Low-dusting multi-functional material and method for manufacturing the same

Abstract

This invention provides a low-dusting, multi-functional material that suppresses dust generation associated with sliding and other processes, and an efficient method for manufacturing the same. [Solution] The invention comprises a substrate and an acrylic resin coating layer formed on the surface of the substrate, wherein when the acrylic resin coating layer is measured in the thickness direction by glow discharge emission spectrometry, there exists a depth where the silicon concentration (at%) / carbon concentration (at%) is 0.002 or more and 0.1 or less, and when SEM-EDS analysis is performed with an acceleration voltage of 5.0kV in a cross section parallel to the thickness direction of the acrylic resin coating layer, the number density of silicon-containing particles is 10 particles / 100μm 2 The following is a low-dusting, multi-functional material characterized in that silicon-containing particles are regions within the white dots identifiable by SEM observation where the silicon concentration in the EDS analysis results is 2.5 at% or more higher compared to the peripheral areas that do not include the white dots within the probe diameter.

Description

[Technical Field]

[0001] The present invention relates to a multi-functional material with suppressed dust generation and a method for manufacturing the same. The multi-functional material with suppressed dust generation can be suitably used, for example, in the manufacture of semiconductor devices such as LSIs and ultra-large-scale integrated circuits (ULSIs) and liquid crystal panels, as well as in pellicles used in lithography processes to prevent foreign matter from adhering to photomasks and reticles. [Background technology]

[0002] In various electronic devices and precision machinery, dust generated from sliding parts and dust adhering to various components can cause malfunctions and shorten the lifespan of the equipment. Furthermore, when dust is generated from the pellicle used in the manufacture of semiconductor devices such as LSIs and ultra-large-scale integrated circuits (ULSIs) and liquid crystal panels, it becomes impossible to form good patterns using lithography.

[0003] Semiconductor devices such as LSIs and ultra-large-scale integrated circuits (LSIs) and liquid crystal panels have patterns formed by irradiating semiconductor wafers or liquid crystal masters with light (lithography). However, if a master with dust adhering to it is used, the dust absorbs and / or inverts the light, resulting in poor pattern transfer (for example, pattern deformation or unclear edges). As a result, the quality and appearance of semiconductor devices and liquid crystal panels are impaired, leading to problems such as reduced performance and manufacturing yield.

[0004] For this reason, lithography processes are usually carried out in a cleanroom, but even in such an environment, it is not possible to completely prevent dust from adhering to the exposure plate. Therefore, it is common to provide a pellicle on the surface of the exposure plate to protect against dust. The pellicle consists of a pellicle frame and a pellicle film stretched over the pellicle frame, and is installed so as to surround the pattern area formed on the surface of the exposure plate. If the focus is set on the pattern on the exposure plate during lithography, even if dust adheres to the pellicle film, that dust will not affect the transfer.

[0005] However, it is difficult to completely suppress dust generation from the pellicle during transportation and movement. In response to this, for example, Patent Document 1 (Japanese Patent Application Publication No. 07-43892) discloses a pellicle characterized by having paint coated on the side surface or the entire surface of the pellicle frame by electrodeposition coating.

[0006] In the pellicle described in Patent Document 1 above, the paint is coated on the sides or the entire surface of the pellicle frame by electrodeposition coating. As a result, the coating film is not uneven or porous like an anodized layer, and the coating surface is uniform and smooth, thus completely preventing dust generation during the transportation or movement of the pellicle. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 07-43892 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] However, even if the coating surface of the pellicle described in Patent Document 1 is uniform and smooth, the sliding properties and durability of the coating layer are not sufficient, and it is difficult to completely suppress dust generation from the coating layer. In addition, if the coating layer contains second-phase particles, the detachment of these particles due to sliding becomes a problem. Furthermore, as a means of fixing the pellicle film, not only a pellicle frame consisting of a single part is sometimes used, but also a pellicle assembly consisting of multiple members that are engaged by mechanical fixing means utilizing elasticity. In this case, since there are mechanical engagement points, the requirement for low dust generation from the constituent members becomes even greater.

[0009] In view of the problems of the prior art described above, the object of the present invention is to provide a low-dusting multi-functional material that suppresses the generation of dust associated with sliding and the like, and an efficient method for manufacturing the same. [Means for solving the problem]

[0010] In order to achieve the above objective, the inventors of this invention have diligently researched low-dusting, multi-functional materials and efficient manufacturing methods thereof. As a result, they have found that forming a silicon-containing acrylic resin coating layer on the outermost surface of the substrate is extremely effective, leading to the present invention.

[0011] In other words, the present invention is Substrate and The substrate has an acrylic resin coating layer formed on its surface, When the aforementioned acrylic resin coating layer is measured in the thickness direction by glow discharge emission analysis, there exists a depth where the silicon concentration (at%) / carbon concentration (at%) is between 0.002 and 0.1. When SEM-EDS analysis was performed on a cross-section parallel to the thickness direction of the acrylic resin coating layer with an acceleration voltage of 5kV, the number density of silicon-containing particles was 10 particles / 100μm 2 The following: The silicon-containing particles are regions within the white dots identified by SEM observation where the silicon concentration in the EDS analysis results is 2.5 at% or higher compared to the peripheral areas that do not include the white dots within the probe diameter. We provide a low-dusting, multi-functional material characterized by the following:

[0012] The most distinctive feature of the low-dusting, multi-functional material of the present invention is that a silicon-containing acrylic resin coating layer is formed on the outermost surface of the substrate. The inclusion of silicon in the acrylic resin coating layer increases its hardness and improves its abrasion resistance. Furthermore, since silicon is uniformly distributed within the acrylic resin coating layer and does not exist as compound particles of a size and number that would cause dust, compound particles do not detach from the acrylic resin coating layer and become a source of foreign matter. Moreover, the inclusion of silicon in the acrylic resin coating layer can suppress the elution of ions (especially organic acids).

[0013] Furthermore, in the low-dusting multifunctional material of the present invention, when the acrylic resin coating layer is measured by glow discharge emission analysis in the thickness direction, there exists a depth to which the silicon concentration (at%) / carbon concentration (at%) is 0.002 or more and 0.1 or less. The existence of a depth in the acrylic resin coating layer to which the silicon concentration (at%) / carbon concentration (at%) is 0.002 or more and 0.1 or less allows for sufficient silicon to be contained in the acrylic resin layer, thereby reliably obtaining the effect of increased hardness and the effect of suppressing eluted ions.

[0014] Furthermore, in the low-dusting multi-functional material of the present invention, when SEM-EDS analysis was performed with an acceleration voltage of 5.0 kV in a cross-section parallel to the thickness direction of the acrylic resin coating layer, the number density of silicon-containing particles was 10 particles / 100 μm. 2 The following applies. Here, silicon-containing particles are defined as regions within the white dots with a diameter of 100 nm or more, identifiable by SEM observation, where the silicon concentration in the EDS analysis results is 2.5 at% higher than that of the surrounding areas not included in the probe diameter. The SEM probe diameter is also affected by measurement conditions other than the acceleration voltage, but "surrounding areas not included in the probe diameter" means that the white dots of interest are not within the measurement area of ​​the EDS (the probe diameter is approximately 3-5 nm when the acceleration voltage is 5.0 kV). It is preferable to perform SEM-EDS analysis with 5 or more fields of view when calculating the number density of silicon-containing particles. By controlling the size and number of silicon-containing compound particles in this way, even when silicon is contained in the acrylic resin coating layer, dust generation from the acrylic resin coating layer can be suppressed very effectively.

