JPH11314237A - Diboride coated press surface for abrasion-resistant laminated sheet, and manufacture of press surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the scratch-resistant strength of the surface of a press plate for manufacturing a decorative panel. SOLUTION: The press surface of a press plate for manufacturing a decorative panel having alumina particles bonded to the pressed surface thereof from resin impregnated paper is a flat surface coated with diboride selected from a group consisting of hafnium diboride, molybdenum diboride, tantalum diboride, titanium diboride, tungsten diboride, vanadium diboride, zirconium diboride and a mixture of them and having a Vickers hardness of at least 2,000. Desirable diboride is titanium diboride and zirconium diboride. The most desirable diboride is titanium diboride. The color, glossiness and surface appearance of a laminated sheet pressed by a titanium diboride coated press plate are substantially the same to those of the laminated sheet by the press plate before coating.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated wear-resistant press plate used for producing a wear-resistant decorative plate, coating of the press plate, and production of a laminated plate using the press plate.
Grit, such as alumina grains, on the pressed surface of the abrasion resistant veneer will scratch the pressed plate and subsequently degrade the appearance of the laminate made from the pressed plate. The press plate of the present invention is particularly useful for producing a wear-resistant high gloss decorative plate.

[0002]

BACKGROUND OF THE INVENTION In the manufacture of decorative boards, a laminate of resin-impregnated paper is pressed against a press plate under temperature and pressure conditions that cure the resin and bond the laminates together. The high gloss press plate gives the laminate a high gloss surface.
The patterned surface gives the laminate a patterned surface. Such press plates are extremely uniform, with even the smallest of irregularities being minimized. The quality of a high gloss polishing press plate can be determined by examining the reflected image on its surface and closely examining the optical shift of said reflected image. The grit on the surface of the laminate causes fine scratches on the stainless steel press plate normally used for the production of decorative plates, thus impairing the fine finish of said press plate. Press plates are also scratched by press plate handling equipment and by debris from presses or materials used to make laminates (Laurence, U.S. Pat.
44,375).

[0003] A melamine resin-coated decorative board has a temperature of about 230
~ 310 ° F (110 ~ 155 ° C) and pressure about 300 ~
Pressed at 2000 psi (20-136 bar), desirably about 750-1500 psi (51-102 bar). Heating to said temperature and cooling to room temperature causes substantial expansion and contraction of said laminate and press plates. Since the expansion and contraction of the laminate and the press plate are different, the grit on the pressed surface of the laminate will move across the press plate surface.

The glossiness of a gloss-finished laminate is 70-100.
+ Is specified in the American Electrical Manufacturers' Association (NEMA) standard issue number LD3. It is specified that the patterned high gloss finish laminate has a gloss of 21-40. For calibrating a gloss meter for measuring 60 degree angle glossiness,
A black glass with a gloss of 94 ± 1 measured at an angle of 60 ° is specified as NEMA standard 3.13.2.

[0005] Even irregularities that can be seen only with a microscope of a high gloss press plate may give visible surface defects to the high gloss surface of the laminate. Any scratches on the high gloss press plate will cause visible surface defects on the high gloss side of the laminate and reduce the gloss level.

[0006] The grit on the decorative surface of the laminate provides the abrasion resistance, a commercially desirable property of the laminate. In the production of decorative boards, alumina particles are generally used as grit. The Vickers hardness of alumina is measured by IM Press, issued by CRC Press (1992).
1800-2, "Tribology: Friction and Wear of Industrial Materials" by IM Hutchings.
000. Useful particle size range is about 1
0 to about 75 microns. A grit of about 25-60 microns is desirable. Optimal wear resistance is about 40 to 60
Obtained in the micron size range (Lane)
Et al., U.S. Pat. No. 3,798,111).

It has been disclosed that alumina particles having a maximum particle size of 9 microns are effective in providing an abrasion resistant surface to a glossy decorative board. Abrasion resistance is defined as the resistance of a glossy laminate to loss of gloss when the surface of the laminate is subjected to the sliding body's wear effect. It is observed that laminates exposed to the above abrasion effects do not meet NEMA LD 3.01 which is a requirement for being considered abrasion resistant. However, it is disclosed that if the grit particle size is maintained below 9 microns, the glossy press plate will not be substantially scratched (Lex et al., US Pat. No. 4,971,855). .

