WO2022124002A1 - Procédé de fabrication de produit moulé par impression, procédé de formation de motif et procédé de fabrication de pièces - Google Patents

Procédé de fabrication de produit moulé par impression, procédé de formation de motif et procédé de fabrication de pièces Download PDF

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Publication number
WO2022124002A1
WO2022124002A1 PCT/JP2021/041619 JP2021041619W WO2022124002A1 WO 2022124002 A1 WO2022124002 A1 WO 2022124002A1 JP 2021041619 W JP2021041619 W JP 2021041619W WO 2022124002 A1 WO2022124002 A1 WO 2022124002A1
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molded product
curable composition
group
surface treatment
manufacturing
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PCT/JP2021/041619
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English (en)
Japanese (ja)
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泰吾 赤▲崎▼
武司 大幸
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東洋合成工業株式会社
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Publication of WO2022124002A1 publication Critical patent/WO2022124002A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/10—Surface shaping of articles, e.g. embossing; Apparatus therefor by electric discharge treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/14—Surface shaping of articles, e.g. embossing; Apparatus therefor by plasma treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

Definitions

  • Some aspects of the present invention relate to a method of manufacturing an imprinted molded product. In addition, some other aspects of the present invention relate to pattern forming methods. In addition, some other aspects of the present invention relate to a method of manufacturing a part using the pattern forming method.
  • Imprint lithography has the advantage of being able to produce patterns at a lower cost than ordinary photolithography, and has been attracting attention in recent years.
  • a curable composition is applied onto a substrate to form a curable composition layer, and then the curable composition layer is brought into contact with a mold having an uneven pattern. Subsequently, the curable composition layer is cured by heat or light to obtain a molded product to which the uneven pattern is transferred.
  • Patent Document 1 discloses a roll-to-roll process in which an imprint molded product produced on a flexible substrate is wound into a sheet.
  • the molded product of such a roll-to-roll process is wound up, if the molded product is formed on both sides of the substrate, the surface of the molded product on one side of the substrate and the surface of the molded product on the other side of the substrate. Come in contact with.
  • the molded product is formed on only one surface of the substrate, the surface of the molded product and the other surface of the substrate come into contact with each other.
  • the present inventors applied at least one surface treatment selected from the group consisting of plasma irradiation and corona treatment to the cured imprint molded product to obtain the surface of the molded product. It has been found that a molded product having excellent surface slipperiness can be obtained by setting the average roughness of the center line in a specific range, and some aspects of the present invention have been completed.
  • One aspect of the present invention is a step (a) of forming a curable composition layer using a curable composition, and a step (b) of bringing the curable composition layer into contact with a mold having an uneven pattern. ),
  • It has a step (d) of subjecting to a surface treatment to obtain an imprint molded product having a first surface, and the imprint having the center line average roughness of the first surface of 0.5 nm or more by the above surface treatment.
  • This is a method for manufacturing a molded product.
  • Another aspect of the present invention is a step (a) of forming a curable composition layer using a curable composition, and a step of bringing the curable composition layer into contact with a mold having an uneven pattern.
  • (B) a step (c) of curing the curable composition layer to obtain a cured layer having an uneven pattern, and at least a part selected from the group consisting of plasma irradiation and corona treatment on at least a part of the cured layer. It comprises a step (d) of performing one surface treatment and converting the surface of the cured layer into a first surface, and the center line average roughness of the first surface is set to 0.5 nm or more by the above surface treatment. It is a pattern forming method.
  • Another aspect of the present invention is a method for manufacturing parts using the above pattern forming method.
  • the method for producing an imprinted molded product according to one aspect of the present invention tends to impart slipperiness to the surface of the molded product.
  • One aspect of the present invention is a method for manufacturing an imprinted molded product having the above steps.
  • the curable composition examples include a composition containing a polyfunctional monomer, a polymerization initiator and the like.
  • a polyfunctional monomer is a compound having two or more polymerizable groups in one molecule.
  • the polymerizable group includes a radically polymerizable group such as a (meth) acryloyl group, a vinyl group, an allyl group, a propargyl group, a group having an alkenylene group and a group having an alkynylene group; and an ionic polymerizable group such as an epoxy group and an oxetanyl group. Group; etc.
  • a acryloyl group means both “acryloyl group” and “methacryloyl group”.
  • (Meta) acrylate” also means both “acrylate” and “methacrylate”.
  • “(Meta) acrylic” also means both “acrylic” and "methacrylic”.
