JP2006310189A - Metal etching product with insulating treatment applied - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal etching product with an insulating treatment aplied with high insulation reliability. <P>SOLUTION: The metal etching product with an insulating treatment applied has barrier ribs 2 formed on the surface of a metal substrate 1, a concave part 3 between the barrier ribs 2, 2, an insulation film 4 to cover the barrier ribs 2 and the concave part 3. A thickness of the insulation film 4 is 0.5 μm or more and 20 μm or less, a thickness T1 of an insulation film 4a formed on the barrier rib 2 of the insulation film 4 is set to be thicker (T1>T2) than a thickness T2 of an insulation film 4b formed on the concave part 3. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a metal-etched product that has been subjected to suitable insulation treatment for use in flat panel display members such as plasma display panels (PDP) and field emission displays (FED).

In recent years, as a member for flat panel displays such as a plasma display panel (PDP) and a field emission display (FED), a metal material subjected to an insulation treatment instead of a conventional insulator such as glass has been studied.
The metal material can be processed into a large aspect ratio in a large area by wet etching. Particularly, when a plate material is used, the dimensional accuracy in the thickness direction is stable as ± several μm. It can be used as a PDP partition wall or a FED spacer. Moreover, since it is excellent in heat dissipation, it can also serve as a shield for electromagnetic waves and electrical noise.

In addition, the insulating material used for the above-described insulation treatment needs to be resistant to the thermal history (about 350 to 550 ° C.) received during the panel assembling process, and has a sufficient withstand voltage (about 500 to 1000 V). Since it is necessary to ensure, a high melting point containing a metal oxide or metal nitride such as Si or Al, or an oxide such as SiO ₂ , Ba 0, B ₂ O ₃ , Na ₂ O, TiO ₂ or Nd ₂ O ₅ Glass or the like is used.
As a product to which this metal material is applied, a PDP partition has been proposed (Patent Document 1). Conventionally, the barrier ribs have been formed in a stripe shape by sandblasting on the surface of the glass substrate serving as a back plate on the cell forming side. However, when a metal material is used, the barrier ribs are formed on the metal substrate by wet etching. Finely processed, and insulation treatment is applied to the partition wall. Thereby, the metallic partition which has insulation can be produced. As this insulation treatment, an insulation treatment method for forming a dielectric containing glass by an electrodeposition method is used.

Other insulating treatments include, for example, a method of forming an oxide on a substrate surface using a spray method (Patent Document 2), a vapor phase growth method (Patent Document 3), and a liquid phase growth method (Patent Document 4). An open-air chemical vapor deposition method (CVD method) (Patent Document 5), a glass film forming method by powder electrostatic coating (Patent Document 6), and the like have been proposed.
Japanese Patent Laid-Open No. 03-205738 JP 2000-277021 A JP 2004-22403 A Japanese Patent Laid-Open No. 2004-22404 Japanese Patent Laid-Open No. 2003-132802 Japanese Patent Laid-Open No. 2001-195978

By the way, in the conventional insulating process by the electrodeposition method or the spray method, there is a problem in that the insulating property may be lowered because bubbles are generated and remain in the insulating layer when the film is formed. In addition, since the film thickness of the corner formed by etching is reduced by the heat flow of the insulating layer during firing, there is a problem that it is difficult to ensure insulation. In particular, when the pattern is high-definition, there is a possibility that the hole is filled with the heat-flowed insulator.
In addition, in the insulating treatment by the vapor phase growth method, there is a problem that it is difficult to obtain a sufficient withstand voltage because the film thickness of the insulating material is low and the obtained insulating layer is thin. .

  In addition, unlike the ordinary vapor phase growth method, open-air type CVD does not have a decompression process, so it is easy to carry in and out of materials, and continuous film formation is possible. However, it is necessary to heat the metal substrate to a high temperature in order to promote a thermochemical reaction during film formation. When a metal substrate is heated to a high temperature, a black oxide is generated on the surface of the substrate, resulting in a decrease in adhesion to the insulating film, resulting in a decrease in brightness when peeling or display is made. There was a problem such as.

In addition, in powder electrostatic coating, the insulating film becomes dense because the glass melts during firing, but the melted glass agglomerates due to surface tension, resulting in a thin film thickness of the insulating film at the corners. There is a problem that the withstand voltage characteristics are not sufficient.
In addition, the surface of the metal plate that is not in contact with the powder is oxidized during firing, resulting in a problem that adhesion with the insulating film cannot be ensured.
As described above, it is difficult to ensure sufficient insulation in the conventional insulation treatment. In particular, when the PDP partition is formed of a metal material, it is difficult to ensure sufficient insulation of each cell. However, it has not yet been commercialized.