[0015] When SEM-EDS analysis was performed at an acceleration voltage of 5.0 kV on a cross-section parallel to the thickness direction of the acrylic resin coating layer, the number density of silicon-containing particles was 5 particles / 100 μm. 2 Preferably, the following conditions apply. Furthermore, the number density of silicon-containing particles is 1 particle / 100 μm. 2 The following is most preferable: By suppressing the number density of silicon-containing particles, dust generation from the acrylic resin coating layer can be more reliably suppressed.

[0016] In addition, in the low-dust-generating multifunctional material of the present invention, it is preferable that the base material is made of any one of aluminum, aluminum alloy, stainless steel, titanium, titanium alloy, magnesium, magnesium alloy, carbon, or a combination of two or more of these. Although the base material of the low-dust-generating multifunctional material can be a material capable of anion electrodeposition (electrification) under a basic solution, by selecting the base material from these materials, characteristics such as strength, light weight, and corrosion resistance can be imparted to the low-dust-generating multifunctional material as required.

[0017] In addition, in the low-dust-generating multifunctional material of the present invention, it is preferable that the acrylic resin coat layer is formed through an oxide film formed on the surface of the base material. By forming the acrylic resin coat layer through the oxide film, the adhesion of the acrylic resin coat layer can be improved, and arbitrary coloring can also be performed.

[0018] In addition, in the low-dust-generating multifunctional material of the present invention, it is preferable that the acrylic resin coat layer contains a polymer having a carboxyl group. When the acrylic resin coat layer has a carboxyl group, when the acrylic resin coat layer is exposed to hot water or the like, a portion containing the carboxyl group is released from the skeleton of the acrylic resin due to thermal decomposition or the like and is detected as an organic acid. On the other hand, as a result of silicon being uniformly distributed in the acrylic resin coat layer of the low-dust-generating multifunctional material of the present invention, the release of the carboxyl group can be suppressed.

[0019] In addition, in the low-dust-generating multifunctional material of the present invention, it is preferable that the polymer in the acrylic resin coat layer has an -O-Si-O- skeleton. When the polymer in the acrylic resin coat layer has an -O-Si-O- skeleton, in addition to effectively suppressing the release of the carboxyl group from the acrylic resin coat layer, it is possible to more surely achieve an increase in the hardness of the acrylic resin coat layer and an improvement in wear resistance.

[0020] Furthermore, in the low-dusting multi-functional material of the present invention, in an ion elution test in which the ion concentration eluted by immersion in pure water at 90°C for 1 hour is measured, the surface area is 100 cm². 2 Preferably, the elution concentrations in 100 ml of pure water are 50 ppb or less for acetate ions, 150 ppb or less for formate ions, 5 ppb or less for oxalate ions, 5 ppb or less for sulfate ions, 5 ppb or less for nitrate ions, 5 ppb or less for nitrite ions, 10 ppb or less for chloride ions, 5 ppb or less for phosphate ions, and 20 ppb or less for ammonium ions. By suppressing the ion elution amount of the low-dusting multifunctional material to these values, for example, when the low-dusting multifunctional material is used as a pellicle frame, haze generation during lithography can be effectively suppressed.

[0021] The present invention also provides a pellicle frame and a pellicle assembly characterized by containing the low-dusting multi-functional material of the present invention. Since the low-dusting multi-functional material of the present invention suppresses dust generation associated with sliding and the like, it can be suitably used in pellicle frames where dust generation associated with sliding is a problem.

[0022] Furthermore, the present invention is The process involves preparing an aqueous solution containing silicate ions, A paint preparation step for obtaining an electrodeposited paint by mixing an anionic electrodeposited paint with the aqueous solution, The process includes a coating step of forming an acrylic resin coating layer on the surface of a substrate using the aforementioned electrodeposition paint. We also provide a method for manufacturing a low-dusting, multi-functional material characterized by the above.

[0023] By using an electrodeposition coating prepared by mixing an aqueous solution containing silicate ions with an anionic electrodeposition coating, it is possible to form an acrylic resin coating layer on the surface of a substrate in which silicon is uniformly distributed without localization.

[0024] In the method for producing a low-dusting multifunctional material of the present invention, it is preferable that the anionic electrodeposition coating contains an acrylic resin. By including an acrylic resin in the anionic electrodeposition coating, the ionic properties can be improved compared to the substrate state.

[0025] Furthermore, in the method for producing the low-dusting multifunctional material of the present invention, it is preferable that the pH of the electrodeposited paint after the paint preparation step is 8 to 12. By setting the pH of the electrodeposited paint after the paint preparation step to 8 to 12, a suitable ratio of silica to the acrylic resin and other skeletal components in the anionic electrodeposited paint can be achieved.

[0026] Furthermore, in the low-dusting multi-functional material of the present invention, it is preferable to set the applied voltage in the electrodeposition coating process to less than 140V in the coating process for forming an acrylic resin coating layer on the surface of the substrate. By setting the applied voltage in the electrodeposition coating to less than 140V, it is possible to suppress the coarsening of silicon-containing particles in the acrylic resin coating layer. [Effects of the Invention]

[0027] According to the present invention, it is possible to provide a low-dusting multi-functional material in which the generation of dust associated with sliding and other movements is suppressed, and an efficient method for manufacturing the same. [Brief explanation of the drawing]

[0028] [Figure 1] This is a schematic cross-sectional view showing a plate-shaped, low-dusting, multi-functional material, which is one embodiment of the present invention. [Figure 2] This is a schematic cross-sectional view showing a pellicle frame, which is one aspect of the present invention. [Figure 3] This graph shows the relationship between sputtering time and silicon concentration (at%) / carbon concentration (at%) in the actual plate material 1'. [Figure 4] This graph shows the relationship between sputtering time and silicon concentration (at%) / carbon concentration (at%) in comparative plate material 1. [Figure 5] This graph shows the relationship between sputtering time and silicon concentration (at%) / carbon concentration (at%) in comparative plate material 6'. [Figure 6] This is a secondary electron image of the actual plate material 1'. [Figure 7] This is the elemental distribution of Si corresponding to Figure 6. [Figure 8]This is the elemental distribution of Si corresponding to Figure 6. [Figure 9] This is the EDS spectrum at point 1 in Figure 7. [Figure 10] This is the EDS spectrum at point 2 in Figure 8. [Figure 11] This is a secondary electron image of comparison plate material 6. [Figure 12] This is the elemental distribution of Si corresponding to Figure 11. [Figure 13] This is the elemental distribution of Si corresponding to Figure 11. [Figure 14] This is the EDS spectrum at point 1 in Figure 12. [Figure 15] This is the EDS spectrum at point 2 in Figure 13. [Figure 16] These are the results of the dust generation test for test material 1'' and comparison material 1'. [Figure 17] This shows the results of the dust generation test for test material 1''' and comparison material 1''. [Modes for carrying out the invention]

[0029] The following describes in detail representative embodiments of the low-dusting multifunctional material and its manufacturing method according to the present invention with reference to the drawings, but the present invention is not limited to these embodiments. In the following description, the same or corresponding parts are denoted by the same reference numerals, and redundant descriptions may be omitted. Also, since the drawings are for conceptual explanation of the present invention, the dimensions of each component shown and their ratios may differ from those of the actual components.

[0030] 1.Low dust generation multifunctional material (1) Board material Figure 1 is a schematic cross-sectional view showing a plate-shaped low-dusting multifunctional material according to one embodiment of the present invention. In the low-dusting multifunctional material 1, an anodic oxide film 4 is formed on the surface of a plate-shaped substrate 2, and an acrylic resin coating layer 6 is formed on the surface of the anodic oxide film 4.