  • polyfunctional monomer having a radically polymerizable group examples include linear aliphatics such as ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate and 1,9-nonanediol di (meth) acrylate.
  • Etc. such as branched aliphatic polyfunctional (meth) acrylates; 1,4-cyclohexanediol di (meth) acrylates, 1,4-cyclohexanedimethanol di (meth) acrylates, tricyclodecanedimethanol di (meth) acrylates, etc.
  • the polyfunctional monomer may be a urethane (meth) acrylate synthesized by a reaction between a polyfunctional isocyanate and a (meth) acrylate having a hydroxy group.
  • the polyfunctional isocyanate include linear aliphatic diisocyanates such as hexamethylene diisocyanate; cyclic aliphatic diisocyanates such as isophorone diisocyanate; and aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate.
  • Examples of the (meth) acrylate having a hydroxy group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
  • urethane (meth) acrylate as the polyfunctional monomer, the flexibility of the molded product is improved, and the pattern tends to be less likely to be damaged when the molded product is released from the mold.
  • the polyfunctional monomer having a radically polymerizable group may be an oligomer such as polyethylene glycol di (meth) acrylate.
  • the alicyclic contained in the cyclic aliphatic polyfunctional (meth) acrylate may be a single alicyclic such as cyclopentane or cyclohexane, or a condensed alicyclic such as decalin, tricyclodecane, adamantane and norbornane, and pyrrolidine, pyrrolidone and tetrahydrofuran. It may be a heteroaliphatic ring such as.
  • the aromatic ring contained in the aromatic polyfunctional (meth) acrylate may be a monoaromatic ring such as benzene, a fused aromatic ring such as naphthalene, anthracene and fluorene, or a heteroaromatic ring such as furan, pyridine and thiophene. May be.
  • the alicyclic or aromatic ring may be directly bonded to the polymerizable group by a single bond, or may be bonded via a divalent linking group.
  • Examples of the divalent linking group include an alkylene group, a carbonyl group, an oxygen atom, an ester group, an aminodiyl group, an alkylaminodiyl group, a urethane bond, a sulfur atom, a dialkylsilylene group, a diarylsilylene group and a combination thereof.
  • At least one methylene group contained in the polyfunctional monomer may be substituted with a divalent substituent such as a carbonyl group, an oxygen atom, an aminodiyl group, an alkylaminodiyl group, a sulfur atom, a dialkylsilylene group and a diallylsilylene group.
  • a divalent substituent such as a carbonyl group, an oxygen atom, an aminodiyl group, an alkylaminodiyl group, a sulfur atom, a dialkylsilylene group and a diallylsilylene group.
  • Examples of the polyfunctional monomer in which the methylene group is substituted with an oxygen atom include a polyfunctional monomer having an alkylene oxide chain such as an ethylene oxide chain, a butylene oxide chain and a perfluoroethylene oxide chain.
  • Examples of the polyfunctional monomer in which the methylene group is substituted with a dialkylsilylene group or a diarylsilylene group include a polyfunctional monomer having a silicon-containing chain such as a dimethylsiloxane chain, a diphenylsiloxane chain, a dimethylsilazane chain and a diphenylsilazane chain.
  • At least one hydrogen atom of the polyfunctional monomer is substituted with a monovalent substituent such as a hydroxy group, a carboxy group, a cyano group, a nitro group, a halogen atom, an alkyl halide group, a trialkylsilyl group and a triarylsilyl group. It may have been done.
  • a monovalent substituent such as a hydroxy group, a carboxy group, a cyano group, a nitro group, a halogen atom, an alkyl halide group, a trialkylsilyl group and a triarylsilyl group.
  • the halogen include fluorine, chlorine, bromine and iodine.
  • the number of polymerizable groups contained in the polyfunctional monomer is appropriately selected depending on the required characteristics of the imprinted product, preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 to 3. By setting the number of polymerizable groups in a specific range, there is a tendency that both mechanical strength and flexibility of the imprinted molded product can be achieved at the same time.
  • the polyfunctional monomer a plurality of types of polyfunctional monomers having different numbers of polymerizable groups may be used in combination.
  • the polyfunctional monomer preferably has 6 to 100 carbon atoms, more preferably 10 to 50 carbon atoms, and even more preferably 15 to 30 carbon atoms.
  • the carbon number includes the carbon number of the polymerizable group, the divalent linking group, the divalent substituent and the monovalent substituent.
  • the double bond equivalent of the polyfunctional monomer is preferably 50 to 1000, more preferably 60 to 800, and even more preferably 80 to 500.
