TW201210852A - Apparatus for manufacturing mold for nanoimprinting and method of manufacturing mold for nanoimprinting - Google Patents

Abstract

The present invention generally relates to an apparatus for manufacturing a mold for nanoimprinting which carries out an anodic oxidation treatment of an aluminum substrate by using an electrolyte solution, wherein at least a material of a surface of a portion contacting the electrolyte solution is a metal or an alloy thereof, in which an amount of metal elution is less than 0.2 ppm/cm<SP>2</SP> per unit when soaked in 80ml of the electrolyte solution at room temperature for 450 hours; and a method of manufacturing a mold for nanoimprinting which carries out an anodic oxidation treatment by an electrolysis solution using the apparatus for manufacturing the mold for nanoimprinting. The present invention can provide an apparatus for manufacturing a mold for nanoimprinting which can suppress metal elution into an electrolysis solution when carrying out an anodic oxidation treatment, and a method of manufacturing a mold for nanoimprinting.

Description

[Technical Field] The present invention relates to a device for manufacturing a nanoimprint mold, and a method for producing a nanoimprint mold having a porous structure on its surface. The present application is based on Japanese Patent Application No. 2010-167139, filed on Jan. 26,,,,,,,,,,,,,,,,,,,,, The article of the fine uneven structure (porous structure) of the cycle exhibits an antireflection effect, a lotus effect, and the like. In particular, it is known that a concavo-convex structure called a moth-eye structure is an effective means of anti-reflection by continuously increasing the refractive index from the refractive index of air toward the refractive index of the material of the article. A method of forming a fine concavo-convex structure on the surface of an article, and using a mold having an inverted structure in which the fine concavo-convex structure is formed on the surface, and transferring the fine concavo-convex structure of the die to the surface of the article (nano imprint method) It is attracting attention. As a method of producing a mold for imprinting, a method of forming an inverted structure of a fine concavo-convex structure on the surface of a substrate by a lithography method is common.丄 = 年 年 年 年 年 年 年 年 年 年 年 年 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 201210852 - Factory 11 In addition, it is also proposed to perform anodizing treatment using a positive electrode such as polyvinyl chloride = processing device = [Prior Art Document] [Patent Document] [Patent Document 1] Anodization tank of each oxidation treatment apparatus such as an anodized aluminum square as described in Patent Document 1 is described in Japanese Patent Laid-Open Publication No. H07-224369. Or a heat exchange member or a metal electrolyte such as ruthenium, etc., so if it is reversed, the solution of the solution is extremely contacted with the electrolyte solution, etc. A metal such as titanium or sharp is eluted into the electrolytic solution, and r is easily colored. As a result, the dissolved metal adheres to the obtained contamination, or the foreign matter during the imprinting of the nano-imprint, and the method of oxidizing the carrier The resistance of the anode is solved, but the strength is weak, because Durability is good. Branch, #_转, hot-coating coating, there are problems such as heat exchange efficiency or temperature (four) drop. Therefore, when the substrate is anodized, it is required to use an anodizing of the metal. Anodizing of various components such as tanks or heat exchangers ^ 201210852 . Equipment, and metal [invention] No dissolution into the electrolyte. A hair; !tcII invention completed in the above situation, the purpose is to raise 11^ The present invention is as follows: (1) A manufacturing apparatus for a nanoimprinting mold, which is capable of suppressing the elution of a gold-plated electrolyte during the anodizing treatment, and a manufacturing apparatus of the nano-imprinting mold. The apparatus for manufacturing a nanoimprint mold for anodizing an aluminum substrate with an electrolytic solution, wherein at least a portion of the surface of the portion in contact with the electrolytic solution is a metal or an alloy thereof under the following conditions, [conditions The amount of elution per unit surface of the metal which has been immersed in an 80 mL electrolyte for 450 hours at room temperature is 0.2 ppm/cm 2 or less. (2) The nanoimprint as described in (1) Mold making In the apparatus for manufacturing a nanoimprint mold according to (2), the surface of the portion in contact with the electrolytic solution is made of ruthenium or an alloy thereof. The apparatus for manufacturing a nanoimprint mold according to the above aspect, wherein the material of the surface of the portion in contact with the electrolytic solution is a button or an alloy thereof. (5) For imprinting as described in (1) (6) The apparatus for manufacturing a nanoimprint mold according to (5), wherein a material of a surface of the portion in contact with the electrolytic solution is tantalum or an alloy thereof. (7) The apparatus for manufacturing a nanoimprint mold according to (5), wherein a material of a surface of the portion in contact with the electrolytic solution is a button or an alloy thereof. (8) A method for producing a mold for nanoimprinting, which is characterized in that an electrolytic solution is anodized on an aluminum substrate to produce a mold for forming a nanoimprint having a porous structure, and is characterized in that: The apparatus for manufacturing a nanoimprint mold using a material of at least a portion of the surface in contact with the electrolytic solution is a material for a metal imprinting mold of the following conditions, and anodizing treatment is carried out. [Condition] It has been immersed in 8 at a temperature. The amount of elution per unit surface of the metal in the case of 〇mL of the electrolytic solution was 〇2 ppm/cm2 or less. (9) The method for producing a nanoimprint mold according to (8), wherein the electrolyte solution is oxalic acid. (10) The method for producing a mold for nanoimprint according to (9), wherein a material of a surface of the portion in contact with the electrolytic solution is a fault or an alloy thereof. (11) The method for producing a mold for nanoimprint according to (9), wherein a material of a surface of the portion in contact with the electrolytic solution is la or an alloy thereof. (2) The method for producing a mold for nanoimprint according to (8), wherein the electrolytic solution is sulfuric acid. (13) The method for producing a mold for nanoimprint according to (12), wherein the material of the portion in contact with the electrolytic solution is sharp or an alloy thereof. (14) The method for producing a mold for nanoimprint according to (12), wherein the material of the surface of the portion in contact with the electrolytic solution is a group or the effect of the invention of 201210852 "f invention" according to the present invention In the anodizing treatment in which the metal is eluted into the electrolytic solution, the manufacturing apparatus of the mold for the production of the nano-printing mold can be used, and the embodiment of the present invention will be described in detail below. UV: electron beam, _, and The hot-line, etc.) is a manufacturing device for the ray and anode nanoimprint embossing die. The anode substrate is flat on the surface of the substrate: 5' and the anode on the surface of the substrate is formed into a too + concave-convex shape for the nano ride. Oxidation treatment device. "Room temperature" in the present invention means 25 〇c. In the small month, "the amount of elution per unit surface of the metal in the case of 450 hours of immersion in 80 mL of electrolyte at a temperature of less than 02 fm/cm" means that the metal sheet has been immersed. The elution amount per unit area in the case of 45 μm of the electrolytic solution of j) mL at room temperature was within the above range. [Manufacturing Apparatus of Nano Imprinting Die] Fig. 1 is a cross-sectional view showing an example of a manufacturing apparatus of a nanoimprinting mold of the present invention. The apparatus for manufacturing a nanoimprinting mold 10 includes an anodizing bath 12 filled with an electrolyte, an upper cover 16 covering an upper portion of the anodizing bath 12, and a peripheral edge formed with electricity for receiving overflow from the anodizing tank 12.