[0008] The use of a 410 stainless steel pressed plate hardened by nitriding to make a high gloss decorative board is disclosed. After pressing 100 high gloss decorative boards with 6 micron and 15 micron grit, the gloss level of the pressed laminate remained 'good' to 'very good'. The nitridized press plate exposed to the 6 micron grit was re-buffed after 234 uses and further reduced by at least 103 to produce acceptable quality laminates.
Was able to use it once. Nitrided press plates exposed to 30 micron grit had poor durability. Rockwell of the 410 stainless steel press plate used for nitriding (Roc
kwell) The "C" scale hardness is 38 to 45,
Rock nitride “C” scale hardness of the nitrided surface is 60 ~
70. American Institute of Metals (ASM), “Metal Handbook, Mechanical Testing”, ninth
Equivalent Vickers hardness of 410 stainless steel is about 3 based on the conversion table published in Volume 8 (1985), Volume 8.
70 to 440. The equivalent Vickers hardness of nitrided 410 stainless steel is about 500-1000 based on the conversion table published in ASM, Metal Handbook, Mechanical Testing, 9th Edition (1985), Volume 8 (Lawrence, U.S. Pat. No. 5,244,375).

A laminate having an average particle size of 35 μm coated alumina on its surface (Mead Corporation)
n) PGA822 overlay, commercially available from
Was pressed with a high gloss press plate coated with titanium nitride.
After ten presses, the titanium nitride coated press plate had about 15 scratches per square centimeter. Control 4
The 10 stainless steel plate had about 500 scratches per square centimeter. Vickers of titanium nitride (V
Ickers) hardness is published by CRC Press (1992
Years) by IM Hutchings, “Tribology:
"Friction and wear of industrial materials" specifies 1200 to 2000.

The control press plate and the press plate coated with titanium nitride were cut from the same stainless steel press plate. The abrasion was visible under an optical microscope at a magnification of 40x. Titanium nitride was coated on a 410 stainless steel high gloss press plate with a magnetron sputter coater. The use of a magnetron sputter coating apparatus to apply a titanium nitride coating is described in Surface and Coating Technology.
, pp. 49 (1991), "Multi-Cathode, Unbalanced Magnetron Sputtering Apparatus" by Sproul. The use of magnetron sputter coating equipment for cleaning surfaces to be coated is described in New Solid Films, Vol. 33 (1976) Schiller et al., "New Sputter Cleaning for Metal Substrates." Equipment ".

Further, the color of the laminate pressed by the titanium nitride coated press plate was different from the color of the laminate pressed by the control press plate. American Society for Testing and Materials (ASTM) D2244 color difference compared to reference (± 0.5)
If it is smaller than ΔE, it is considered that the color is in the range recognized as the same color as the reference. The ASTM D2244 color difference between the reference and the laminate pressed with the titanium nitride coated press plate was greater than (0.5) ΔE. The titanium nitride-coated press plate and the laminated plate pressed therewith had a bronze color. The control press plate and the laminate pressed therewith did not exhibit a bronze color. ASTM when compared to a reference for a laminated plate pressed with a control press plate
D2244 color difference was less than (0.5) ΔE.

A cutting tool with an iron substrate was sputter coated with 2-6 microns of titanium diboride. The sputtering was performed using a broad beam ion source with an argon or krypton ion beam accelerated at 1300-1800 volts. A titanium diboride target was placed as the cathode. The tool is at about 200 ° C. (392
° F). Sputtering was performed under a vacuum of about 4-6 milliTorr. The Vickers microhardness of titanium diboride is very high, generally about 3600,
Not only is it significantly higher than other diborides, but also substantially higher than other carbides or nitrides. Titanium diboride also has high densities, eg, 88% of theoretical density, low resistivity, eg, 30 micro-ohm-centimeter, about 40,0
High strength of 00 psi, and 20-800 ° C (68-
It is particularly noted for having a coefficient of thermal expansion of about 8.1 × 10 −6 in the temperature range of 1472 ° F. (Moskowitz et al., US Pat. No. 4,822).
0,392).