  • double bond equivalent represents the monomer mass per mole of the carbon-carbon double bond possessed by a polymerizable group such as a (meth) acryloyl group, a vinyl group, an allyl group and an alkenylene group.
  • a polymerizable group such as a (meth) acryloyl group, a vinyl group, an allyl group and an alkenylene group.
  • the unit is g / mol.
  • the polymerization initiator examples include a photoradical polymerization initiator having a skeleton such as an acetophenone skeleton, a benzylketal skeleton or a phosphinoxide skeleton; a photoionic polymerization initiator having a skeleton such as a sulfonium skeleton, an iodonium skeleton or an acyloxime skeleton; an azo compound and Thermal radical polymerization initiators such as peroxides; and thermal ion polymerization initiators such as phenolic resins, amine compounds and carboxylic acid anhydrides; and the like.
  • a photoradical polymerization initiator having a skeleton such as an acetophenone skeleton, a benzylketal skeleton or a phosphinoxide skeleton
  • a photoionic polymerization initiator having a skeleton such as a sulfonium skeleton, an iodonium
  • photoradical polymerization is preferable from the viewpoint of curing shrinkage and the like, and as the polymerization initiator, a photoradical polymerization initiator is preferable.
  • the light used for curing includes infrared rays, visible rays, ultraviolet rays, excimer lasers, extreme ultraviolet rays, electromagnetic waves such as X-rays and gamma rays, and particle beams such as electron beams and alpha rays.
  • the curable composition may further contain a monofunctional monomer.
  • the monofunctional monomer is a compound having one polymerizable group in one molecule.
  • Examples of the polymerizable group of the monofunctional monomer include the same groups as the polymerizable group of the polyfunctional monomer.
  • Examples of the monofunctional monomer having a radically polymerizable group include linear aliphatic monofunctional (meth) acrylates such as methyl (meth) acrylate, n-butyl (meth) acrylate and lauryl (meth) acrylate; isobutyl (meth) acrylate.
  • Bifurcated aliphatic monofunctional (meth) acrylates such as isoamyl (meth) acrylates and isononyl (meth) acrylates; cyclic aliphatic monofunctional (meth) acrylates such as cyclohexyl (meth) acrylates, isobornyl (meth) acrylates and adamantyl (meth) acrylates.
  • Aromatic monofunctional (meth) acrylates such as phenyl (meth) acrylates and phenoxyethyl (meth) acrylates; aromatic monofunctional vinyl compounds such as styrene and vinylnaphthalene; and heterocyclic fats such as N-vinylpyrrolidone. Group monofunctional vinyl compounds; and the like.
  • the alicyclic contained in the cyclic aliphatic monofunctional (meth) acrylate may be a monoalicyclic ring such as cyclopentane or cyclohexane, or a condensed alicyclic ring such as decalin, tricyclodecane, adamantane and norbornane, and pyrrolidine and pyrrolidone. And may be a heteroaliphatic ring such as tetrahydrofuran.
  • the aromatic ring contained in the aromatic monofunctional (meth) acrylate and the aromatic monofunctional vinyl compound may be a monoaromatic ring such as benzene, a fused aromatic ring such as naphthalene, anthracene and fluorene, and furan and pyridine. And may be a heteroaromatic ring such as thiophene. Further, the alicyclic ring, the aromatic ring or the heterocycle may be directly bonded to the polymerizable group by a single bond, or may be bonded via a divalent linking group.
  • Examples of the divalent linking group include an alkylene group, a carbonyl group, an oxygen atom, an ester group, an aminodiyl group, an alkylaminodiyl group, a urethane bond, a sulfur atom, a dialkylsilylene group, a diarylsilylene group and a combination thereof.
  • At least one methylene group contained in the monofunctional monomer may be substituted with a divalent substituent such as a carbonyl group, an oxygen atom, an aminodiyl group, an alkylaminodiyl group, a sulfur atom, a dialkylsilylene group and a diarylcilylene group.
  • a divalent substituent such as a carbonyl group, an oxygen atom, an aminodiyl group, an alkylaminodiyl group, a sulfur atom, a dialkylsilylene group and a diarylcilylene group.
  • Examples of the monofunctional monomer in which the methylene group is substituted with an oxygen atom include a monofunctional monomer having an alkylene oxide chain such as an ethylene oxide chain, a butylene oxide chain and a perfluoroethylene oxide chain.