a flow tank portion 14 of the S 8 201210852ρι 解 solution; a storage tank 18 for temporarily storing the electrolyte; and a flow passage 20 for flowing the electrolyte received by the flow tank portion 14 toward the storage tank 18 to be sent to the return passage 24 The electrolyte solution of the storage tank 18 is placed on the lower side of the aluminum substrate 3A at the supply port 22 near the bottom of the anodizing tank 12, and the outlet 26 is placed in the middle of the return flow path 24; the rectifying plate 28 And adjusting the flow of the electrolytic solution ejected from the supply port 22; the axial center 34 is inserted into the hollow cylindrical aluminum substrate 3〇 which becomes the anode, and the central axis '% is horizontally held; the driving device ( The illustration is omitted, and the central axis 32 of the axial center % (the center and the axis of the base material 30) is used as a rotation axis to rotate the shaft center % and the base material 30; one cathode plate 36, which holds the base The material 38 is disposed opposite to each other; the power source 38 is electrically connected to the central axis 32 of the shaft 34 and the two cathode plates 36' and the temperature regulating mechanism 4', which adjusts the electrolyte 6^1 of the storage tank 18. The exhaust pump 26 is a flow that forms an electrolyte from the storage tank 18 through the return flow path 24 toward the anodizing tank 12, and is pressed from the supply port 22 to eject the liquid 'by the bottom of the anodizing tank 12 toward The flow of electrolyte on the person. # The rectifying plate 28 is a plate-like member in which two or more through holes are formed by the flow of the electrolyte which is ejected from the supply σ22 from the entire portion of the anodizing tank 12, which is substantially increased from the ground. The drive unit (not shown) in which the surface 3G and the supply unit are disposed substantially horizontally is connected to the center shaft 32 of the sleeve 34 by a t-piece (not shown) such as a ring-shaped chain or a gear: = 1 piece of cathode plate 36 "with respect to the central axis of the domain material 3G in parallel with 201210852. The manner in which the gap material 30 is separated" is described as the substrate 3. Converters and the like: A thermal adhesive which uses water or oil as a heat medium, but has a problem of poor durability. In addition, when the coating is applied, there is a heat exchange: === ί:= two, = 接 ==:: is caused by the metal eluted and the electrolytic _ the electrolyte is colored, which will cause the dissolved metal to adhere. The reason for the mixing of the mold obtained and the contamination of the mold or the foreign matter at the time of nano imprinting. When a large amount of metal is eluted into the electrolytic solution, the formed positive film may not become a desired shape, which is clarified by the research of the present invention. By suppressing the elution of the metal into the electrolyte, it is possible to efficiently produce an anodic embossing mold of an anodic oxide film having a desired shape. Further, when the width of the mold is widened, the apparatus for manufacturing the above-mentioned mold - also becomes large-sized, and thus the metallic members are in contact with the electrolytic solution. Μ has also become bigger. A view on the stable production of molds for nanoimprinting

201210852 -----rHI = 4==The metal piece of the metal material of each member made of metal is dissolved in γ4, α1ρρηι/(^. If the amount of dissolution is greater than the ratio ==/ The metal to be eluted is in the form of an anodized skin. Further, there is a case where a metal mold is produced from a mold manufactured by a device including a member having a dissolved amount of nr, and thus metal or the like is detected. From the point of view of the stable production of molds for nanoimprinting, the amount of elution from the metal in each of the pieces to 80 mL of the electrolyte is preferably 0 ppm/cm to 〇·2 ppm/ Cm2, more preferably 〇ppm/cm2~〇"ppm/cm2. The apparatus for manufacturing a nanoimprint mold of the present invention uses, for example, oxalic acid as the electrolyte solution, at least the surface of the portion in contact with the electrolyte. The material may be a group or an alloy thereof, or a mixture thereof or an alloy thereof. Further, when sulfuric acid is used as the electrolytic solution, for example, the material of the surface of at least the portion in contact with the electrolytic solution may be a button or an alloy thereof, or ruthenium or the like. An alloy. Therefore, the apparatus for manufacturing a nanoimprint mold of the present invention is In general, 'titanium, niobium, tantalum, and niobium are materials having acid resistance and corrosion resistance', but their resistance varies greatly depending on the type of acid, etc. The required performance also differs depending on the application to be used. Especially in the case of manufacturing a mold for nanoimprint by anodization, since it is necessary to highly control the shape of the mold to manufacture a precise molded body, In the case of a material having general eye resistance and money resistance, there is a situation in which the performance is not sufficient. 201210852 -----Γιι situation. The inventors conducted an effort to study the results and clarified that by anodizing In the case of manufacturing a mold for nanoimprinting, it is particularly preferable to use a predetermined metal, and it is clear that a preferable metal is also different depending on the type of electrolytic solution used for anodization. The mold for nanoimprint of the present invention The manufacturing apparatus may be at least at least in contact with electrolysis, and the surface of the portion in contact with the material is a metal j having a specific physical property or less, referred to as a "specific metal" or an alloy thereof, in particular, A valley easily contact member with the electrolytic solution (iv) is part of a particular metal or alloy only cover strains. The metal to be determined by ^^t(4) means that the electrolyte eluted to 80 is a metal having an electrolysis of PPm/Cm2 or less. In the case of using, for example, oxalic acid, the metal may be exemplified as neon or erroneous. In the case where the group = Wei is used as the electrolytic solution, as the specific metal, the portion connected to the electrolytic solution is, for example, the supply port 22 is etched, the upper cover 16, the storage tank 18, and the downstream flow path 2 are provided. . The inner side of the pump 24 and the inner side of the pump, or the portion of the rectifying plate 由 is formed by the temperature of the specific metal Μ 4 mechanism and the electrolyte solution. The temperature mechanism 40 is used to control the 1 rate is poor, fine fine "When the temperature adjustment mechanism 4G is used, there is a possibility that the concentration of the Wei solution is closely controlled. The specific metal or the portion where the two electrolytes are in contact with each other can also read the surface of the member containing other materials. get on_