In order to solve the above problems, a method of forming an insulating layer by forming polysilazane on the surface of a metal substrate and firing the film has been proposed.
The polysilazane here is an inorganic polymer based on a silazane having a Si-N bond and soluble in an organic solvent. A solution obtained by dissolving the polysilazane in an organic solvent is used as a coating solution. Alternatively, by baking in a steam-containing atmosphere, the polysilazane in the coating solution reacts with water to become dense high-purity silica that is amorphous.

Since this polysilazane is high-purity silica, it has a heat resistance of 1000 ° C. or higher and a withstand voltage of about 30 kV / mm, but when the film thickness is a certain thickness or higher, a temperature of 350 ° C. to 550 ° C. in the atmosphere. There was a problem that cracks occurred when firing at. This is considered to occur due to the internal stress of polysilazane itself accumulated during firing and the difference in thermal expansion from the metal substrate. In order not to generate cracks in this firing process, the film thickness is less than 3 μm. Is the limit.
For example, when polysilazane is formed on a metal substrate so as to have a film thickness of 2.5 μm, and then fired in the air, the withstand voltage of the obtained insulating film is about 200 to 350 V in an actual measurement value. It is not possible to obtain a sufficient withstand voltage.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a metal etching product that has been subjected to an insulation process with high insulation reliability.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have formed an insulating film made of a mixture of a silicon-based material and powder on the concavo-convex shape of the metal substrate, and the thickness of this insulating film is reduced to 0. It was found that if the thickness was controlled to be not less than 5 μm and not more than 20 μm, the insulation reliability of the metal etching product was improved, and the present invention was achieved.

  That is, the metal-etched product subjected to the insulation treatment according to claim 1 of the present invention is a metal-etched product obtained by performing insulation treatment on one or both surfaces of the metal member, and any one of the metal members An uneven shape is formed on one surface or both surfaces, and an insulating film having a substantially uniform film thickness is formed on the uneven shape, and the film thickness at the corner of the uneven shape of the insulating film is the film at the other portion. The thickness of the insulating film is approximately 0.5 μm or more and 20 μm or less.

  The metal-etched product subjected to insulation treatment according to claim 2 is a metal-etched product obtained by performing insulation treatment on one or both surfaces of a metal member, wherein the metal member has one or more through holes. An insulating film having a substantially uniform film thickness is formed on the one surface or both surfaces including the inner surface of the through hole, and the film thickness on the one surface or both surfaces of the insulating film is determined by the opening end of the through hole. The thickness of this insulating film is 0.5 μm or more and 20 μm or less.

  The metal-etched product subjected to the insulation treatment according to claim 3 is a metal-etched product obtained by performing an insulation treatment on one or both surfaces of a metal member, and any one or both surfaces of the metal member. The metal member is formed with one or more through holes, and an insulating film having a substantially uniform film thickness is formed on the uneven shape including the inner surface of the through hole. The film thickness at the corners of the uneven shape of the film and the opening end of the through hole is substantially the same as the film thickness at the other part of the uneven shape and the inner surface of the through hole. It is 5 μm or more and 20 μm or less.

  The metal-etched product subjected to the insulation treatment according to claim 4 is the metal-etched product subjected to the insulation treatment according to claim 1 or 3, wherein the thickness of the insulating film formed on the uneven-shaped convex portion is It is characterized by being thicker than the thickness of the insulating film formed in the concave and convex portions.

  The metal-etched product subjected to the insulation treatment according to claim 5 is the metal-etched product subjected to the insulation treatment according to claim 2 or 3, wherein the metal-etched product is formed on any one or both surfaces of the concave-convex shape. The thickness of the insulating film is greater than the thickness of the insulating film formed on the inner surface of the through hole.

  The metal-etched product subjected to the insulation treatment according to claim 6 is the metal-etched product subjected to the insulation treatment according to any one of claims 1 to 5, wherein the insulating film comprises a silicon-based material and powder. It is characterized by comprising.

  The metal-etched product subjected to the insulation treatment according to claim 7 is the metal-etched product subjected to the insulation treatment according to claim 6, wherein the thermal expansion coefficient of the powder is larger than that of the silicon-based material, and the metal member It is characterized by being smaller.

  The metal-etched product subjected to the insulation treatment according to claim 8 is the metal-etched product subjected to the insulation treatment according to claim 6 or 7, wherein the dielectric constant of the powder is 10 or less.

  The metal-etched product subjected to the insulation treatment according to claim 9 is the metal-etched product subjected to the insulation treatment according to claim 6, 7 or 8, wherein the average particle size of the powder is 0.3 μm or more and 5 μm or less. It is characterized by being.

  The metal-etched product subjected to the insulation treatment according to claim 10 is the metal-etched product subjected to the insulation treatment according to any one of claims 6 to 9, wherein the powder includes the silicon-based material and the powder. 60 volume% or more and 80 volume% or less is contained with respect to the total volume.