[0031] The size and shape of the base material 2 are not particularly limited as long as they do not impair the effects of the present invention, and can be appropriately determined according to the application of the low-dusting multi-functional material 1, but for example, it can be a plate material of 50 mm × 50 mm × 3 mm.

[0032] The base material 2 is preferably made of one of the following: aluminum, aluminum alloy, stainless steel, titanium, titanium alloy, magnesium, magnesium alloy, or carbon, or a combination of two or more of these. By selecting the base material of the low-dust multifunctional material 1 from these materials, properties such as strength, lightness, and corrosion resistance can be imparted to the low-dust multifunctional material 1 as needed.

[0033] The acrylic resin coating layer 6 may be formed directly on the surface of the substrate 2, but it is preferable that it be formed via the anodic oxide film 4. By forming the acrylic resin coating layer 6 via the anodic oxide film 4, the adhesion of the acrylic resin coating layer 6 can be improved, and any desired coloring can be applied.

[0034] The thickness of the anodic oxide film 4 is not particularly limited as long as it does not impair the effects of the present invention, but it is preferably 1 to 15 μm. A thickness of 1 μm or more allows for the formation of a homogeneous anodic oxide film 4, while a thickness of 15 μm or less suppresses a decrease in the strength of the anodic oxide film 4.

[0035] The acrylic resin coating layer 6 contains silicon. The inclusion of silicon in the acrylic resin coating layer 6 increases its hardness and improves its abrasion resistance. In addition, since silicon is uniformly distributed in the acrylic resin coating layer 6 and does not exist as compound particles of a size and number that would cause dust, compound particles do not detach from the acrylic resin coating layer 6 and become a source of foreign matter. Furthermore, the inclusion of silicon in the acrylic resin coating layer 6 can also suppress the elution of ions (especially organic acids).

[0036] Furthermore, the acrylic resin coating layer 6 has a depth to which, when measured by glow discharge emission spectrometry in the thickness direction of the acrylic resin coating layer 6, the silicon concentration (at%) / carbon concentration (at%) is between 0.002 and 0.1. The existence of a depth in the acrylic resin coating layer 6 where the silicon concentration (at%) / carbon concentration (at%) is between 0.002 and 0.1 ensures that the acrylic resin coating layer contains sufficient silicon. Moreover, "silicon concentration (at%) / carbon concentration (at%)" is an indicator of the silicon content in the acrylic resin coating layer 6, and by limiting the lower limit to a high level of 0.003, 0.005, or 0.01, a sufficient amount of silicon can be more reliably contained in the acrylic resin coating layer 6 according to that level. Here, the analytical conditions for glow discharge emission spectrometry are not particularly limited as long as they do not impair the effects of the present invention, and appropriate analytical conditions can be used depending on the state of the acrylic resin coating layer 6.

[0037] Furthermore, in the acrylic resin coating layer 6, when SEM-EDS analysis was performed with an acceleration voltage of 5.0 kV in a cross-section parallel to the thickness direction of the acrylic resin coating layer, the number density of silicon-containing particles was 10 particles / 100 μm. 2 The following applies. Here, silicon-containing particles are defined as regions within the white dots with a diameter of 100 nm or more that are identifiable by SEM observation, where the silicon concentration in the EDS analysis results is 2.5 at% higher than that of the surrounding areas not included in the probe diameter. When calculating the number density of silicon-containing particles, it is preferable to perform SEM-EDS analysis over 5 or more fields of view. By controlling the size and number of silicon-containing particles in this way, even if the acrylic resin coating layer 6 contains silicon, dust generation from the acrylic resin coating layer 6 can be suppressed very effectively. Here, the conditions for SEM-EDS observation are not particularly limited as long as they do not impair the effects of the present invention, and appropriate observation (measurement) conditions may be used depending on the state of the acrylic resin coating layer 6.

[0038] Furthermore, the number density of silicon-containing particles is 5 particles / 100 μm 2 Preferably, the following conditions apply: The number density of silicon-containing particles is 1 particle / 100 μm. 2It is even more preferable that the following conditions are met: By ensuring that silicon-containing particles are not detected by SEM-EDS observation, dust generation from the acrylic resin coating layer 6 can be more reliably suppressed.

[0039] Because the plate-shaped, low-dusting, multi-functional material 1 possesses the above-mentioned characteristics, it can be suitably used in various applications where dust particle generation prevention (weather resistance and sliding properties) is required.

[0040] (2) Pellicle frame As another embodiment of the low-dusting multifunctional material of the present invention, Figure 2 shows a schematic cross-sectional view in which the low-dusting multifunctional material is used as a pellicle frame. In the pellicle frame 10, the frame material 12 is the base material 2, an anodic oxide film 4 is formed on the surface of the frame material 12, and an acrylic resin coating layer 6 is formed on the surface of the anodic oxide film 4.

[0041] The frame material 12 can be any of the following: aluminum, aluminum alloy, stainless steel, titanium, titanium alloy, magnesium, magnesium alloy, or carbon, or a combination of two or more of these, but it is preferable to use aluminum or an aluminum alloy. Examples of aluminum or aluminum alloys include 1000 series aluminum, 3000 series aluminum alloy, 5000 series aluminum alloy, 6000 series aluminum alloy, 7000 series aluminum alloy, and Al-Ca alloy.

[0042] Examples of 1000 series aluminum include A1050, A1050A, A1070, A1080, A1085, A1100, A1200, A1N00 and A1N30 as listed in JIS standards; examples of 3000 series aluminum alloys include A3003, A3103, A3203, A3004, A3104, A3005 and A3105 as listed in JIS standards; and examples of 5000 series aluminum alloys include A5005 and A5N01 as listed in JIS standards. Examples of aluminum alloys include A5021, 5N02 and A5042, and examples of 6000 series aluminum include A6101, A6003, A6005, A6N01, A6151 and A6063 as listed in JIS standards, and examples of 7000 series aluminum alloys include A7001, A7003, A7005, A7010, A7020, A7049, A7050, A7075, A7090, A7091, A7178, A7475 and A7N01.

[0043] Furthermore, the Al-Ca alloy is not particularly limited as long as it does not impair the effects of the present invention, and various conventionally known Al-Ca alloys can be used. However, it is preferable to use an Al-Ca alloy that achieves both a low Young's modulus and excellent rollability through control of the crystal structure, grain size, and shape of the Al4Ca precipitates.

[0044] Furthermore, the method for manufacturing the frame material 12 is not particularly limited, and for example, various conventionally known methods for manufacturing aluminum or aluminum alloy materials can be used. As the frame material 12, for example, a powder sintered body processed as a hot extruded material or an aluminum alloy ingot that has been plastically deformed can be used. In addition, heat treatment may be applied as appropriate if necessary.

[0045] The shape of the pellicle frame 10 is not particularly limited as long as it does not impair the effects of the present invention, and can be various conventionally known shapes depending on the shape of the exposure master plate. Generally, the planar shape of the pellicle frame 10 is ring-shaped, rectangular, or square, and has a size and shape that covers the circuit pattern portion provided on the exposure master plate. The pellicle frame 10 may also be provided with air pressure adjustment vents, dust removal filters for said vents, jig holes, etc.

[0046] The height (thickness) of the pellicle frame 10 is preferably 1 to 10 mm, more preferably 2 to 7 mm, and most preferably 3 to 6 mm. By setting the height (thickness) of the pellicle frame 10 to these values, deformation of the pellicle frame 10 can be suppressed, and good handling performance can be ensured.