S 12 201210852 . Use after /π. When the coating is performed, the thickness of the layer containing the specific metal or its alloy is preferably 1 or more, more preferably 1 G or more. When the thickness is i μιη or more, the effect of suppressing elution of the metal into the electrolytic solution is likely to continue. In addition, even if the component is damaged, the internal material is not easily exposed. Preferably, the alloy is an oxide of the specific metal or an element such as crane, #, and carbon added to the specific gold shot. Specifically, it is exemplified by oxidative error, tartaric acid, smectite, noodle, yoshi yue δ gold, carbonized sulphate, ruthenium alloy, and tannic acid chain. The apparatus for manufacturing a nanoimprint mold of the present invention described above, the material-like metal or the metal of the surface of at least the portion in contact with the electrogram, can thereby inhibit the metal from being eluted toward the electrolyte during the anodizing treatment. Therefore, the coloring of the electrolyte can be prevented. The apparatus for manufacturing a nano-imprinting mold of the present invention is suitable as a device for forming a nano-imprinting mold having a porous structure, and is a mold for nanoimprinting in which metal adhesion is reduced. Further, in an electrolytic solution in which the metal has been dissolved, it may be difficult to form a predetermined shape of the riding scale, but by suppressing the elution of the metal into the electrolytic solution, the desired mold can be efficiently produced, and the present invention can be efficiently produced. The nanoimprinting mold obtained by printing the enamel &amp; device has less contamination and can suppress foreign matter incorporation during nanoimprinting. Further, the apparatus for manufacturing a nanoimprint mold of the present invention is in contact with an electrolytic cell. Since the material of the surface of [^ is made of metal, it is possible to ensure durability = and 'the heat exchanger has better *, , father conversion rate, or temperature control than the case where it is coated with Na, so it can be efficiently _ The substrate was anodized at 13 ^jir 201210852. [Manufacturing method j of the nanoimprinting mold j, the nanoimprinting mold of the present invention (hereinafter, simply referred to as "mold") is produced by using at least a material of the surface of the electrolytic solution to be a specific metal. Or the alloy of its alloy riding device (4), the substrate is anodized with an electrolyte. Therefore, it is excellent in the financial properties of the liquid transfer, and the elution of the metal can be suppressed. The method for producing a nanoimprint mold according to the present invention includes the step of performing anodizing treatment on a substrate by an electrolytic solution, and forming a porous structure having two or more pores on the surface of the upper phase. The method of producing green here is to perform the above anodizing treatment in the following apparatus (10): at least the surface of the surface of the electrolyte is immersed in an electrolytic solution of 80 mL at room temperature for 45 hours. In the case where the surface of the metal unit of the metal is eluted, it is set as an alloy of a metal of 〇 2 ppm/cm 2 or less. In the method for producing a mold of the present invention, if the material of the surface of the portion in contact with the electrolytic solution is a device for manufacturing a nanoimprinting mold of a specific metal or an alloy thereof, and the wire is anodized with an electrolytic solution, The other steps are not specific, but preferably have the following steps (4) to (f). (a) a step of forming an oxide film on the surface of an aluminum substrate by anodizing the reduced material under a mosquito voltage in an electrolyte towel. (8) A step of removing the oxide film and forming a dot on the surface of the secret material. Rolling billion 扪 201210852 . -----rll (c) In the electrolyte, the aluminum substrate is anodized again, and the pores are formed into a film having pores. (d) The step of expanding the diameter of the pores. Step ^. After the step (4), the anodization is again performed in the electrolytic solution (the step (d) and the step (e) are repeated, and the anodic oxidation pattern having two or more pores is formed on the J surface. Steps are explained. 8 Further, in the steps (4), (c), and (7), the surface of the portion of the portion in contact with the electrolyte is a nano-pressure (four) mold for the alloy of the alloy. Step (a): As shown in Fig. 2, the shot substrate 3 is anodized to form an oxide film 44 having pores 42. Examples of the shape of the aluminum substrate include a roll shape, a circular tube shape, and a flat plate shape. In order to smooth the surface state, it is preferable to grind == by mechanical polishing, buffing, chemical polishing, and electrolytic polishing treatment (surname processing). The material may be used to remove the oil used in the shape specified by Wang Cheng. Therefore, it is preferred to carry out advanced degreasing treatment before anodizing. The purity of the product is preferably 99% or more, more preferably 99 5% or more. Good - 99.8% or more. The purity of the impurities is low, then the anode has been carried out. In the case of the formation of the condensed film, the unevenness of the size of the fine particles due to the segregation of the impurities, or the regularity of the pores obtained by the anodic oxidation may be reduced. Examples of the electrolytic solution include oxalic acid and sulfuric acid. Aqueous solution \ These electrolytes may be used singly or in combination of two or more. When an aqueous oxalic acid solution is used as the electrolyte: The concentration of the aqueous oxalic acid solution is preferably 0.7 Μ or less. If the concentration of the aqueous oxalic acid solution exceeds 0.7 Μ, it exists. When the current value is too high, the surface of the scale is thick. When the voltage is 30 V to 60 V, anodized aluminum having a regular fine pore having a period of 1 〇〇 nm can be obtained. When the voltage is higher than the range or lower than the range, there is a tendency for the regularity to decrease. The temperature of the electrolytic solution is preferably 60 ° C or lower, more preferably 453⁄4 or less. If the temperature of the