  The metal-etched product subjected to the insulation treatment according to claim 11 is the metal-etched product subjected to the insulation treatment according to any one of claims 6 to 10, wherein the silicon-based material is a hydrolyzate of polysilazane. It is characterized by that.

  The metal-etched product subjected to the insulation treatment according to claim 12 is the metal-etched product subjected to the insulation treatment according to any one of claims 6 to 11, wherein the powder is an inorganic fine powder. And

  The metal-etched product subjected to the insulation treatment according to claim 13 is the metal-etched product subjected to the insulation treatment according to any one of claims 6 to 12, wherein the metal member is a metal made of Fe or Ni It is characterized by being an Fe-based alloy containing one or more selected from Cr, Co and the balance being Fe and inevitable impurities.

  The metal-etched product subjected to the insulation treatment according to claim 14 is the metal-etched product subjected to the insulation treatment according to any one of claims 1 to 13, wherein the metal member is a metal plate for a flat panel display. It is characterized by being.

According to the metal etching product subjected to the insulation treatment of the present invention, an uneven shape is formed on one or both surfaces of the metal member, and an insulating film having a substantially uniform film thickness is formed on the uneven shape, The film thickness of the insulating film at the corners of the concavo-convex shape is substantially the same as the film thickness at other portions, and the thickness of the insulating film is 0.5 μm or more and 20 μm or less. There is no risk of the thickness being reduced, and sufficient insulation can be secured. Therefore, the insulation reliability of the insulating film can be increased.
Furthermore, if this metal member is applied to a metal plate for a flat panel display, the insulation of each cell can be sufficiently secured, and the insulation reliability of the flat panel display can be enhanced.

According to the other metal-etched product of the present invention, one or more through holes are formed in the metal member, and the film thickness is substantially uniform on one or both surfaces including the inner surface of the through hole. An insulating film is formed, the film thickness on the one or both surfaces of the insulating film is substantially the same as the film thickness at the opening end of the through hole, and the thickness of the insulating film is 0.5 μm or more and 20 μm or less. Therefore, there is no possibility that the film thickness of the insulating film in the corner portion becomes thin, and sufficient insulation can be ensured. Therefore, the insulation reliability of the insulating film can be increased.
Furthermore, if this metal member is applied to a metal plate for a flat panel display, the insulation of each cell can be sufficiently secured, and the insulation reliability of the flat panel display can be enhanced.

According to the metal etching product subjected to still another insulation treatment of the present invention, the metal member is formed with a concavo-convex shape on one or both surfaces thereof, and at least one through hole is formed in the metal member, An insulating film having a substantially uniform film thickness is formed on the concavo-convex shape including the inner surface of the through-hole, and the film thickness at the corners of the concavo-convex shape and the opening end of the through-hole is set to the concavo-convex shape. Since the thickness of the other portion and the inner surface of the through-hole is substantially the same, and the thickness of the insulating film is 0.5 μm or more and 20 μm or less, there is no possibility that the thickness of the insulating film at the corner portion is reduced, Insulation can be sufficiently secured. Therefore, the insulation reliability of the insulating film can be increased.
Furthermore, if this metal member is applied to a metal plate for a flat panel display, the insulation of each cell can be sufficiently secured, and the insulation reliability of the flat panel display can be enhanced.

The best mode of the metal etching product which performed the insulation process of this invention is demonstrated.
This embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.

“First Embodiment”
FIG. 1 is a cross-sectional view showing a metal-etched product subjected to insulation treatment according to the first embodiment of the present invention. In the figure, 1 is a metal substrate (metal member), and 2 is the surface (one surface) of the metal substrate. The partition walls constituting the concavo-convex convex portions formed in 3, 3 is a concavo-convex concave portion formed between the partition walls 2, and 4 is an insulating film formed so as to cover the partition wall 2 and the concave portion 3.
The thickness of the insulating film 4 is preferably 0.5 μm or more and 20 μm or less, more preferably 3.0 μm or more and 20 μm or less, and still more preferably 5.0 μm or more and 20 μm or less. Of this insulating film 4, the thickness T1 of the insulating film 4a formed on the partition wall 2 is set to be larger than the thickness T2 of the insulating film 4b formed in the recess 3 (T1> T2).

  In this insulating film 4, the thickness T 1 of the insulating film 4 a formed on the partition wall 2 is thicker than the thickness T 2 of the insulating film 4 b formed on the recess 3 (T 1> T 2). There is no possibility that a thin portion is formed in the insulating film 4a, and the insulation reliability of the entire insulating film 4 is increased.