[0013] The control conditions for the sputter coating are as follows:
Of Vacuum Science Technology (Jou
rnal of Vacuum Science Te
(Chnology), Vol. 11, No. 4 (1974)
"The Influence of Device Geometry and Control Conditions on the Structure and Topography of Thick Sputtered Coatings," Thornton, July / August, 2008, and the American Institute of Metals (U.S. Pat. No. 44073, Metals, Ohio).・ Park location) “Metal Handbook” 9th edition (1982)
), Vol. 5, pp. 412-416, in "Sputtering" by Thornton et al.

[0014]

AST compared with a reference
There is a need for hard coatings on press plates, endless belts, and other pressed surfaces that give the laminate only a color with a MD2244 color difference of less than (± 0.5) ΔE.
There is a need for a coating that can be applied to the pressed surface without changing the finished appearance of the pressed surface. Greater than 10 microns,
Desirably, there is a demand for a pressed surface which does not scratch even when used for pressing a laminate coated with alumina particles larger than 25 microns. ASTM 2457, when used for pressing a laminate having a 60 degree square gloss higher than 70, a pressed surface that is not scratched is particularly required even if the surface of the laminate is coated with alumina particles of 25 to 60 microns. ing.

[0015]

SUMMARY OF THE INVENTION Hafnium diboride, molybdenum diboride, tantalum diboride, titanium diboride, tungsten diboride, vanadium diboride, or zirconium diboride, or mixtures thereof. The color, gloss and surface appearance of a laminate made of a pressed surface coated with a diboride selected from the group consisting of substantially the same as the color and gloss of the laminated plate made of the pressed surface before applying the coating. Now I know that will not change. The preferred diboride for coating the pressed surface of the laminate is titanium diboride or zirconium diboride. The most desirable diboride for coating the pressed face of the laminate is titanium diboride. From a commercial point of view, titanium diboride is more commonly used for surface coatings than other diborides, since titanium diboride can be sputter coated at higher deposition rates than other diborides of the present invention. it is conceivable that.

The diboride coating of the present invention should be at least 2000, preferably at least 2000, sufficient to abrasion-freely press laminates having 25 to 60 microns or more of alumina particles on the surface to be pressed. It is applied to the surface on which the laminate is pressed to have a Vickers hardness of 2200. A coating of about 3 microns has sufficient hardness to resist abrasion by alumina grains on the pressed face of the laminate. The hardness of the coating can be controlled in a planar magnetron sputter coating apparatus by a technician skilled in the use of such an apparatus.

The diboride coating of the present invention can be applied to the press surface with sufficient adhesive strength for use in pressing high pressure laminates. It is considered sufficient if the minimum value of the adhesion strength measured by the diamond scratch adhesion strength test is 1.6, preferably 1.8 kgf (kgf). Diboride coatings thicker than 6 microns have reduced adhesion strength due to stresses generated during coating.

The adhesion of the diboride coating of the present invention to the press surface is enhanced by thoroughly cleaning the press surface prior to placing the press surface in a magnetron sputter coater. The adhesion is further enhanced by etching the press surface prior to applying the titanium diboride coating in a magnetron sputter coating apparatus. Cleaning, anodic etching, cathodic etching and radio frequency (RF) etching are performed by methods known to those skilled in the art of using magnetron sputter coating equipment. It has been found that applying a titanium layer directly on the pressed surface prior to applying the diboride coating of the present invention further enhances the adhesion of the diboride. Improving adhesion by cleaning, etching and using the intermediate layer between the coating and the substrate is known to those skilled in the art of using magnetron sputter coating equipment.

[0019]

The present invention will be described below in detail with reference to examples.

The black, high gloss, high pressure laminates were pressed with titanium diboride coated press plates shown in Table 1. These press plates are subjected to AST of the laminate before coating with titanium diboride.
MD2457, finished at 60 degrees square gloss of about 100. The ASTM D2244 color difference between the reference and the laminate pressed with the titanium diboride coated press plate shown in Table 1 was less than (0.5) ΔE. The glossiness and color difference in Table 1 are the average of the measured values for ten laminated boards.

