide, and the second conductive material is titanium oxide or tin oxide coated with antimony-containing tin oxide. Glass lining.   5. The addition amount of ruthenium dioxide to the glass frit is 2% by weight to 15% by weight, and the addition amount of titanium oxide coated with antimony-containing tin oxide to the glass frit is 6% to 30% by weight. The multilayer conductive glass lining described.   The multilayer conductive glass lining according to claim 4, wherein the amount of ruthenium dioxide added to the glass frit is 2 wt% to 15 wt%, and the amount of tin oxide added to the glass frit is 10 wt% to 20 wt%. .   7. The thickness according to claim 1, wherein a thickness of the second overlaid conductive glass lining layer on the surface layer side is larger than a thickness of the first overlaid conductive glass lining layer on the lower layer side. Multi-layer conductive glass lining.   A structure made of a multilayer conductive glass lining comprising the multilayer conductive glass lining according to any one of claims 1 to 7. An undercoating normal glass lining layer fired without adding a conductive material to the glass frit;
Overcoating normal glass lining layer baked without adding conductive material to glass frit,
A first overlying conductive glass lining layer fired by adding a first conductive material to a glass frit; and
At least four glass lining layers including a second overlying conductive glass lining layer that is baked by adding a second conductive material different from the first conductive material to the glass frit on the metal substrate. Construction method of multilayer conductive glass lining to be constructed. The first conductive material is an indium compound, an antimony compound, a noble metal or a noble metal compound;
The second conductive material is any one of titanium oxide coated with antimony-containing tin oxide, tin oxide, barium sulfate coated with antimony-containing tin oxide, phosphorus-containing tin oxide, or barium sulfate coated with tin oxide. The construction method of the multilayer electroconductive glass lining of 9.   The indium compound is indium oxide or tin oxide-containing indium oxide, the antimony compound is antimony oxide, or antimony oxide-containing tin oxide, and the noble metal or noble metal compound is any one of platinum, silver, ruthenium dioxide, or iridium dioxide. The construction method of the multilayer conductive glass lining according to claim 10.   12. The multilayer conductive material according to claim 9, wherein the first conductive material is ruthenium dioxide, and the second conductive material is titanium oxide or tin oxide coated with antimony-containing tin oxide. How to make a glass lining.   The amount of ruthenium dioxide added to the glass frit is 2% by weight to 15% by weight, and the amount of titanium oxide coated with antimony-containing tin oxide to the glass frit is 6% by weight to 30% by weight. The construction method of the multilayer electroconductive glass lining of description.   The multilayer conductive glass lining according to claim 12, wherein the addition amount of ruthenium dioxide to the glass frit is 2 wt% or more and 15 wt% or less, and the addition amount of tin oxide to the glass frit is 10 wt% or more and 20 wt% or less. Construction method.   The thickness of the second overlaid conductive glass lining layer on the surface layer side is set to be larger than the thickness of the first overlaid conductive glass lining layer on the lower layer side. The construction method of the multilayer electroconductive glass lining of description.   The method for applying a multilayer conductive glass lining according to any one of claims 9 to 15, wherein an average particle size of the second conductive material added to the glass frit is 0.2 µm or less.