[0047] The cross-sectional shape of the pellicle frame 10 is not particularly limited as long as it does not impair the effects of the present invention, and can be various conventionally known shapes, but it is preferable that it be a quadrilateral with parallel upper and lower sides. The upper side of the pellicle frame 10 needs to have a width for stretching the pellicle film, and the lower side needs to have a width for providing an adhesive layer for bonding to the exposure plate. For this reason, it is preferable that the widths of the upper and lower sides of the pellicle frame 10 be about 1 to 3 mm.

[0048] The flatness of the pellicle frame 10 is preferably 20 μm or less, and more preferably 10 μm or less. Improving the flatness of the pellicle frame 10 reduces the amount of deformation of the pellicle frame 10 when the pellicle is attached to the exposure plate. The flatness of the pellicle frame 10 can be calculated by measuring the height at a total of eight points: four points at each corner of the pellicle frame 10 and four points in the center of each of the four sides. A virtual plane is then calculated, and the flatness of the pellicle frame 10 is calculated by subtracting the lowest point from the highest point among the distances from this virtual plane.

[0049] The film thickness of the anodic oxide film 4 is not particularly limited as long as the effects of the present invention are not impaired, but it is preferably 1 to 15 μm. By setting the film thickness to 1 μm or more, a uniform anodic oxide film 4 can be formed, and by setting it to 15 μm or less, a decrease in the strength of the anodic oxide film 4 can be suppressed.

[0050] In the acrylic resin coat layer 6 formed on the surface of the anodic oxide film 4, when the acrylic resin coat layer 6 is measured by glow discharge optical emission spectrometry in the layer thickness direction, there is a depth at which the silicon concentration (at%) / carbon concentration (at%) is 0.002 or more and 0.1 or less, and the silicon is uniformly distributed without being localized in the acrylic resin coat 6, so that eluted ions (especially organic acids) can be extremely effectively suppressed. In addition, since the acrylic resin coat layer 6 contains silicon, the acrylic resin coat layer 6 can be made harder and its abrasion resistance can be improved. Since the silicon is uniformly distributed in the acrylic resin coat layer 6 and does not exist as coarse particles, particles do not drop off from the acrylic resin coat layer 6 to become a foreign matter generation source.

[0051] Here, in the present invention, glow discharge optical emission spectrometry (GD-OES) is used for measuring the silicon content of the acrylic resin coat layer 6. For example, in the case of EPMA measurement, when silica particles are dispersed in the acrylic resin coat layer 6 or the like, it is difficult to evaluate the average silicon content in the acrylic resin coat layer 6 when the silicon is present in a scattered manner. On the other hand, in the case of GD-OES, since the measurement result is obtained as an average value in a measurement range of several mmφ, the average silicon content of the acrylic resin coat layer 6 can be evaluated.

[0052] [[ID=1,2,3,5,6,7,9,10,11]] (These tags are just preserved as they are without translation as they seem to be some kind of identifiers or specific notations in a technical context.) Regarding the distribution of silicon in the acrylic resin coat layer 6, when SEM-EDS analysis is performed at an acceleration voltage of 5.0 kV on a cross section parallel to the layer thickness direction of the acrylic resin coat layer, the number density of silicon-containing particles is 10 particles / 100 μm 2The following characteristics apply. Here, silicon-containing particles are defined as regions within the white dots with a diameter of 100 nm or more that are identifiable by SEM observation, where the silicon concentration in the EDS analysis results is 2.5 at% or higher compared to the surrounding areas that do not include the white dots within the probe diameter.

[0053] The type of polymer in the acrylic resin coating layer 6 is not particularly limited as long as it does not impair the effects of the present invention, and various conventionally known polymers used as acrylic resins can be used, but it is preferable that the polymer has an -O-Si-O- skeleton. Having an -O-Si-O- skeleton in the polymer in the acrylic resin coating layer 6 effectively suppresses the release of carboxyl groups (parts including COO and COOH) from the acrylic resin coating layer 6, and even if they are released, it is possible to prevent them from eluting outside the acrylic resin coating layer 6. Furthermore, having an -O-Si-O- skeleton in the polymer in the acrylic resin coating layer 6 makes it possible to more reliably achieve higher hardness and improved wear resistance of the acrylic resin coating layer 6.

[0054] In an ion elution test, the Pellicle Frame 10 was immersed in pure water at 90°C for 1 hour to measure the eluted ion concentration, and its surface area was 100 cm². 2 Preferably, the elution concentrations in 100 ml of pure water are 50 ppb or less for acetate ions, 150 ppb or less for formate ions, 5 ppb or less for oxalate ions, 5 ppb or less for sulfate ions, 5 ppb or less for nitrate ions, 5 ppb or less for nitrite ions, 10 ppb or less for chloride ions, 5 ppb or less for phosphate ions, and 20 ppb or less for ammonium ions. By limiting the ion elution amount of the pellicle frame 10 to these values, haze generation during lithography can be effectively suppressed.

[0055] In Pellicle Frame 10, the brightness index * It is preferable that the L value is 50 or less. The brightness index of the pellicle frame 10 due to blackening. *By setting the L value (lightness index according to Hunter's color difference formula) to 50 or less, it becomes easier to prevent scattering of exposure light and to perform inspections for foreign matter adhesion before use.

[0056] For blackening the pellicle frame 10, for example, dyes, pigments, natural coloring, and electrolytic coloring can be used. From the viewpoint of providing lightfastness, it is preferable to use pigments, natural coloring, and electrolytic coloring.

[0057] 2. Method for manufacturing low-dust multi-functional material The present invention provides a method for producing a low-dusting, multi-functional material, comprising the steps of: preparing an aqueous solution containing silicate ions; preparing a coating by mixing an anionic electrodeposition coating with the aqueous solution containing silicate ions to obtain an electrodeposition coating; and forming an acrylic resin coating layer on the surface of a substrate using the electrodeposition coating. Each step will be described in detail below.

[0058] (1) Step of preparing an aqueous solution containing silicate ions This process is for obtaining an aqueous solution containing silicate ions for use in the paint preparation process. An aqueous solution containing silicate ions can be obtained, for example, by dissolving sodium silicate or potassium silicate in purified water.

[0059] Furthermore, it is not always necessary to prepare an aqueous solution containing silicate ions when manufacturing low-dust multi-functional materials; the aqueous solution containing silicate ions may be procured in solution form.

[0060] (2)Paint adjustment process The paint preparation process involves mixing the aqueous solution obtained in the process of preparing an aqueous solution containing silicate ions with an anionic electrodeposition paint to obtain the electrodeposition paint to be used in the coating process.

[0061] The mixing ratio of the aqueous solution containing silicate ions and the anionic electrodeposition paint is preferably adjusted so that, when the final acrylic resin coating layer 6 is measured by glow discharge emission analysis, there exists a depth at which the silicon concentration (at%) / carbon concentration (at%) is between 0.002 and 0.1, and more preferably so that there exists a depth at which it is between 0.01 and 0.1.

[0062] The anionic electrodeposition coating is not particularly limited as long as it does not impair the effects of the present invention, and various conventionally known anionic electrodeposition coatings can be used. For example, commercially available acrylic / melamine coatings or water-soluble acrylic coatings can be used as anionic electrodeposition coatings.

[0063] The pH of the electrodeposited paint after the paint preparation process is preferably 8 to 12, and more preferably 9 to 11. By setting the pH of the electrodeposited paint after the paint preparation process within this numerical range, a suitable ratio of silica to the acrylic resin and other skeletal components in the anionic electrodeposited paint can be achieved.