electrolytic solution exceeds 60 ° C, it is generated. The phenomenon of "burning", cracking of pores, or surface melting and regular disorder of pores. Case where an aqueous sulfuric acid solution is used as an electrolyte: sulfuric acid The concentration of the solution is preferably 〇.7 M or less. When the concentration of the aqueous sulfuric acid solution exceeds 0.77 Torr, the current value becomes too high and the constant voltage cannot be maintained. When the formation voltage is 25 V to 30 V, An anodized aluminum having a regular pore of 63 nm in periodicity can be obtained. There is a tendency for the regularity to decrease regardless of whether the formation voltage is higher than the range or lower than the range. The temperature of the electrolytic solution is preferably 3 Torr. (The following is more preferably 203⁄4 or less. If the temperature of the electrolyte exceeds 3G °C, the phenomenon of so-called "job" occurs, the pores are broken, or the surface is melted and the pores are regularly disordered. 20121085^ Anodized aluminum in which pores are arranged at relatively large intervals of 100 nm or more can be easily obtained as compared with the case where sulfuric acid is used as the electrolytic solution. When anodized alumina is used as a mold, if the pore spacing is small, it is difficult to ensure mold release property, and therefore it is preferred to use oxalic acid as an electrolytic solution. Step (b): As shown in Fig. 2, the oxide film 44 is temporarily removed to become an anode-oxidized pore generating point 46, whereby the regularity of the pores can be improved. As a method of removing the oxide film, a method of dissolving it in an insoluble state and selectively transferring the scale to a solution towel can be mentioned. As such a solution, for example, a chromic acid/phosphoric acid mixed solution or the like can be mentioned. Step (c): As shown in Fig. 2, if the aluminum substrate having been removed from the oxide film is again subjected to cations and oxygen, an oxide film 44 having columnar pores 42 is formed. The anodization may be carried out under the same conditions as in the step (4). The longer the anodization, the deeper the pores can be obtained. Step (d): As shown in Fig. 2, a process of expanding the diameter of the pores 42 (hereinafter referred to as a pore-expansion domain) is performed. The fine weave treatment is a treatment in which the diameter of the pores obtained by the anodization is enlarged by being immersed in a solution in which the emulsified membrane is dissolved. As such a test, for example, an aqueous phosphoric acid solution or the like. The outer diameter of the shell M 〇 is enlarged, and the diameter of the pore is larger. In the step (d), it is difficult to use a portion of the surface of the 201210852 that is at least free from contact with the electrolyte. By means of the thief county, it is also possible to suppress the dissolution of the metal toward the solution when the pore diameter is enlarged. As a result, it is possible to prevent the coloring of the solution or the metal from being applied to the mold, so that contamination of the mold or foreign matter in the case of nanoimprinting can be more effectively suppressed. y In addition, since the metal is used as the material of the portion in contact with the solution, the durability of the pore diameter expansion processing device can be ensured. Step (e): As shown in FIG. 2, if anodization is performed again, a small-diameter columnar pore 42 extending downward from the bottom of the cylindrical pore 42 is formed, and anodization is performed as long as the step is performed. (a) It can be carried out under the same conditions. The longer the anodization, the deeper the pores can be obtained. Step (f): As shown in FIG. 2, when the pore diameter expanding process of the step (4) and the anodization of the step (e) are repeated, the pores 42 having a shape having a diameter continuously decreasing from the opening portion toward the depth are formed. The oxide film 44, so that the surface of the aluminum substrate 30 has an anode body (a porous oxide film of aluminum (oxypis)) is occupied by the mold body. Finally, it is preferred to end with a step. The number of repetitions is preferably 3 or more, more preferably 5 or more. When the number of right repetitions is two or less, the diameter of the pores is discontinuously reduced. Therefore, the effect of reducing the reflectance of the porous (moth-eye structure) formed using the anodized alumina having such pores is not sufficient. ^ 201210852 .ir type of enumeration: general conical shape, pyramid shape, and 0 column shape, k is as conical shape and pyramidal and depth direction orthogonal (four) pore cross-sectional area from the most continuous continuous reduction shape. The average interval between the pores 42 is toward or below the wavelength of visible light. The pores 42_ average interval is 20 or more. The range of the average interval between the pores 42 is preferably 20 nm or more and 4 nm or less, more preferably 50 nm, such as Λ9. Above the surface, 25-/. Upper I&quot;the following 'and further better distance to the center of the adjacent two 42') = the center of the second 42 to the adjacent pores are averaged (four) ί received 5 · the value obtained by the coffee hole 2 the depth of the average interval is the leg In the case of the case, it is preferably _nm, more preferably 12G_ (four) is preferably 15 〇 〇 β 进 β β β β β β β β β 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉~3.0. The mold body 48 obtained by the step (1) can be transferred to the town of 48 to form a 201210852 as a mold release agent, preferably having a functional group capable of forming a chemical bond with the anodization of the aluminum substrate. Moulding agent. Specifically, it is preferable that the polyoxanol resin, the fluororesin, and the fluorine compound are excellent in mold release property and excellent in adhesion to the mold main body, and it is preferable to have a linalool group. Or a hydrolyzable thiol group, particularly preferably a fluorine compound having a hydrolyzable thiol group. A commercially available product of a gas compound having a hydrolyzable dream base is fluoroalkyl decane, KBM-7803 (manufactured by Shin-Etsu Chemical Co., Ltd.), and "Opt〇〇l" series (manufactured by Daikin Industries Co., Ltd.). ),as well as