Although it does not restrict | limit especially as a material of the metal substrate 1, For example, when using this metal substrate as a metal partition of PDP, 1 type, or 2 or more types selected from the metal which consists of Fe, or Ni, Cr, Co An Fe-based alloy containing Fe and the inevitable impurities is preferably used.
When this metal product is used as a metal partition wall of a PDP, it undergoes a thermal cycle of 450 to 500 ° C. in the panel assembly process. When the difference in thermal expansion between the front and rear glass, which is a component of the panel, and the metal partition is large, thermal stress is generated, and the panel is damaged and cannot function as an image display device.

In order to prevent this, it is preferable that the partition walls approximate the thermal expansion coefficients of the front plate and the back plate. For example, as a glass substrate for the front plate or the back plate of PDP, soda lime glass or high strain point glass having a thermal expansion coefficient of about 8 × 10 ⁻⁶ / ° C. is used. An Fe—Ni-based alloy containing 40 to 52 mass% of Ni and the balance being Fe and inevitable impurities is suitable. Among the Fe—Ni alloys, an Fe—Ni alloy containing 46 to 50% by mass of Ni is particularly preferable. These Fe—Ni-based alloys can be made to have a thermal expansion coefficient close to that of the glass and can easily form a fine pattern by an etching method, and thus are suitable for a metal partition wall substrate.

The insulating film 4 contains a silicon-based material and powder.
As the silicon material, a hydrolyzate of polysilazane is preferable.
Polysilazane is an inorganic polymer based on (SiH ₂ —NH) _n and preferably has a molecular weight in the range of 600 to 1000.

Here, the reason why polysilazane is preferred is as follows.
(1) It is applied to the surface of the substrate and fired at a temperature of 300 ° C. to 500 ° C., whereby dense high-purity silica that is amorphous is obtained.
(2) Since SiO ₂ of polysilazane does not contain carbon in (SiH ₂ —NH) _n , adhesion with ceramics, glass, metal material, etc. is good. In addition, unlike the sol-gel method, there is no risk of film shrinkage or residual carbon problems during thermal decomposition, and cracks are relatively unlikely to occur.

(3) Since firing in the atmosphere is possible, continuous processing can be performed without using a special apparatus such as a vacuum environment or film formation conditions.
(4) Since the baking is performed with the entire surface of the substrate covered with polysilazane, there is no possibility that the surface of the metal substrate is oxidized.
(5) Do not use environmentally harmful substances such as lead.

By the way, when polysilazane is diluted in a solvent alone and coated, the critical film thickness is about 3 μm and the withstand voltage is about 200 to 350 V, so that a sufficient withstand voltage cannot be obtained. When the film thickness is 3 μm or more, the internal stress of the polysilazane portion itself and the difference in thermal expansion from the metal substrate (the thermal expansion coefficient of SiO ₂ is 0.6 × 10 ⁻⁶ / ° C. Cracks which are considered to occur due to a thermal expansion coefficient of the material of 5 to 20 × 10 ⁻⁶ / ° C. are generated.

Therefore, in the present invention, as a method of suppressing the breakdown voltage improvement by increasing the thickness of the insulating layer and the generation of cracks associated therewith, a powder having a thermal expansion coefficient larger than that of a silicon-based material and smaller than that of a metal material, for example, An insulating layer is formed by mixing an oxide or nitride such as Al, or BaO, B ₂ O ₃ , Na ₂ O, TiO ₂ , Nd ₂ O ₅ or the like with a silicon-based material. In this method, the mixed powder serves as a buffer material during the heat history of the base material and suppresses the generation of cracks.

Since this powder exhibits a thermal buffering effect in the insulating layer, it is necessary to maintain the powder shape during the sintering of polysilazane, and the softening temperature thereof must be higher than the firing temperature of polysilazane (350 to 550 ° C.). There is.
In addition, the average particle diameter of the powder is preferably 0.3 μm or more and 5 μm or less when the thickness of the insulating film 3 is about 20 μm at maximum in consideration of the withstand voltage.

This powder preferably has a dielectric constant of 10 or less.
For example, when applied as an insulating layer of a metal partition wall of a PDP that forms electrical wiring on the partition wall, the insulating layer between the electrical wiring and the metal partition wall acts as a dielectric, resulting in electrical loss. Of course, the insulating layer of the present invention needs to have sufficient insulating properties. However, in consideration of the above contents, it is possible to reduce electrical loss by lowering the dielectric constant. Therefore, in the present invention, since a mixture of a silicon-based material (dielectric constant of about 3) and powder is used for the insulating layer, the dielectric constant of the powder is set to 10 or less.

Since it is more preferable that the dielectric constant of the powder is lower, it is preferably 5 or less. Furthermore, since the dielectric constant of the silicon-based material is about 3, it is more preferable that the dielectric constant of the powder is about 3.
Considering the above, the material of the powder used as the insulating layer of the present invention is a metal oxide or nitride such as Si or Al, BaO, B ₂ O ₃ , Na ₂ O, TiO ₂ , Nd ₂ O ₅ or the like. And high melting point glass.