[0021]

[Table 1]

Further, using a high-gloss press plate 3000-2 and a control press plate, an average particle size of 35
7 high-pressure, black, high-gloss laminates with μ alumina particles
Sixty sheets were pressed. Using the above press plate, about 100
The laminate was pressed at 0 psi (68 bar) and 280 ° F (138 ° C). The pressed surface of the laminate is 3
A commercially available overlay sheet (Mead PGA822) with 5 micron alumina grit. The press plate 3000-2 and the control press plate are AS
TM D2457, cut from a high gloss 410 stainless steel press plate finished to a 60 degree square gloss of about 100. Press plate 3000-2 and the control press plate are approximately 12 inches by 11 inches in size. Press plate 3000-2 was coated with about 5 microns of titanium diboride using a magnetron sputter coating apparatus. The titanium diboride coating was applied in 17 scans, covering about 3000 Angstroms of titanium diboride per scan. Others were used as controls.

ASTM of the first black, high-gloss laminated plate pressed with the control press plate and having alumina particles having an average particle size of 35 μm on the surface to be pressed.
D2244 color difference was about (0.25) ΔE. 1 of black, high gloss laminates pressed by press plate 3000-2
The ASTM D2244 color difference of the sheet compared to the reference was about (0.15) ΔE.

The first sheet of the black laminate pressed with the control press plate had an ASTM D2457, 60 degree square gloss of about 100. 760 pressed on control press plate
ASTM D2457, 60-degree square glossiness of the second laminate was less than 70. After pressing about 160 laminates, the 60 ° square gloss of the laminate pressed with the control press plate was less than 90. Laminates having a 60 degree angle gloss of less than 90 are not considered commercially acceptable as high gloss laminates.

760 pressed with a press plate 3000-2
The ASTM D2457, 60-degree square glossiness of the black laminates was about 100. After pressing the 760 black laminates, the scratches were examined microscopically and none were found. The control press plate had numerous scratches.

The surface appearance of the laminate pressed with the press plate shown in Table 1 was not different from that of the laminate pressed with the control press plate.

[0027] Titanium diboride was coated on the high gloss press plate using a magnetron sputter coating apparatus using a number of conditions. Also, a coating of at least 3 microns is required to achieve a Vickers hardness of at least 2000, and it is believed that a coating thickness of 6 microns or more reduces the adhesion strength. Hardness and bond strength, as known to those skilled in the art, are determined by the pressure and temperature at which a press plate is coated with the diboride of the present invention, and the power used to coat the press plate with the diboride of the present invention. Amps and volts).

Hereinafter, referred to as “press plate 3000-3”
A patterned press plate and a control press plate coated with titanium diboride were coated on more than 450 pressed surfaces with an average grain size of 35.
Used to press high-pressure, black, patterned laminates with micron alumina particles. About 1000 psi (68 bar)
And at 280 ° F. (138 ° C.). The press plate 3000-3 and the control press plate have an ASTM D2457, 60 degree square gloss of about 10 of the laminated plate.
From a patterned 630 stainless steel press plate finished to Press plate 3000-3 and the control press plate are approximately 12 inches by 12 inches in size. Press plate 3000-3 was coated with about 6 microns of titanium diboride in a magnetron sputter coater. The titanium diboride coating was applied in 20 scans, covering about 3000 Angstroms of titanium diboride per scan.

ASTM D2 of the first of the black, patterned laminates pressed with the control press plate, compared to a reference
The 244 color difference was about (0.22) ΔE. Press plate 3
The ASTM D2244 color difference of the black, high gloss laminates pressed at 000-3 compared to the reference is about (0.08) Δ
E.

The first laminate of the black laminated plate pressed with the control press plate had an ASTM D2457, 60 degree square glossiness of about 9.5. 450 pressed on a control press plate
ASTM D2457, 60-degree square glossiness of the second black laminate was about 8. The ASTM D2457, 60-degree square glossiness of the black laminated plate pressed with the press plate 3000-3 was about 10.

The surface appearance of the laminate pressed with the press plate 3000-3 was not different from that of the laminate pressed with the control press plate.

Press plate and press plate 3000-3 shown in Table 1
Was cleaned and then etched under radio frequency conditions in a planar magnetron sputter coater. Next, these press plates were coated with titanium diboride by the magnetron sputter coating apparatus under the following conditions on average.