NovecEGC-1720 (manufactured by Sumitomo 3M Co., Ltd.) and the like. As a treatment method using a mold release agent, the following methods G) and (II) can be used, and the surface of the mold main body on which the porous structure is formed can be uniformly treated by the release agent. In particular, the method (II) in which the mold body is immersed in the diluted solution of the release agent is applied to the surface of the mold body having the side of the porous structure. The method (I) is preferably a method having the following steps (g) to (h): (g) a step of washing the mold body with water. (h) the body is cut and removed, and the body is removed. Step of water droplets on the surface. The step of immersing the fluoride in a dilute solution obtained by diluting a hydrolyzed zeayl 1 fluorinated product with a solvent. (1) slowly lifting the phase mold body from the solution of]

S 20 201210852 I - Γ For the mold body (k) If necessary, follow the step of heating and humidifying at a later stage (“). (1) A step of drying the mold body. Step (g): (2) π 棂 棂 附着 附着 附着 附着 附着 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 And the impurities (the step (h) is to remove the visible water droplets. The air is blown to the mold body, and the step (i): as a solvent for dilution, a solvent such as a fluorine-based solvent or an alcohol-based solvent may be used. It is preferable to uniformly coat the external mold release agent solution as t', as «Off, publication: New (four), perfluorohexane H ^ cycline, perfluoro {3 · dimethylcyclohexane, And the concentration of the fluorine compound having a hydrolyzed (tetra) group is preferably from 0.01% by mass to 2% by mass. The immersion time is preferably 丨 minutes to 3 〇 minutes. The impregnation temperature is preferably 〇. (:~5〇. (:. Step (j): When the impregnated mold body is lifted from the solution, it is preferable to use an electric lifter or the like to lift it at a fixed speed and suppress the swing at the time of lifting. 21 201210852 Therefore, the coating unevenness can be reduced. The lifting speed is preferably 1 mm/sec to 1 〇mm/sec. Step (k): * Place the mold body under heating and humidification at a later stage than step (1). In this case, the conversion of the fluorine compound (de-plating) is converted into a group, and the reaction of the above-mentioned slightly-examined table is sufficiently performed, and the fixing property of the fluorine compound is improved. 4〇°c~1〇〇.匚 The humidifying condition is preferably a relative humidity of 85% or more. The standing time is preferably from 10 minutes to 1 day. Step (1): in the step of drying the mold body, The mold body can be dried, or it can be heated and dried in a strong ship. The drying temperature is preferably 3〇°c~i5〇°c. The drying time is preferably 5 minutes to 300 minutes. The surface of the water can be confirmed by the mold ^ =: = mold agent has been processed. Has been carried out by the release agent The water contact angle of the surface of the body is preferably 60. Above, it is better to process the 90-solution filling, and the mold release property is good. ^ In the above-mentioned Lai Ri (4) The surface of the portion to be used is made of a specific metal or an alloy thereof, and the fresh liquid/combination is prevented. Thereby, the coloring of the electrolyte can be prevented δ 22 201210852 * writ or the adhesion of the metal to the mold, thereby suppressing the contamination of the mold. In addition, according to the present invention, since the metal is used as the material of the surface of the portion in contact with the electrolytic solution, the durability of the apparatus for manufacturing the nanoimprinting mold can be ensured. Compared with the case where the plastic is applied, the heat exchange rate or the temperature control of the heat exchanger is also excellent, so that a mold for nanoimprinting which forms an anodized aluminum having a desired shape can be efficiently produced. Item having a porous structure] An article having a porous structure on its surface is produced, for example, by using the manufacturing apparatus shown in Fig. 3. The active energy ray-curable resin composition is supplied from the tank 52 to the surface. The roll mold 5 of the porous structure (not shown) is interposed between the strip-shaped film 72 that moves along the surface of the roll mold 50. The roll mold 50 and the pinch pressure are adjusted by the pneumatic cylinder 54. The nip roller 56 'clamps the film 72 and the active energy ray-curable resin composition so that the active 线 line curable resin composition uniformly spreads between the film 72 and the roll-shaped mold 50' while filling the domain mold In the concave portion of the porous structure of 5G, the active energy ray illuminating device below the roll-shaped mold 5G = 8 曰 permeable film 72, and the active energy ray-curable lion composition is irradiated with active energy straight line, and the living energy is tilted. The strand curing tree is cured, whereby a hardened resin layer 74 of a porous f structure to which the surface of the roll mold 50 is transferred is formed. The film 72 23 .11 . 11201210852 having the hardened resin layer 74 formed on the surface thereof is peeled off from the roll mold 5G by peeling off the light 60, whereby the article redundancy as shown in Fig. 4 is obtained. As the active energy ray i 58, it is preferably a high pressure mercury lamp and a metallization lamp, etc. The illumination in this case is mJ/cm2 to 10000 rnJ/cm2.里平乂佳马 1〇〇 Film 72 is a light transmissive film. Examples of the material of the film include propylene resin, polycarbonate, stupid vinyl resin, polylaid, cellulose resin, and