The content of the powder is 60% by volume or more and 80% by volume or less with respect to the silicon-based material. Preferably they are 65 volume% or more and 75 volume% or less.
When the content of the powder is less than 60% by volume, the ratio of polysilazane increases, cracks are likely to occur due to the internal stress of the polysilazane portion itself and the thermal expansion difference from the metal base material, and coating is performed on a thick film. Because it becomes difficult. On the other hand, when the content exceeds 80% by volume, since the polysilazane is small, the powders are not bonded to each other, and therefore do not have a film shape.

Next, the manufacturing method of this metal etching product is demonstrated.
FIG. 2 is a spray coating apparatus used when manufacturing this metal etching product. In the figure, reference numeral 11 denotes a spray nozzle, which atomizes a coating solution obtained by diluting a mixture of a silicon-based material and powder with an organic solvent. The spraying is performed on the surface of the substrate.

The spray nozzle 11 is installed vertically with a certain distance A from the metal substrate 1, and sprays the finely divided coating liquid 13 and at the same time keeps the distance A constant while keeping the nozzle in the horizontal direction. The coating liquid 13 is sprayed and applied to the surface of the metal substrate 1 by scanning the plate or moving the metal substrate in the horizontal direction.
Here, coating is performed by controlling the flow rate of the coating liquid, the flow rate of the gas, the distance A between the nozzle 11 and the metal substrate 1, the scanning speed of the nozzle 11, and the stroke width.

  As shown in FIG. 3, the spray nozzle 11 introduces gas from the gas inlet 17, injects it from the gas outlet 15, and sucks the coating liquid from the coating liquid inlet 16 communicating with the coating liquid outlet 14. The coating liquid is crushed with a gas to be sprayed, atomized and sprayed. At this time, a negative pressure P is generated at the position of the coating liquid inlet 16 due to the principle of the Venturi tube. Here, when the coating liquid is supplied from the coating liquid supply tank (not shown) to the coating liquid inlet 16, the coating liquid is sucked from the coating liquid inlet 16 toward the coating liquid outlet 14.

  The coating liquid sent out from the coating liquid jet port 14 is mixed with the gas ejected from the gas jet port 15, and is crushed by the gas to form fine droplets. It ejects toward the surface of the substrate 1. In order to perform spraying of the coating liquid continuously, positive pressure is applied to the coating liquid supply tank by a positive pressure supply means (not shown), and the coating liquid with respect to the negative pressure P at the coating liquid inlet 16 What is necessary is just to adjust so that the pressure of the liquid level upper part of a supply tank may always become only predetermined pressure high.

The flow rate of the coating liquid ejected from the tip of the nozzle 11 is controlled between 0.05 and 20 mL / min. A preferable range of this flow rate is 0.1 to 10 mL / min.
If the flow rate of the coating liquid is less than 0.05 mL / min, the organic solvent may be excessively volatilized until the sprayed droplets reach the substrate 2, or the amount of the coating liquid will be extremely small. Therefore, the efficiency of the manufacturing process is not good. Moreover, when it exceeds 20 mL / min, the amount of the coating liquid reaching the substrate 1 is too large, and the gas flow rate, the distance A between the nozzle 11 and the metal substrate 1, the scanning speed of the nozzle 11, the stroke width, etc. are adjusted. Even so, it becomes difficult to perform the desired application.

The flow rate of the gas injected from the gas outlet 15 is controlled between 0.05 and 25 L / min. A preferable range of this flow rate is 0.1 to 12 L / min.
This is because if the gas flow rate is less than 0.05 L / min, the coating solution is not sufficiently crushed, the particle size becomes large, and it becomes difficult to make fine particles. Moreover, when it exceeds 25 L / min, there is too much gas amount with respect to a coating liquid, As a result, a coating liquid will rise and coating efficiency will fall.

In order to manufacture a metal etching product using this spray coating apparatus, first, a photosensitive resist is applied to one or both sides of the surface of a metal substrate, and patterning is performed so as to open a desired portion where a hole shape is to be formed by etching. To do. Next, by spraying a corrosive solution such as ferric chloride solution on the resist pattern, the metal in the portion where the resist is opened is etched to form a half-etched shape or a shape having a through hole in the metal substrate. Let Thereafter, the resist pattern is stripped using a stripping agent such as alkali.
Thereby, a metal substrate having one or both of an uneven shape and a through hole formed on the surface is produced.