[0064] (3) Coating process The coating process is a process for forming an acrylic resin coating layer 6 on the surface of the substrate using the electrodeposition paint obtained in the paint preparation process.

[0065] The electrodeposition coating is an anionic electrodeposition coating, and by using an anionic electrodeposition coating method in which the object to be coated is used as the anode, the amount of gas generated during electrodeposition can be reduced, and the formation of defects such as pinholes in the acrylic resin coating layer 6 can be suppressed.

[0066] The electrodeposition coating method is not particularly limited as long as it does not impair the effects of the present invention, and can be carried out according to conventionally known methods. For example, the substrate 2 can be immersed in an energized bath filled with electrodeposition paint, and current can be applied with the substrate 2 as the anode. The electrodeposition coating conditions are also not particularly limited and can be appropriately selected from a wide range depending on the type of material of the substrate 2, the type of electrodeposition paint, the size and shape of the energized bath, the thickness of the resulting acrylic resin coating layer 6, etc. For example, typically the bath temperature (electrodeposition paint temperature) can be 10 to 50°C, the applied voltage 10 to 450V, and the voltage application time 30 seconds to 20 minutes.

[0067] The electrodeposited substrate 2 is removed from the energized tank and subjected to heat treatment as necessary. The conditions for the heat treatment are not particularly limited as long as they do not impair the effects of the present invention, and conventionally known heating conditions applied to electrodeposited coating films may be applied. The heat treatment includes pre-drying and curing heating, with curing heating performed after pre-drying. Pre-drying can be performed by holding at 60-140°C for 3-30 minutes. Curing heating can be performed by holding at 150-220°C for about 10-60 minutes. Alternatively, for example, a baking treatment at 230°C for 60 minutes may be performed at the end of the heat treatment.

[0068] (4) Other processes It is preferable to apply an anodic oxidation treatment to the substrate 2 before electrodeposition coating to form an anodic oxidation film 4. The conditions for the anodic oxidation treatment are not particularly limited as long as they do not impair the effects of the present invention, and various conventionally known anodic oxidation treatments can be used.

[0069] Furthermore, the lightness index is determined by at least one of dyes, pigments, natural coloring, and electrolytic coloring. * It is preferable to have a color development step to adjust the L value. The color development method using dyes, pigments, natural color development, and electrolytic coloring is not particularly limited as long as it does not impair the effects of the present invention, and various conventionally known color development methods can be used.

[0070] Lightness index of low-dusting multi-functional material 1 by the color development process *By lowering the L value, it can be suitably used as a pellicle frame 10 that facilitates the prevention of exposure light scattering and inspection for foreign matter adhesion before use. Here, from the viewpoint of preventing exposure light scattering and inspection for foreign matter adhesion before use, the brightness index is reduced by blackening. * It is preferable to keep the L value below 50.

[0071] Here, by forming a transparent acrylic resin coating layer 6 on the outermost surface of the blackened pellicle frame 10, the pellicle frame 10 is given a blackish color, making it easier to detect foreign objects during foreign object inspection, and a pellicle frame 10 with the amount of ion elution reduced to the absolute minimum can be obtained.

[0072] Although typical embodiments of the present invention have been described above, the present invention is not limited to these, and various design modifications are possible, all of which fall within the technical scope of the present invention. [Examples]

[0073] ≪Example 1≫ A JIS A7075 aluminum alloy (JIS A7075-T6) sheet material, measuring 50mm x 50mm x 3.0mm thick and treated with the tempering symbol T6 as specified in JIS H0001, was subjected to anodic oxidation under an acidic solution. Subsequently, the anodic oxidation film was colored by Ni electrolytic coloring. Next, an acrylic resin coating layer was formed on the anodic oxidation film by electrodeposition coating. The electrodeposition coating used was a paint stock solution containing acrylic resin and melamine resin as resin components, and isopropanol, butyl alcohol, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether as solvent components, diluted with water and mixed with a 52-57% sodium silicate solution. The mixing ratio was 334g of paint stock solution, 666g of water, and 5g of sodium silicate solution (52-57 wt%, Fujifilm). The pH of the resulting electrodeposition coating was 9.8. Next, the plate material was immersed in an electrostatic tank filled with electrodeposition paint, and an acrylic resin coating layer was formed by applying current with the plate material as the anode, thereby obtaining the experimental plate material 1. The applied voltage was 25V, and the voltage application time was 3 minutes. After that, it was baked at a temperature of 200°C for 30 minutes. The thickness of the formed acrylic resin coating layer was measured to be approximately 3 μm. When only the applied voltage during the formation of the acrylic resin coating layer was changed to 100V, the thickness of the acrylic resin coating layer became approximately 5 μm (experimental plate material 1'). When only the applied voltage during the formation of the acrylic resin coating layer was changed to 80V, the thickness of the acrylic resin coating layer became approximately 4 μm (experimental plate material 1''). When only the applied voltage during the formation of the acrylic resin coating layer was changed to 140V, the thickness of the acrylic resin coating layer became approximately 10 μm (experimental plate material 1'''').

[0074] Example 2 A JIS A7075 aluminum alloy (JIS A7075-T6) sheet material, measuring 50mm x 50mm x 3.0mm thick and treated with the tempering symbol T6 as specified in JIS H0001, was anodized under an acidic solution. The anodized coating was then colored with an organic dye. Next, an acrylic resin coating layer was formed on the anodized coating by electrodeposition. The electrodeposition paint used was a concentrate containing acrylic resin as the resin component and isopropyl alcohol, ethylene glycol mono-n-butyl ether, and 1-butanol as solvent components, diluted with water and mixed with a 52-57% sodium silicate solution. The mixing ratio was 500g of concentrate, 500g of water, and 5g of sodium silicate solution (52-57 wt%, Fujifilm). The resulting electrodeposition coating had a pH of 10. Next, the plate material was immersed in an electrostatic tank filled with electrodeposition paint, and an acrylic resin coating layer was formed by applying current with the plate material as the anode, thereby obtaining the experimental plate material 2. The applied voltage was 100V, and the voltage application time was 1 minute. After that, firing was performed in three stages: 100°C for 10 minutes, 180°C for 60 minutes, and 230°C for 60 minutes.

[0075] Example 3 A JIS A7075 aluminum alloy (JIS A7075-T6) sheet material, measuring 50mm x 50mm x 3.0mm thick and treated with the tempering symbol T6 as specified in JIS H0001, was subjected to anodic oxidation under an acidic solution. Subsequently, the anodic oxidation film was colored by Ni electrolytic coloring. Next, an acrylic resin coating layer was formed on the anodic oxidation film by electrodeposition coating. The electrodeposition coating used was a paint stock solution containing acrylic resin as the resin component and isopropyl alcohol, ethylene glycol mono-n-butyl ether, and 1-butanol as solvent components, diluted with water and mixed with a 52-57% sodium silicate solution. The mixing ratio was 500g of paint stock solution, 500g of water, and 5g of sodium silicate solution (52-57 wt%, Fujifilm). The pH of the resulting electrodeposition coating was 10. Next, the plate material was immersed in an electrostatic tank filled with electrodeposition paint, and an acrylic resin coating layer was formed by applying current with the plate material as the anode, thereby obtaining the experimental plate material 3. The applied voltage was 140V, and the voltage application time was 1 minute. Subsequently, firing was performed in three stages: at a temperature of 100°C for 10 minutes, at a temperature of 180°C for 60 minutes, and at a temperature of 230°C for 60 minutes. The thickness of the formed acrylic resin coating layer was measured to be approximately 15 μm.