[0033]

[Table 2]

Three types of high gloss press plates of the present invention having a size of about 4 feet × 8 feet were prepared. These press plates are referred to as press plates 3-1, 3-2, and 3-3. The press plate was coated with titanium diboride under planar magnetron discharge conditions.

The press plates 3-1, 3-2 and 3-3 are
Anodically etched in a planar magnetron sputter coater under the following conditions on average and then coated with titanium and titanium diboride. The press plate was chemically cleaned before being placed in the sputter coater. The temperature of the press plate during etching and coating is about 300 ° F
(149 ° C.). At this temperature, the press plate did not warp.

[0036]

[Table 3]

High pressure, black, with more than 1200 sheets of alumina particles with an average particle size of 35 microns on the surface to be pressed
Press plate 3-3 was used for pressing the high gloss laminate. After pressing the 1200 laminated plates, a pressed plate 3-3
Was examined for scratches, but none were found. The titanium diboride coating on the pressed plates 3-1 and 3-2 was separated from the stainless steel substrate before the number of pressed laminates was less than 100.

The zirconium diboride coated high gloss press plate and the control press plate of the present invention were used to press ten black and high gloss laminates, respectively. Of the pressed laminate,
ASTM D2244 color difference compared to reference is about (0.2
6) ΔE, ASTM D2457, 60 degree square gloss was about 100. There was no difference in the surface appearance of the laminates pressed with the zirconium diboride coated and symmetric press plates.

The zirconium diboride coated high gloss press plate of the present invention was used for pressing ten black, high gloss laminates having alumina particles having an average particle size of 35 microns on the surface to be pressed. The laminate was pressed at about 1000 psi (68 bar) and 280 ° F (138 ° C). 3
A commercially available overlay sheet with 5 micron alumina grit (PGA822 from Mead) is the pressed surface of the laminate. After pressing the ten laminates, no scratches were seen on the pressed plates.

The zirconium diboride press plate has an ASTM D2457, 60 degree square gloss of about 100 of the laminated plate.
And cut from a high gloss 410 stainless steel pressed plate. Two press plates, approximately 12 inches by 12 inches in size, were cut from the press plates.
One was coated with about 5 microns of zirconium diboride in a planar magnetron sputter coater. The press plate was etched under radio frequency conditions for about 15 minutes before applying the zirconium diboride coating. On average in a planar magnetron sputter coating apparatus,
Sixteen micron zirconium diboride coatings were applied in 15 scans while depositing approximately 4,000 ° of zirconium diboride per scan.

[0041]

[Table 4]

A 6 inch × 6 inch (15.24 inch) coated with titanium nitride by a magnetron sputter coating apparatus.
(cm × 15.24 cm), the black laminate was pressed. The test results shown in Table 3 are average results of five laminated plates pressed by each press plate.

[0043]

[Table 5]

The glossiness of the laminate pressed with the titanium nitride-coated press plate was lower than the glossiness of the laminate pressed with the control press plate. The color of the laminate pressed with the titanium nitride coated press plate was significantly different from the color of the laminate pressed with the uncoated control press plate. The titanium nitride-coated press plate and the laminate pressed with the titanium nitride-coated press plate exhibited a bronze color.

A 6 inch × 6 inch (15.24 inch) coated with niobium nitride using a magnetron sputter coating apparatus.
(cm × 15.24 cm), the black laminate was pressed. The test results shown in Table 4 are average results of five laminated plates pressed by each press plate.

[0046]

[Table 6]

The gloss of the laminate pressed with the niobium nitride coated press plate was lower than the gloss of the laminate pressed with the press plate before coating. The color of the laminate pressed with the press plate coated with niobium nitride was significantly different from the laminate pressed with the press plate before coating.

The black laminate was pressed with a 6 inch × 6 inch (15.24 cm × 15.24 cm) press plate coated with diamond-like carbon with a magnetron sputter coater. The laminate adhered to the diamond-like carbon coated press plate and broke when the laminate was pulled away from the press plate.