Next, the metal substrate is sequentially degreased and washed with water, and then the coating liquid composed of a mixture of polysilazane and powder is applied to the surface using the spray coating apparatus described above.
As this coating solution, a solution in which a powder is mixed with a polysilazane solution having a concentration of 0.5% to 45% by weight, which is dissolved in a solvent such as xylene, terpene, solvesso, or dibutyl ether, is used.
The content of the powder is 60% or more and 80% or less by volume with respect to polysilazane. Preferably they are 65% or more and 75% or less.

In this spray coating apparatus, the coating liquid and gas are sprayed from the tip of the spray nozzle 11, and the coating liquid is atomized by the gas and sprayed onto the surface of the metal substrate 1. The spray nozzle 11 is installed vertically with a certain distance A from the metal substrate 1, and at the same time as spraying, the nozzle 11 or the metal substrate 1 is placed in the horizontal direction while keeping the distance A between the nozzle 11 and the metal substrate 1 constant. Scan.
Coating is performed by controlling the flow rate of the coating liquid, the flow rate of gas, the distance A between the nozzle 11 and the metal substrate 1, the scanning speed of the nozzle 11, and the stroke width.

After this coating solution is applied, it is dried, fired in the atmosphere or in an atmosphere containing water vapor, and an SiO ₂ film is formed on the metal substrate 1. The reaction from polysilazane to SiO ₂ proceeds at 350 ° C. to 550 ° C., but a high temperature of 400 ° C. or higher is preferable to make the film dense. Incidentally, the reaction to obtain a SiO ₂ polysilazane was fired in air is expressed by the following equation.
(SiH ₂ —NH) + O ₂ → SiO ₂ + NH ₃
The metal etching product of this embodiment can be manufactured by the above.

“Second Embodiment”
FIG. 4 is a cross-sectional view showing a metal-etched product subjected to insulation treatment according to the second embodiment of the present invention. The metal-etched product according to this embodiment is different from the metal-etched product according to the first embodiment described above. This is that the insulating film 21 is formed on both surfaces of the metal substrate 1, one or more through holes 22 are formed in the metal substrate 1, and the insulating film 23 is formed on the inner surface of the through hole 21.

The thicknesses of the insulating films 21 and 23 are preferably 0.5 μm or more and 20 μm or less, more preferably 3.0 μm or more and 20 μm or less, and further preferably 5.0 μm or more and 20 μm or less. The thickness T3 of the insulating film 21 formed on both surfaces of the metal substrate 1 is set to be larger than the thickness T4 of the insulating film 23 formed on the inner surface of the through hole 21 (T3> T4).
Here, since the thickness T3 of the insulating film 21 is set so as to be thicker than the thickness T4 of the insulating film 23 (T3> T4), there is no possibility that a thin portion is formed at the joint between the insulating film 21 and the insulating film 23. The insulation reliability of the insulating films 21 and 23 is increased.

Examples of the present invention and comparative examples will be described below.
"Example 1"
A 300 μm thick Fe—Ni alloy foil was alkali degreased and bonded to the surface of a commercially available dry film resist substrate having a thickness of 20 μm. Next, it is exposed with a photomask having a pattern of 270 × 810 μm and having a short hole, sprayed with an alkaline aqueous solution, and a photoresist pattern having the same shape and the same dimensions as the photomask on an Fe-50% Ni alloy. Formed.
Then, etching was performed by spraying a ferric chloride solution, and a half-etched metal flat plate was produced leaving a dry film resist. Subsequently, the aqueous solution of caustic soda was sprayed to remove the photoresist, and the rib shape of the metal partition wall for PDP could be produced.

This substrate was again alkali degreased, washed with water, and then coated with a coating solution obtained by mixing polysilazane and alumina powder (average particle size 0.7 μm). Polysilazane was dissolved in xylene and adjusted to a ratio of 25% by weight. Moreover, the alumina powder was mixed so as to have a volume ratio of 70% with respect to polysilazane.
For the coating, a spray method in which a gas and a coating solution were sprayed at the same time was used. The distance between the substrate and the nozzle is 40 mm, the coating liquid spray rate is 2.0 mL (liter) / min, the gas spray rate is 8.0 L / min, and the nozzle is 300 mm / sec in parallel with the etched substrate. Scanning was performed, and coating was performed so that the film thickness was 25 μm uniformly in the surface.

Thereafter, drying is performed until the solvent is sufficiently volatilized in the atmosphere, and firing is performed in the atmosphere at 480 ° C. for 60 minutes to form an insulating layer in the rib shape of the above-mentioned metal partition wall for PDP without causing cracks or the like. did it.
When the PDP metal partition wall subjected to the insulation treatment is cut perpendicularly to the longitudinal direction of the short shape and the cross section is observed, the cross sectional shape shown in FIG. 1 is obtained, and a wet etching method is used on the surface of the metal substrate 1 for PDP. It was confirmed that partition walls were formed and an insulating layer was formed on the entire surface of the metal substrate 1 using a spray coating method.