[0076] ≪Example 4≫ A JIS A7075 aluminum alloy (JIS A7075-T6) sheet material, measuring 50mm x 50mm x 3.0mm thick and treated with the tempering symbol T6 as specified in JIS H0001, was subjected to anodic oxidation under an acidic solution. Subsequently, the anodic oxidation film was colored by Ni electrolytic coloring. Next, an acrylic resin coating layer was formed on the anodic oxidation film by electrodeposition coating. An acrylic resin type paint concentrate containing acrylic resin as the resin component and triethylamine, ethylene glycol mono-n-butyl, isopropyl alcohol, methyl methacrylate, and ethyl acrylate as solvent components was diluted with water and mixed with a sodium silicate solution. The mixing ratio was 200g of paint concentrate, 800g of water, and 5g of sodium silicate solution (52-57wt%, Fujifilm). The pH of the resulting electrodeposited coating was 10. Next, the plate material was immersed in an energized tank filled with electrodeposition paint, and an acrylic resin coating layer was formed by applying current with the plate material as the anode, thereby obtaining the experimental plate material 4. The applied voltage during electrodeposition painting was 140V, and the voltage application time was 1 minute. After that, it was baked at a temperature of 180°C for 30 minutes. The thickness of the formed acrylic resin coating layer was measured to be approximately 15 μm.

[0077] ≪Comparative Example 1≫ A paint stock solution containing acrylic resin and melamine resin as resin components, and isopropanol, butyl alcohol, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether as solvent components, was diluted with water and used as is without mixing with a sodium silicate solution. The mixing ratio was 334g of paint and 666g of water. The pH of the resulting electrodeposited paint was 7.7. Next, a plate material was immersed in an energized tank filled with the electrodeposited paint, and an acrylic resin coating layer was formed by applying current with the plate material as the anode, thereby obtaining comparative plate material 1. The applied voltage was 100V, and the voltage application time was 3 minutes. After that, it was baked at a temperature of 200°C for 30 minutes. The thickness of the formed acrylic resin coating layer was measured to be approximately 3 μm. When only the applied voltage during the formation of the acrylic resin coating layer was changed to 80V, the film thickness of the acrylic resin coating layer became approximately 3 μm (comparative plate material 1'). When only the applied voltage during acrylic resin coating layer formation was changed to 140V, the thickness of the acrylic resin coating layer became approximately 8μm (comparison plate material 1'').

[0078] ≪Comparative Example 2≫ A JIS A7075 aluminum alloy (JIS A7075-T6) sheet material, measuring 50 mm x 50 mm x 3.0 mm thick and treated with the tempering symbol T6 as specified in JIS H0001, was subjected to anodic oxidation under an acidic solution. The anodic oxidation film was then colored with an organic dye. Next, an acrylic resin coating layer was formed on the anodic oxidation film by electrodeposition coating. The electrodeposition paint used was a diluted solution of paint stock containing acrylic resin as the resin component and isopropyl alcohol, ethylene glycol mono-n-butyl ether, and 1-butanol as solvent components. The mixing ratio was 500 g of paint stock and 500 g of water. The resulting electrodeposition paint had a pH of 7.9. Next, the sheet material was immersed in an electrostatic tank filled with the electrodeposition paint, and an acrylic resin coating layer was formed by applying current with the sheet material as the anode, obtaining comparative sheet material 2. The applied voltage was 100 V, and the voltage application time was 1 minute. Afterward, the cakes were baked in three stages: 100°C for 10 minutes, 180°C for 60 minutes, and 230°C for 60 minutes.

[0079] ≪Comparative Example 3≫ A JIS A7075 aluminum alloy (JIS A7075-T6) sheet material, measuring 50 mm x 50 mm x 3.0 mm thick and treated with the tempering symbol T6 as specified in JIS H0001, was subjected to anodic oxidation under an acidic solution. Subsequently, the anodic oxide film was colored by Ni electrolytic coloring. Next, an acrylic resin coating layer was formed on the anodic oxide film by electrodeposition coating. The electrodeposition paint used was a paint stock solution containing acrylic resin as the resin component and isopropyl alcohol, ethylene glycol mono-n-butyl ether, and 1-butanol as solvent components, diluted with water. The mixing ratio was 500 g of paint stock solution and 500 g of water. The pH of the resulting electrodeposition paint was 7.9. Next, the sheet material was immersed in an electrostatic tank filled with the electrodeposition paint, and an acrylic resin coating layer was formed by applying current with the sheet material as the anode, thereby obtaining comparative sheet material 3. The applied voltage was 140 V, and the voltage application time was 1 minute. Subsequently, the material was fired in three stages: 100°C for 10 minutes, 180°C for 60 minutes, and 230°C for 60 minutes. The thickness of the formed acrylic resin coating layer was measured to be approximately 15 μm.

[0080] ≪Comparative Example 4≫ A JIS A7075 aluminum alloy (JIS A7075-T6) sheet material with dimensions of 50 mm x 50 mm x thickness of 3.0 mm, treated with the tempering symbol T6 as specified in JIS H0001, was subjected to anodic oxidation under an acidic solution. Subsequently, the anodic oxidation film was colored by Ni electrolytic coloring. Next, an acrylic resin coating layer was formed on the anodic oxidation film by electrodeposition coating. An acrylic resin type paint stock solution containing acrylic resin as the resin component and triethylamine, ethylene glycol mono-n-butyl, isopropyl alcohol, methyl methacrylate, and ethyl acrylate as solvent components was diluted with water and mixed with a sodium silicate solution. The mixing ratio was 200 g of paint stock solution and 800 g of water. The pH of the resulting electrodeposited paint was 7.8. Next, the sheet material was immersed in an electrostatic tank filled with the electrodeposited paint, and an acrylic resin coating layer was formed by applying an electric current with the sheet material as the anode, thereby obtaining comparative sheet material 4. In the electrodeposition coating process, a voltage of 140V was applied for a duration of 1 minute. Following this, a baking process was performed at 180°C for 30 minutes. The thickness of the formed acrylic resin coating layer was measured to be approximately 15 μm.

[0081] ≪Comparative Example 5≫ A JIS A7075 aluminum alloy (JIS A7075-T6) sheet material, measuring 50 mm x 50 mm x 3.0 mm thick and treated with the tempering symbol T6 as specified in JIS H0001, was subjected to anodic oxidation under an acidic solution. Subsequently, the anodic oxide film was colored by Ni electrolytic coloring. Next, an acrylic resin coating layer was formed on the anodic oxide film by electrodeposition coating. The electrodeposition paint used was a stock solution containing acrylic resin as the resin component and isopropyl alcohol, ethylene glycol mono-n-butyl ether, 1-butanol, and polyether-modified polydimethylsiloxane as solvent components. The pH of the resulting electrodeposition paint was 7.7. Next, the sheet material was immersed in an energized tank filled with the electrodeposition paint, and an acrylic resin coating layer was formed by applying current with the sheet material as the anode, thereby obtaining comparative sheet material 5. The applied voltage was 100 V, and the voltage application time was 1 minute. Afterward, the cakes were baked in two stages: 15 minutes at 110°C and 30 minutes at 180°C.