(triacetylcellulose) ^ ^ J The hardened resin layer 74 is a film containing a cured product of an active composition to be described later, and has a porous structure on its surface, and it is known that the structure of the article 7 使用 when using an anodized mold is The porous structure of the surface of the anodized oxide is transferred and formed into two convex portions 76 including a cured product of the active energy ray-curable resin composition. The means of anti-reflection of the rate of return from air. The horse has a flat contact between the convex portions below the wavelength of visible light, that is, mi and two 7 use the mold of the fourth (4) to form a convex material, and the average interval between the six portions is about i00 nm, and the γ is 150 nm or less. More preferably, it is 200 lungs or less, and from the viewpoint that the average interval between the convex portions is easy to form a convex portion, it is preferably 5^24 201210852 of 20 nm or more. The average interval between the convex portions is preferably in the range of 20 nm to 400 nm, more preferably 50 nm to 300 nm, and still more preferably 9 Å to 25 Å. The average interval between the convex portions is measured by an electron microscope to measure the distance between adjacent convex portions (the distance from the convex (four) to the center of the adjacent convex portion) and the measurement is performed. The values are averaged. In the case where the southness of the convexity p is 1 〇〇 (10) at an average interval, it is preferably 80 nm 5 〇〇 nm ′ or more preferably 12 〇 nm to 4 〇〇 nm, and particularly preferably (9) nm to 300 nm. When the height of the right convex portion is 8 〇 nm or more, the reflectance is sufficiently lowered' and the wavelength dependence of the reflectance is small. When the height of the convex portion is 500 nm or less, the scratch resistance of the convex portion becomes good. The height of the convex portion is a value obtained by measuring the distance between the most prominent portion of the convex portion and the lowest portion of the _ portion when the electron microscope is observed at a magnification of 30,000 times. _ The longitudinal outline of the convex part (the height of the convex part / the flat separation between the convex parts) is preferably -, ', 廿. ~ 5.0, more preferably j 2~4 〇, especially good) 5~3 Bu Ruo Above the part, the reflectance is sufficiently reduced. When the longitudinal and lateral directions of the convex portion are .0 or less, the scratch resistance of the convex portion becomes good. The shape of the convex portion is preferably positively increased in the direction of the height in the direction of the height 3 = the shape in the depth direction, and the cross-sectional shape in the two directions of the four directions is a shape such as a triangle, a trapezoid, or a bell shape. The difference between the refractive index of 〇2 and the refractive material of the film 72 is preferably not more than αι, and particularly preferably 〇.〇5 or less. If the refractive index is 25 201210852 ίί二二' then the reflective material structure at the interface between the cured resin layer 74 and the film 72, if the surface is formed of a hydrophilic material from a hydrophobic surface, a super-preparative hardening resin can be obtained. The material of layer 74 has a water contact angle of preferably 9 Å. generation:. The pore structure is shown in Table 120. Take Bu. - It is more preferably 110 or more, and particularly preferably the upper right water contact angle is 9 〇 0 or more, which exerts sufficient anti-pumping.难以 It is difficult to attach because it is necessary to prevent icing. The range of the water contact angle of the surface of the fine concavo-convex structure when the material of the surface 74 is hydrophobic is u: r: 180. In the following, it is particularly preferable that the water-contacting material of the two-surface water is a hydrophilic structure and the surface of the porous structure is _ _ attached, so that sufficient antifouling property is exhibited. In view of the fact that the pores of the hardened resin layer 74 are resistant to the change of the reflectance of the hardened resin layer 74 and the reflectance thereof, the fine concavo-convex structure when the material of the rubbing layer 74 is hydrophilic is suppressed. The range is preferably 3. Above, 3〇. Below, it is more preferably 3. Up, 23 or less, especially good 3. Above, 2ι. the following. (Active energy ray curable resin composition)

S 26 201210852pif The active energy ray-curable resin composition contains a polymerizable compound and a polymerization initiator. As the polymerizable compound, a known compound can be used, and examples thereof include a monomer having a free silk heterozygous and/or surface ionomerizable bond, a valency polymer, and a reactive polymer. Further, the active energy ray-hardening resin composition may also contain a non-reactive polymer and an active energy ray sol-gel reactive composition. In addition, examples of the polymerization initiator include a known photopolymerization initiator, a thermal polymerization initiator, and a polymerization initiator which is subjected to an electron beam curing reaction. Further, the water contact angle of the surface made of the hole (4) of the hardened resin layer 74 was 90. As described above, it is preferred to use a fluorine-containing compound or a polyoxo compound to form a four-dimensional energy-hardening resin composition. Further, water 25 is used to make the surface of the porous structure of the resin layer 74 hard. Hereinafter, it is preferable to use an active energy ray-curable resin which can form a hydrophilic material using a group containing at least a hydrophilic monomer. In view of the fact that it imparts scratch resistance or water resistance, it contains a crosslinkable oxime functional monomer. Further, the multi-t capable monomer may be _ (that is, the hydrophilic polyfunctional single &quot; active conjugated linear curable resin composition may also contain other single [use] as the use of the article 70, : anti-reflective articles, anti-fog substances 27 2〇12l〇852. Products, anti-fouling articles, and water-repellent articles, more specifically, anti-reflection for display, car instrument cover, car mirror, car window The light-emitting efficiency improving member of the organic or inorganic electroluminescence, the solar cell member, etc. Further, the article having a porous structure on the surface is not limited to the article 70 of the illustrated example. For example, the hardened resin layer 74 may not be provided. On the other hand, a porous structure is formed directly on the surface of the film 72. However, from the viewpoint of efficiently forming a porous structure using the roll mold 5, it is preferable to form a porous structure on the surface of the cured resin layer 74. [Example] [Test Example] The following is a description of the test examples. In the following Test Examples 1-1 to 1-4, Test Examples 24 to 4, the anodic oxidation of the apparatus for manufacturing a nanoimprint mold was confirmed. The resistance of the metal of the material of each member such as a groove or a heat exchanger to the electrolyte or the resistance of the metal to the material of each member of the pore diameter expansion processing apparatus to the solution is generally compatible with the use of the group. (Ta), lanthanum (Ti), titanium (Ti), and niobium (Nb), and immersed in an electrolyte or a solution (hereinafter, collectively referred to as "treatment liquid") The concentration of the metal in the treatment liquid. In the test example, as the electrolytic solution used for the anodizing treatment, the aqueous oxalic acid solution was used as the solution for the pore diameter expansion treatment, and the acid-filled water was used. The concentration of some of the oxalic acid aqueous solution is adjusted to 2.7% by mass, and the sulfuric acid aqueous solution is adjusted to 丨5 mass% as long as it is used for the actual anodizing treatment or the pore diameter expansion treatment:

S 28 201210852u Further, when the metal piece is immersed in the treatment liquid, the temperature of the treatment liquid is higher, and the elution promoting effect of the metal is higher. However, this test example is carried out at room temperature. Here, "room temperature" means 25. (In addition, 'Inductively Ccmpled Plasma' ICP) luminescence spectroscopic mass spectrometer (high-frequency inductive coupling mass analysis) using high-sensitivity and high-precision measurement in a short time (Testing Example 1-1 &gt; A test piece (5 〇 cm &gt;&lt; 2.5 cm, thickness 1 mm) of the monomer group was used as a 2.7 mass% aqueous oxalic acid solution as a treatment liquid at room temperature. After immersing for 450 hours, the metal piece was taken out from the treatment liquid, and the concentration of the metal eluted into the treatment liquid was measured in the following manner. First, 1 mL of the treatment liquid after the metal piece was taken out, and then the treatment liquid was transferred. A 50 mL measuring bottle was diluted with 50 mL of pure water to prepare a sample for measurement. Then 'CID horse frequency electro-concentration spectroscopic analysis device (Thermo)

"IRIS Advantage AP" manufactured by Fisher Scientific Co., Ltd. As an ICP emission spectroscopic mass spectrometer, the wavelength of the metal in the measurement sample is measured by selecting the wavelength at which the sensitivity is optimal for each metal. The results are shown in Table 1. &lt;Test Example 1-2 to Test Example 1-4 (Example 1 to Example 4 in Table 1), Test Example 2-1 to Test Example 2-4 (Comparative Example 1 to Comparative Example 4 in Table 1) &gt; In addition to changing the type of the treatment liquid and the metal as shown in Table 1, a sample for measurement was prepared in the same manner as in Test Example-1 by 29 201210852, and the concentration of the metal was measured and used as a sulfuric acid aqueous solution. Μ% by mass aqueous sulfuric acid solution. ^ The results are shown in Table 1. In addition, "&gt;" of the elution amount of Table 1 indicates that the metal is a concentration lower than the detection limit. [Table 1] ------ Example---- Electrolyte-grain metal Ta dissolution amount (ppm) Dissolution amount per unit area (Dpm/cm2) 2 3 Oxalic acid__sulfuric acid Zr Ta U.16 0.006 4 lighter than you | sulfuric acid Nb 1 2.6 0.1 ~~~~ oxalic acid Nb Ti 220 8.3 3 __skin acid Zr 1200 —6.4 45.3 0.24 L Ti ----—2500 94.3 — „ As can be clearly seen according to Table 1, The amount of elution of the parent unit area of cerium and zirconium is less than ppm·2 ppm or less with respect to the aqueous oxalic acid solution. Further, it is clear that the amount of the solution per unit area of the sulphur and the aqueous solution of sulphurium @1 is 〇 2 ppm or less is less. In the production of a mold for nanoimprinting using oxalic acid as an electrolytic solution, it is more suitable as a material for the portion in contact with the electrolytic solution, and the second external measurement is performed on the anode. It can inhibit the dissolution of the Jinle electrolyte. The 奈 is used as the electrolyte of the electrolyte. (4) The manufacturing equipment of the mold pushes the material of the contact part of the liquid, which is suitable for sharpness or sharpness. It can suppress the metal to the electrolyte during the sharp and oxidative treatment. Dissolution. The concentration of metal in titanium in oxalic acid is high, and the metal is easily dissolved out everywhere 201210852. = duck, woven _ High concentration, metal two electricity two == =:: heart print ==; make == material of the part in contact with the electrolyte ❶ metal ^ ^ make (four) 2.7 mass% of oxalic acid solution will be diluted with the above == liquid dilution 3 times the obtained solution was used as an electrolytic solution, and was subjected to electrolytic polishing in a perchloric acid/ethanol mixed solution (volume ratio of 1/4) of a 50 mm x 5 mm x mm thick &amp; Q ^ simple. / 0 of a towel aluminum substrate. The plate (purity is an oxalic acid solution in an amount of 27% by mass), and the solution obtained by dissolving the grass I in which each metal piece is impregnated is three times the obtained electrolytic solution, and M is performed on the above-mentioned weaving under the condition of noun and temperature= Anodizing. After removing the anodic emulsification treatment (4) - part, in the section Qian Ming i minutes ' then use a field emission scanning electron microscope (manufactured by the company, "purchase"), under the acceleration voltage 3 == Observe the cross section and measure the thickness of the oxide film (Fig. 5). As shown in Fig. 5, the anodization using the oxalic acid solution impregnated with the group or the junction is substantially the same as the case where the oxalic acid solution after the mashing is anodized. Anodizing using an aqueous solution of oxalic acid impregnated with titanium |g and just after adjustment As compared to the case of aqueous oxalic acid solution, an anodic oxide film is thinner, no 31 201 210 852.,. Niobium impregnated in the suspension is attached to the male

The method forms an anodized film of a desired shape and thickness. In the aqueous oxalic acid solution, a suspension of ruthenium was confirmed, which was oxidized on the electrode. [Test Example 3] As an aluminum substrate, it was used for electrolytic polishing of a mixture of 50 mm x 50 mm x 〇.3 mm (99.99%) in a peroxyacid/ethanol mixed solution (volume ratio of 1/4). U-electricity horse Step (a): In a 0.3 oxalic acid aqueous solution, at a voltage of 4 〇 v, a temperature of 16. The aluminum plate was anodized for 6 hours under the conditions of ruthenium. Step (b): The aluminum plate on which the oxide film was formed was immersed in a 6 mass% yttrium phosphate 8 mass% chromic acid mixed aqueous solution for 3 hours, and then the oxide film was removed. Step (c): 'The aluminum plate was anodized for 3 seconds in a 0.3 oxalic acid aqueous solution under a condition of a direct current of 4 Torr and a temperature of 16 °C. Step (d): The aluminum plate on which the oxide film was formed was immersed in a 5 mass% aqueous phosphoric acid solution at 32 ° C for 8 minutes', and then the pore diameter expansion treatment was performed. Step (e): The aluminum plate was anodized for 30 seconds in a 0.3 oxalic acid aqueous solution under a condition of a direct current of 4 Torr V and a temperature of 16 °C.