In the top flat portion of the partition wall 2, the thickness of the insulating film 4 a is 14.3 μm. In the side wall and the recess 3 of the partition wall 2, the thickness of the insulating film 4 b is 6.0 μm. In addition, it was confirmed that an insulating film thicker than the recess 3 was formed.
Further, when the dielectric breakdown voltage measuring apparatus was used to contact the measurement terminal flat plate with the upper part of the partition wall 2 and the dielectric breakdown voltage of the top flat portion was measured, it was 1100 V, indicating a sufficient dielectric breakdown voltage. The relative dielectric constant was 7.2.

"Example 2"
The Fe-42Ni alloy foil having a thickness of 500 μm was degreased with alkali and bonded to the surface of a commercially available dry film resist substrate having a thickness of 20 μm. Next, using a photomask having a pattern of 270 × 810 μm with holes formed in a short shape, the same shape is aligned on the front and back, exposed, then sprayed with an alkaline aqueous solution, and Fe-42Ni alloy A photoresist pattern having the same shape and the same dimensions as the photomask was formed.

  Then, etching was performed by spraying a ferric chloride solution, and a half-etched metal flat plate was produced leaving a dry film resist. Next, the dry film was peeled off with an aqueous caustic soda solution, and positive electrodeposition photoresist Sonne EDUV P-500 (manufactured by Kansai Paint) was coated on the half-etched metal flat plate with a uniform film thickness. Next, the positive photomask was aligned, further exposed, and developed by spraying a sodium carbonate aqueous solution to form a positive electrodeposition photoresist pattern.

  Next, etching is performed by spraying a ferric chloride solution, and further, spraying a caustic soda solution to strip the photoresist to form through holes of a slot pattern having a plate thickness of 500 μm, a pitch of 270 × 810 μm, and openings of 220 × 760 μm. The metal etching product which has was able to be manufactured.

This substrate was again degreased with alkali, washed with water, and then coated with a coating solution in which polysilazane and silica powder (average particle size 0.5 μm) were mixed. Polysilazane was dissolved in xylene and adjusted to a ratio of 30% by weight. Further, the alumina powder was mixed at a volume ratio of 65% with respect to polysilazane.
For the coating, a spray method in which a gas and a coating solution were sprayed simultaneously was used. Here, the distance between the substrate and the nozzle is 50 mm, the spray amount of the coating liquid is 1.0 mL / min, the spray amount of the gas is 10.0 L / min, and the nozzle is moved at a speed of 200 mm / sec in parallel with the etched substrate. Scanning was performed, and coating was performed so that the film thickness was 25 μm uniformly in the surface.

Then, it was dried until the solvent was sufficiently volatilized in the air, and baked at 500 ° C. for 60 minutes in the air, whereby an insulating layer could be formed on the metal etching product having through holes with short patterns.
When the cross section of the metal etched product subjected to the insulation treatment is observed, the cross sectional shape shown in FIG. 4 is obtained. The insulating film 21 is formed on both surfaces of the metal substrate 1 and the inner surface of the through-hole 21 formed in the metal substrate 1 is insulated. It was confirmed that the film 23 was formed.

Further, the thickness of the insulating film 23 is 4.8 μm on the inner surface of the through hole 21, the thickness of the insulating film 21 is 15.6 μm on both surfaces of the metal substrate 1, and the inner surface of the through hole 21 on both surfaces of the metal substrate 1. It was confirmed that a thicker insulating film was formed.
In addition, when a measurement terminal flat plate was brought into contact with the flat portion of the metal substrate 1 and the insulation breakdown voltage of this flat portion was measured with a dielectric breakdown voltage measuring apparatus, it was 1140 V, indicating a sufficient dielectric breakdown voltage. The relative dielectric constant was 4.5.

"Examples 3 to 12"
Except that the components and film thickness of the coating solution were changed as shown in Table 1, PDP metal barrier ribs subjected to the insulation treatment of Examples 3 to 12 were produced in the same manner as in Example 1.
For each of these samples, the film thickness, withstand voltage, and relative dielectric constant were measured in the same manner as in Example 1, and the surface state of the film was observed. The film thickness was measured at two locations, the top flat portion of the partition wall 2 and the concave portion 3.

"Comparative Examples 1-5"
Except that the components of the coating solution, the coating method, and the film thickness were changed as shown in Table 1, metal partitions for PDP subjected to the insulation treatment of Comparative Examples 1 to 5 were produced in the same manner as in Example 1.
For each of these samples, the film thickness, withstand voltage, and relative dielectric constant were measured in the same manner as in Example 1, and the surface state of the film was observed. The film thickness was measured at any one of the two locations of the top flat portion and the concave portion 3 of the partition wall 2 and only the top flat portion of the partition wall 2.
The evaluation results of Examples 3 to 12 and Comparative Examples 1 to 5 are shown in Table 1.