Although specific embodiments of the present invention have been described in detail, it should be understood that various other modifications will be apparent to those skilled in the art without departing from the spirit and scope of the invention. There will be. Therefore, the scope of the claims appended hereto is not limited to the embodiments and description disclosed herein, but rather the claims are regarded by the person skilled in the art as equivalent to the invention. It is to be understood that all features of the patentable novelty belonging to this invention are included, including all features that are conceivable.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI D21H 27/30 D21H 27/30 B // B29K 105: 06 (72) Inventor JT Oliver United States of America 76513 Belton, Chatham Road 710, Beltton

Claims (24)

[Claims] 1. A flat press surface for producing a decorative board from a resin-impregnated paper, wherein the press surface is formed by hafnium diboride, molybdenum diboride, tantalum diboride, A planar surface coated with a diboride selected from the group consisting of titanium boride, tungsten diboride, vanadium diboride, or zirconium diboride or a mixture thereof and having a Vickers hardness of at least 2,000, A flat press surface comprising: 2. A flat pressed surface according to claim 1, wherein said surface is coated with a diboride by a planar magnetron sputter coating apparatus to at least a Vickers hardness of 2200. 3. A flat pressed surface according to claim 1, wherein said surface is coated with a diboride selected from the group consisting of titanium diboride, zirconium diboride or a mixture thereof. 4. A flat pressed surface according to claim 1, wherein said surface is coated with titanium diboride. 5. A flat pressed surface according to claim 1, wherein said surface is first coated with titanium and then coated with diboride by a planar magnetron sputter coating apparatus. 6. The diboride coating having a thickness of at least 3
The flat pressed surface according to claim 1, wherein the surface is a micron. 7. The flat pressed surface according to claim 1, wherein the thickness of said diboride coating does not exceed 6 microns. 8. A press plate having a flat press surface for producing a decorative plate from resin-impregnated paper, wherein the press plate is coated with titanium diboride by a planar magnetron sputter coating apparatus and has a Vickers hardness of at least 2.
000. A press plate comprising a planar surface of 000. 9. The press plate according to claim 8, wherein the flat surface is coated with titanium diboride by a planar magnetron sputter coating apparatus to have a Vickers hardness of at least 2,200. 10. The press plate according to claim 8, wherein the planar surface is first coated with titanium and then with titanium diboride by a planar magnetron sputter coating apparatus. 11. The press plate of claim 8, wherein said titanium diboride coating has a thickness of at least 3 microns. 12. The press plate according to claim 8, wherein the thickness of said titanium diboride coating does not exceed 6 microns. 13. A method for producing a flat press surface for manufacturing a decorative board from a resin-impregnated paper, comprising: applying a desired finish to the flat press surface; removing contaminants from the flat surface; The surface of the plane is coated with a hafnium diboride, molybdenum diboride, tantalum diboride, titanium diboride, tungsten diboride, vanadium diboride, or zirconium diboride by a planar magnetron sputter coating apparatus. A method of producing a flat pressed surface by coating with a diboride selected from the group consisting of these mixtures to have a Vickers hardness of at least 2,000. 14. The method of claim 13, wherein the surface is coated with a diboride by a planar magnetron sputter coating apparatus to have a Vickers hardness of at least 2200. 15. The method according to claim 1, wherein the surface is coated with a diboride selected from the group consisting of titanium diboride, zirconium diboride or a mixture thereof.
3. The method for producing a flat pressed surface according to 3. 16. The method according to claim 13, wherein the surface is coated with titanium diboride. 17. The method according to claim 13, wherein the surface is first coated with titanium and then with diboride by a planar magnetron sputter coating apparatus. 18. The method according to claim 13, wherein the thickness of the diboride coating is at least 3 microns. 19. The method of claim 13, wherein the thickness of the diboride coating does not exceed 6 microns. 20. A method of producing a press plate having a flat press surface for producing a decorative plate from resin-impregnated paper, wherein a desired finish is applied to the flat press surface, and a contaminant is removed from the press surface. And a step of coating the flat surface with titanium diboride to a Vickers hardness of at least 2,000. 21. The method according to claim 20, wherein the flat surface is coated with titanium diboride by a planar magnetron sputter coating apparatus to have a Vickers hardness of at least 2,200. 22. The method according to claim 20, wherein the planar surface is first coated with titanium and then with titanium diboride by a planar magnetron sputter coating apparatus. 23. The method of claim 20, wherein said titanium diboride coating has a thickness of at least 3 microns. 24. A method according to claim 20, wherein the thickness of the titanium diboride coating does not exceed 6 microns.