S 32 201210852 Step (f): The above steps (d) and (e) are repeated four times in total, and finally step (d) is performed to obtain a surface having an average interval of 1 〇〇 nm and a depth of 240 nm. A conical shaped pore-shaped anodized aluminum mold body. Step (g): After gently washing away the aqueous phosphoric acid solution on the surface of the mold body by spraying, the mold body was immersed in running water for 1 minute. Step 〇〇 : Air is blown to the mold body to blow air, and water droplets adhering to the surface of the mold body are removed. Step (i): At a temperature, the mold body is diluted with a thinner HD_ZV (manufactured by Harves Co., Ltd.) to reduce the amount of the solution obtained by the use of optool Dsx (manufactured by Daikin Chemicals Co., Ltd.) 1 minute. Step (j): Slowly lift the mold body at 3 mm/sec from the diluted solution. Step (1): Allow the mold body to air dry for 15 minutes to obtain the one that has been treated by the release agent. In the steps (a), (e), and (e), the apparatus for manufacturing a nanoimprint mold using the produced heat exchanger is anodized. 33 £ 201210852 . π The pores of the mold are removed by removing the anodized portion in the following manner by using a field emission type sweep (four) submicroscope (Nippon Electric 2, 'JSM-74G()F)) Voltage 3 (8) k: Co., Ltd. = surface, and the interval between the pores and the depth of the pores were measured. The heart was 50 times and the average value was obtained. The heart knife was in the case of the test example 3, and the aqueous solution after the mold was manufactured) Carrying out the phase, the result is a yellowing electric job (Zhuo Yu The formula determines the concentration in the electrolyte, and the result is Q 4 ppm. The reason for the yellowing is that the titanium is dissolved into the electrolyte, and the sulphuric acid forms a complex. The mold obtained by the lion is embossed by the nanometer. As a result, foreign matter containing titanium was detected from the surface of the film to be transferred. [Industrial Applicability] The apparatus for manufacturing a mold for nanocompression and the mold for nanoimprinting were used for anodizing. The anodic oxide film of a desired shape can be efficiently produced by suppressing the elution of the metal into the electrolytic solution, and is useful for mass production of the illuminating article, the antifogging article, the antifouling article, and the water repellency. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 2 is a cross-sectional view showing an example of a mold step having an anodized surface on the surface of the apparatus for manufacturing a nanoimprinting device of the present invention. Manufacturing apparatus for articles having a porous structure

S 34 201210852, a structural diagram of an example. Fig. 4 is a cross-sectional view showing an example of an article having a porous structure on its surface. Fig. 5 is a view showing a cross section of a polar oxidized electrode after anodizing treatment by an electron microscope. [Description of main component symbols] 10: Manufacturing apparatus 12 for nano imprinting mold: Anodizing bath 14: Flow groove portion 16: Upper cover 18: Storage tank 20: Flow path 22: Supply port 24: Return flow path 26: Pump 28: Rectifier plate 30: Ming substrate 32: Center shaft 34: Axis 36: Cathode plate 38: Power supply 40. Temperature control mechanism 42: Fine hole 44: Oxide film (anodized aluminum oxide) 35 11 11201210852 46 : Fine hole Production point 48: mold body 50: roll mold 52: tank 54: pneumatic cylinder 56: nip roller 58: active energy ray irradiation device 60: peeling roller 70: article 72: film 74: hardened resin layer 76: convex portion S, 36

Claims (1)

201210852, VII. Application for Patent Fan Park······························································ The material of the surface of the portion where the metal solution is contacted [Condition] αίϊ is immersed in an electrolytic solution of 8 GmL for 45 G hours. The elution amount of the surface of the parent unit of the genus is 0.2 Ppm/cm 2 or less. The raw material of the nano-imprinting mold according to the first aspect of the invention, wherein the electrolyte is oxalic acid. "i such as: ί patent range of the second embodiment of the mold for imprinting = human gold Γ /, the surface of the portion of the contact with the electrolyte is zirconium 4. For example, π 贱 贱 2 The material of the surface of the portion of the nano-imprinted lining that is in contact with the above-mentioned electrolyte is a hammer 5. The apparatus for the nano-riding mold described in the above-mentioned Japanese Patent Laid-Open No. The liquid is sulfuric acid. 6. The mold for the nanoimprinting mold according to item 5 of the patent scope of the invention, wherein the surface of the portion in contact with the electrolyte solution is 铌7. The manufacturing apparatus of the nanoimprinting mold, wherein the surface of the portion in contact with the electrolytic solution is made of a material or an alloy thereof. 37 201210852 &quot; A method for producing a mold for embossing embossing, which uses an electrolytic solution The material is subjected to anodizing treatment to produce a non-meter embossing slab having a porous structure, and is characterized in that: the surface of the portion at least in contact with the electrolyte is made of the following strips - flooded or alloyed thereof Nano embossing mold manufacturing equipment, Anodizing treatment, 2 under conditions [conditions] Γ &gt; The amount of dissolution of the mother's early surface of the metal in the case of the electrolyte solution of 80 mL for 4 5 hrs is Q 2 Peng / coffee 2 or less. For example, please refer to the method for manufacturing a nanoimprinting mold according to item 8 of the patent scope, wherein the electrolyte is oxalic acid. 1 The nano-printing mold according to claim 9 of claim 4 The material of the surface of the portion of the gold imprinting mold described in the above-mentioned first embodiment of the invention is the surface of the portion of the gold imprinting mold described in the above paragraph 9 of the invention. The material is made into a mold for a nanoimprint mold as described in Item No. 8 of the above-mentioned Patent Document No. 11, wherein the electrolyte is sulfuric acid. The soil of the portion of the mold for contact with the above-mentioned electrolyte solution as described in claim 12 of the patent application is the alloy of the alloy. For example, in the mold for nanoimprinting, which is clarified in the scope of Patent Document No. 12, the surface of the portion of the portion where the gold is in contact with the above electrolyte is S 38