[0082] ≪Comparative Example 6≫ A JIS A7075 aluminum alloy (JIS A7075-T6) sheet material, measuring 50 mm x 50 mm x 3.0 mm thick and treated with the tempering symbol T6 as specified in JIS H0001, was subjected to anodic oxidation under an acidic solution. Subsequently, the anodic oxide film was colored by Ni electrolytic coloring. Next, an acrylic resin coating layer was formed on the anodic oxide film by electrodeposition coating. The electrodeposition paint used was a stock solution containing acrylic resin as the resin component and isopropyl alcohol, ethylene glycol mono-n-butyl ether, 1-butanol, and polyether-modified polydimethylsiloxane as solvent components. The pH of the resulting electrodeposition paint was 7.7. Next, the sheet material was immersed in an energized tank filled with the electrodeposition paint, and an acrylic resin coating layer was formed by applying current with the sheet material as the anode, thereby obtaining comparative sheet material 6. The applied voltage was 140 V, and the voltage application time was 1 minute. Subsequently, the material was fired in two stages: 15 minutes at 110°C and 30 minutes at 180°C. The thickness of the formed acrylic resin coating layer was measured to be approximately 15 μm. When only the applied voltage during the formation of the acrylic resin coating layer was changed to 50 V, the thickness of the acrylic resin coating layer became approximately 5 μm (comparative plate material 6').

[0083] [evaluation] (1) Evaluation of ion elution amount The amount of ion elution was evaluated for experimental plates 1 and 2, and comparative plates 1, 2, and 5. Specifically, each plate was placed in a polyethylene bag, 100 ml of pure water was added, and the bag was sealed. The bag was then immersed at 90°C for 1 hour. The extracted water, from which the components eluted from the pellicle frame were extracted, was analyzed using an ion chromatograph (Thermo Fisher Scientific ICS-2100) at a cell temperature of 35°C, a column (IonPacAS11-HC) temperature of 40°C, and an ion flow rate of 1.5 ml / min.

[0084] Acetate ions, formate ions, chloride ions, nitrite ions, nitrate ions, sulfate ions, oxalate ions, phosphate ions, sodium ions, and ammonium ions were detected from the above-mentioned extracted water, and the surface area of ​​the pellicle frame was 100 cm². 2The elution concentration per 100 ml of pure water was determined. The results are shown in Table 1. The quantitative limit (lower limit) of the ion chromatograph used for evaluation varied depending on the ion species, ranging from 0.01 to 0.001 ppm. The units for each value in Table 1 are ppb, and "ND" means that the ion species in question was not quantified.

[0085] [Table 1]

[0086] As shown in Table 1, the amount of ions eluted in the implementation materials 1 and 2, which are low-dusting multi-functional materials of the present invention, can be confirmed to be extremely small. In contrast, the amount of ions eluted increased in comparative materials 1, 2, and 5, with a particularly large amount of acetate ions and formate ions eluting. From these results, it can be seen that the amount of ions eluted can be significantly reduced by adding silicon to the acrylic resin coating layer.

[0087] (2) Abrasion test Abrasion tests were conducted on test plate materials 3 and 4, and comparative plate materials 3, 4, and 6. Specifically, a friction and abrasion testing machine (FPR-2100) manufactured by Resca Co., Ltd. was used, with the following settings: measurement mode: standard rotation measurement, pin material: SUS304 (3 / 16in), load: 150g or 300g, rotation radius: 5mm, measurement time: 60 seconds, rotation speed: 60rpm. The ambient temperature was 23℃ and the ambient humidity was 70%.

[0088] The frictional force of the test plate 3 was 327.1076 mN, and the coefficient of friction was 0.2224. The dynamic coefficient of friction of the test plate 4 at a load of 150 g was 0.37971, and at a load of 300 g it was 0.58118. The frictional force of the comparison plate 3 was 485.7653 mN, and the coefficient of friction was 0.3303. The dynamic coefficient of friction of the comparison plate 4 at a load of 150 g was 0.41560, and at a load of 300 g it was 0.66100. The dynamic coefficient of friction of the comparison plate 6 at a load of 150 g was 0.38049, and at a load of 300 g it was 0.35194.

[0089] Comparing the actual plate 3 with and without the sodium silicate solution, the frictional force and coefficient of friction were significantly reduced in the actual plate 3 with the sodium silicate solution, indicating that the low-dust multi-functional material of the present invention has excellent sliding properties. Furthermore, comparing the actual plate 4 with and without the sodium silicate solution, the dynamic friction coefficient at a load of 150g and the dynamic friction coefficient at a load of 300g were both low in the actual plate 4 with the sodium silicate solution, indicating that the low-dust multi-functional material of the present invention has excellent sliding properties. Here, the acrylic resin coating layer formed on the comparative plate 6 has a composition that is generally considered to exhibit good sliding properties, but the dynamic friction coefficient of the actual plate 4 at a load of 150g was lower than that of the comparative plate 6. From these results, it can be seen that the low-dust multi-functional material of the present invention has excellent sliding properties and effectively suppresses dust generation.

[0090] (3) Vickers hardness test The Vickers hardness of the acrylic resin coating layer was measured for test boards 3 and 4, and comparative boards 3, 4, and 6. A Mitutoyo HM-221 was used for Vickers hardness measurement, with a test force of 0.001 N. The holding time 1 (time to reach the test force) was 4 seconds, the holding time 2 (time to hold the test force) was 15 seconds, and the holding time 3 (time to release the test force) was 4 seconds to measure the Vickers hardness. Ten points were measured in different areas of the acrylic resin coating layer of each board, and the average value was calculated.

[0091] Comparing the actual plate 3 (with and without sodium silicate solution) with the comparative plate 3, the actual plate 3 had a hardness of 20.2 HV, while the comparative plate 3 had a hardness of 17.1 HV. Similarly, comparing the actual plate 4 (with and without sodium silicate solution) with the comparative plate 4, the actual plate 4 had a hardness of 13.8 HV, while the comparative plate 4 had a hardness of 12.5 HV. These results indicate that the hardness of the acrylic resin coating layer increases with the addition of sodium silicate solution. Furthermore, the Vickers hardness of comparative plate 6, which generally exhibits good sliding properties, is 14.9 HV, indicating that the acrylic resin coating layer of the actual plate 3 is significantly harder than this.

[0092] (4) Glow discharge emission analysis Glow discharge emission spectrometry was performed on the acrylic resin coating layer in the thickness direction for the control plate 1', comparison plate 1, and comparison plate 6'. A HORIBA GD-Profiler 2, Marcus-type radiofrequency glow discharge emission surface spectrometry (GD-OES) was used for the analysis. The measurement conditions were: analysis mode: sputtering rate mode, measurement mode: normal, anode diameter: 4 mmφ, gas pressure: 600 Pa, RF output: 35 W, gas replacement time: 30 seconds, BG measurement time: 10 seconds, measurement time: 4 minutes, and acquisition interval: 0.1. For quantitative measurement of standard samples, the measurement conditions were: pre-sputtering: 30 seconds, measurement time: 10 seconds x 5 times. The standard samples used were 153-1, 155-1, SS-1, 2S-N-DC10, 51S-N-DC2, 6070-N-DC1, and SiO2 (indirect calculation). Quantification was performed in at% and C, O, Si, and Al were quantified.

[0093] Based on the obtained measurement results, the silicon concentration (at%) / carbon concentration (at%) at each sputtering time was calculated. The relationship between sputtering time and silicon concentration (at%) / carbon concentration (at%) for the test plate 1', comparison plate 1, and comparison plate 6' is shown in Figures 3, 4, and 5, respectively. It can be seen that the acrylic resin coating layer of the test plate 1' has a depth where the silicon concentration (at%) / carbon concentration (at%) is between 0.02 and 0.1, but this depth does not exist in comparison plate 1 and comparison plate 6'.