According to the evaluation results in Table 1, it was confirmed that Examples 3 to 12 were superior to Comparative Examples 1 to 5 in terms of dielectric strength, relative dielectric constant, and film surface condition.
On the other hand, Comparative Examples 1 to 3 and 5 had cracks and peeling on the surface of the film, and the surface state of the film was very bad. Moreover, although the thing of the comparative example 4 was the surface state body of the film | membrane favorable, both the dielectric strength voltage and the relative dielectric constant were inferior compared with Examples 3-12.

It is sectional drawing which shows the metal etching product of the 1st Embodiment of this invention. It is a schematic diagram which shows the spray coating apparatus used for manufacture of the metal etching product of the 1st Embodiment of this invention. It is sectional drawing which shows the spray nozzle of a spray coating apparatus. It is sectional drawing which shows the metal etching product of the 2nd Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Metal substrate 2 Partition 3 Recessed part 4, 4a, 4b Insulating film 11 Spray nozzle 12 Metal substrate 13 Atmosphere in spraying 14 Coating liquid outlet 15 Gas outlet 16 Coating liquid inlet 17 Gas inlet 21 Insulating film 22 Through-hole 23 Insulation film

Claims (14)

A metal etching product obtained by subjecting one or both surfaces of a metal member to insulation treatment,
An uneven shape is formed on one or both surfaces of the metal member,
An insulating film having a substantially uniform film thickness is formed on the uneven shape,
The film thickness at the corners of the concavo-convex shape of this insulating film is substantially the same as the film thickness at other parts,
A metal-etched product subjected to insulation treatment, wherein the thickness of the insulating film is 0.5 μm or more and 20 μm or less. A metal etching product obtained by subjecting one or both surfaces of a metal member to insulation treatment,
One or more through holes are formed in the metal member;
An insulating film having a substantially uniform film thickness is formed on the one surface or both surfaces including the inner surface of the through hole,
The film thickness on the one surface or both surfaces of the insulating film is substantially the same as the film thickness at the opening end of the through hole,
A metal-etched product subjected to insulation treatment, wherein the thickness of the insulating film is 0.5 μm or more and 20 μm or less. A metal etching product obtained by performing an insulation treatment on one or both surfaces of a metal member,
An uneven shape is formed on one or both surfaces of the metal member, and one or more through holes are formed in the metal member.
An insulating film having a substantially uniform film thickness is formed on the uneven shape including the inner surface of the through hole,
The film thickness at the corners of the concavo-convex shape of the insulating film and the opening end of the through hole is substantially the same as the film thickness at the other part of the concavo-convex shape and the inner surface of the through hole,
A metal-etched product subjected to insulation treatment, wherein the thickness of the insulating film is 0.5 μm or more and 20 μm or less.   4. The metal subjected to insulation treatment according to claim 1, wherein a thickness of the insulating film formed on the concave and convex portion is thicker than a thickness of the insulating film formed on the concave and convex portion. Etching product.   4. The thickness of the insulating film formed on any one or both of the surfaces or the uneven shape is thicker than the thickness of the insulating film formed on the inner surface of the through hole. Metal etched products with the insulation treatment described.   6. The metal-etched product subjected to insulation treatment according to claim 1, wherein the insulating film contains a silicon-based material and powder.   The metal-etched product subjected to insulation treatment according to claim 6, wherein a thermal expansion coefficient of the powder is larger than that of the silicon-based material and smaller than that of the metal member.   8. The metal-etched product subjected to insulation treatment according to claim 6 or 7, wherein the dielectric constant of the powder is 10 or less.   9. The metal-etched product subjected to insulation treatment according to claim 6, wherein an average particle size of the powder is 0.3 μm or more and 5 μm or less.   10. The insulation according to claim 6, wherein the powder is contained in an amount of 60% by volume to 80% by volume with respect to the total volume of the silicon-based material and the powder. Processed metal etching products.   The metal-etched product subjected to insulation treatment according to any one of claims 6 to 10, wherein the silicon-based material is a hydrolyzate of polysilazane.   The metal-etched product subjected to insulation treatment according to any one of claims 6 to 11, wherein the powder is an inorganic fine powder.   The metal member includes a metal composed of Fe or one or more selected from Ni, Cr, and Co, and the balance is an Fe-based alloy composed of Fe and inevitable impurities. A metal-etched product that has been subjected to the insulation treatment according to any one of 1 to 12.   The metal-etched product subjected to insulation treatment according to any one of claims 1 to 13, wherein the metal member is a metal plate for a flat panel display.

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