[0094] (5)SEM-EDS analysis SEM-EDS analysis was performed on the acrylic resin coating layer of sample plate 1' and comparison plate plate 6. A JEOL Ltd. JSM-7200F SEM was used, and a JEOL Ltd. JED-2300F EDS was used. The measurement conditions were an acceleration voltage of 5kV and a working distance of 10mm, and elemental mapping by EDS was performed under the conditions of 0.1 seconds × 100 scans (measurement time approximately 30 minutes).

[0095] Figure 6 shows the secondary electron image of the experimental plate material 1'. The white frame in Figure 6 (area within the white frame: 100 μm²) 2 The area enclosed by the box is the elemental mapping area, and it can be seen that there are almost no white spots in the acrylic resin coating layer. The elemental distribution of Si corresponding to Figure 6 is shown in Figures 7 and 8. There are almost no Si-enriched areas in the acrylic resin coating layer, but a white spot can be seen in the upper right. The EDS spectrum of the white spot (point 1 in Figure 7) is shown in Figure 9, and the EDS spectrum of the area outside the white spot (point 2 in Figure 8) is shown in Figure 10. The Si concentration at point 1 is 4.05 at%, and the Si concentration at point 2 is 1.84 at%, confirming that the white spot at point 1 is a silicon-containing particle. When the number of silicon-containing particles within the white box was measured using this method, it was found to be 1 (number density of silicon-containing particles: 1 particle / 100 μm). 2 ).

[0096] Figure 11 shows the secondary electron image of comparison plate material 6. (Area within the white frame in Figure 11: 100 μm²) 2 The area enclosed by the white box is the elemental mapping area, and it can be seen that many white dots are dispersed in the acrylic resin coating layer. The elemental distribution of Si corresponding to Figure 11 is shown in Figures 12 and 13. Regions where Si is concentrated are scattered in the acrylic resin coating layer, and the EDS spectrum of the white dot (point 1 in Figure 12) is shown in Figure 14, and the EDS spectrum of the area outside the white dot (point 2 in Figure 13) is shown in Figure 15. The Si concentration at point 1 is 3.24 at%, and the Si concentration at point 2 is 0.29 at%, confirming that the white dot at point 1 is a silicon-containing particle. When the number of silicon-containing particles within the white box was measured using this method, it was found to be 131 (number density of silicon-containing particles: 131 particles / 100 μm). 2 ).

[0097] SEM-EDS analysis results show that in the plate material of the present invention, the formation of fine particles in the acrylic resin coating layer, which causes dust generation due to sliding and other movements, is extremely effectively suppressed.

[0098] (6) Dust generation test Dust generation tests were conducted on test plate 1'', test plate 1'''', comparative plate 1', and comparative plate 1''. Specifically, ultrasound was applied to each plate in ultrapure water, and the number of fine particles generated by the application of the ultrasound was measured. An ultrasonic device (US-4) manufactured by SND Corporation was used to apply the ultrasound, and a high-sensitivity turbidimeter / fine particle counter (NP7700T) manufactured by Nippon Denshoku Industries Ltd. was used to measure the number of fine particles.

[0099] More specifically, ultrapure water was placed in a 3L beaker, and ultrasonic waves were applied to each plate material for 1 minute while agitating it in the ultrapure water. After that, the plates were removed, rinsed with 50 ml / minute water, and then 50 ml / minute measurements were taken three times, and the average value was measured. This process was repeated 10 times to measure the number of fine particles per 50 ml. Here, this measurement was to evaluate the amount of dust and debris adhering to the surface of the plate material, as well as dust caused by the acrylic resin coating layer. The durability of the acrylic resin coating layer itself was also evaluated by repeating the ultrasonic application 10 times. The particle sizes measured by the high-sensitivity turbidimeter and fine particle counter used for the measurement were 0.5~1 μm, 1~3 μm, 3~7 μm, 7~12 μm, 12~15 μm, and 15 μm or larger, and the measurement time for each measurement was 60 seconds.

[0100] Figure 16 shows the measurement results for test material 1'' and comparison material 1', and Figure 17 shows the measurement results for test material 1'''' and comparison material 1''. Here, the number of particles on the vertical axis is the total number of all measured particle sizes, and the horizontal axis is the number of measurements. In both examples in Figure 16 and Figure 17, it can be seen that the cleanliness of the plate surface improves as the number of measurements increases, and it can be observed that no cracks or other defects occur in the acrylic resin coating layer. On the other hand, when comparing the number of particles in test material 1'' and comparison material 1' at the same number of measurements, test material 1'' tends to be superior, and similarly, when comparing test material 1'''' and comparison material 1'', test material 1'''' also tends to be superior. [Explanation of Symbols]

[0101] 1...Multifunctional material with low dust generation, 2...Base material, 4. Anodized coating, 6. Acrylic resin coating layer, 10. Pellicle frame, 12. Frame material.

Claims

1. Substrate and The substrate has an acrylic resin coating layer formed on its surface, When the aforementioned acrylic resin coating layer is measured in the thickness direction by glow discharge emission analysis, there exists a depth where the silicon concentration (at%) / carbon concentration (at%) is 0.002 or more and 0.1 or less. When SEM-EDS analysis was performed on a cross-section parallel to the thickness direction of the acrylic resin coating layer with an acceleration voltage of 5 kV, the number density of silicon-containing particles was found to be 10 particles / 100 μm. ２ The following: The silicon-containing particles are regions within the white dots identified by SEM observation where the silicon concentration in the EDS analysis results is 2.5 at% or higher compared to the peripheral areas that do not include the white dots within the probe diameter. A low-dusting, multi-functional material characterized by the following features.

2. The number density of the silicon-containing particles is 5 particles / 100 μm ２ The following: The low-dusting multi-functional material described in claim 1, characterized by the above.

3. The aforementioned base material consists of one of the following: aluminum, aluminum alloy, stainless steel, titanium, titanium alloy, magnesium, magnesium alloy, or carbon, or a combination of two or more of these. A low-dusting multi-functional material according to claim 1 or 2, characterized by the above.

4. The acrylic resin coating layer is formed via an oxide film formed on the surface of the substrate. A low-dusting multi-functional material according to claim 1 or 2, characterized by the above.

5. The acrylic resin coating layer contains a polymer having a carboxyl group. A low-dusting multi-functional material according to claim 1 or 2, characterized by the above.

6. The polymer in the acrylic resin coating layer contains an -O-Si-O- skeleton. A low-dusting multi-functional material according to claim 1 or 2, characterized by the above.

7. The low-dusting multi-functional material described in claim 1 or 2, A pellicle frame and pellicle assembly characterized by the following.

8. The process involves preparing an aqueous solution containing silicate ions, A paint preparation step for obtaining an electrodeposited paint by mixing an anionic electrodeposited paint with the aqueous solution, The process includes a coating step of forming an acrylic resin coating layer on the surface of a substrate using the aforementioned electrodeposition paint. A method for manufacturing a low-dusting, multi-functional material characterized by the following.

9. The aforementioned anionic electrodeposition paint contains an acrylic acid ester. A method for producing a low-dusting multifunctional material according to claim 8, characterized by the above.

10. The pH of the electrodeposited paint after the paint preparation step is 8 to 12. A method for producing a low-dusting multifunctional material according to claim 8 or 9, characterized by the above.

11. In the coating step of forming an acrylic resin coating layer on the surface of the substrate, the applied voltage in electrodeposition coating is set to less than 140V. A method for producing a low-dusting multifunctional material according to claim 8 or 9, characterized by the above.

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