  • Examples of the monofunctional monomer in which the methylene group is substituted with the dialkylsilylene group or the diarylsilylene group include monofunctional monomers having a silicon-containing chain such as a dimethylsiloxane chain, a diphenylsiloxane chain, a dimethylsilazane chain and a diphenylsilazane chain. ..
  • At least one hydrogen atom contained in the monofunctional monomer is substituted with a substituent such as a hydroxy group, a carboxy group, a cyano group, a nitro group, a halogen atom, an alkyl halide group, a trialkylsilyl group and a triarylsilyl group. May be good.
  • a substituent such as a hydroxy group, a carboxy group, a cyano group, a nitro group, a halogen atom, an alkyl halide group, a trialkylsilyl group and a triarylsilyl group. May be good.
  • the halogen include fluorine, chlorine, bromine and iodine.
  • the number of carbon atoms of the monofunctional monomer is preferably 3 to 50, more preferably 4 to 30, and even more preferably 6 to 20.
  • the double bond equivalent of the monofunctional monomer is preferably 50 to 500, more preferably 60 to 400, and even more preferably 80 to 300.
  • the carbon number includes the carbon number of the polymerizable group, the divalent linking group, the divalent substituent and the monovalent substituent.
  • the content of the polyfunctional monomer is preferably 10 to 90 parts by mass, more preferably 20 to 85 parts by mass, still more preferably 30 to 80 parts by mass in 100 parts by mass of the curable composition.
  • the polymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and even more preferably 1 to 10 parts by mass in 100 parts by mass of the curable composition.
  • a monofunctional monomer is used, it is preferably 5 to 80 parts by mass, more preferably 10 to 70 parts by mass, still more preferably 15 to 60 parts by mass, out of 100 parts by mass of the curable composition.
  • the mass ratio of the polyfunctional monomer: the monofunctional monomer is preferably 10: 1 to 1:10, more preferably 6: 1 to 1: 6, and even more preferably 5: 1 to 1: 3. ⁇ 1: 1 is particularly preferable.
  • the solvent is not included in 100 parts by mass of the curable composition.
  • the solvent refers to a liquid compound having no polymerizable group, excluding the polyfunctional monomer, the polymerization initiator and the monofunctional monomer. Reactive diluents and the like having a polymerizable group are not contained in the solvent and are regarded as the monofunctional monomer or the polyfunctional monomer.
  • those usually used for curable compositions can be used.
  • Specific examples thereof include methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether and ethyl lactate.
  • the curable composition may further contain additives in addition to the polyfunctional monomer, the polymerization initiator and the monofunctional monomer.
  • additives include, for example, polymers, mold release agents, adhesion promoters, antioxidants, polymerization inhibitors, solvents, colorants, plasticizers, surfactants, silane coupling agents, fillers, pigments, dyes, acidic compounds and Examples include sensitizers.
  • the amount of the additive added is preferably in a range that does not affect the curability of the curable composition, specifically, 0.01 to 20 parts by mass, preferably 0.05 to 15 parts by mass of 100 parts by mass of the curable composition. By mass is more preferable, and 0.1 to 10 parts by mass is even more preferable.
  • the above-mentioned additive is a (meth) acryloyl group, a vinyl group and an allyl group together with a functional group (perfluoroalkyl group, alkoxysilyl group, oxyalkylene group, phenolic hydroxyl group, amino group, etc.) that functions as an additive.
  • a functional group perfluoroalkyl group, alkoxysilyl group, oxyalkylene group, phenolic hydroxyl group, amino group, etc.
  • It may be a compound having a polymerizable group such as.
  • such a compound having both a functional group and a polymerizable group is regarded as the polyfunctional monomer or the monofunctional monomer, not an additive.
  • the curable composition may be applied to a substrate or a mold having an uneven pattern.
  • a substrate made of a known material can be appropriately selected.
  • metals such as nickel, chromium, titanium, iron, copper, aluminum and stainless steel; non-metals such as glass, quartz and silicon; and polyethylene terephthalate, polyimide, polycarbonate, polycycloolefin, polyethylene, polypropylene and poly.
  • Organic polymers such as vinylidene, polyurethane, polyether sulfone and polytetrafluoroethylene; and the like.
  • a metal thin film may be formed on the surface of the substrate.
  • the mold a mold made of a known material can be appropriately selected.
  • the mold material includes metals such as nickel, chromium, titanium, iron, copper, aluminum and stainless steel; non-metals such as glass, quartz and silicon; and polyethylene terephthalates, polyimides, polycarbonates, polycycloolefins, polyethylenes and polypropylenes.
  • Organic polymers such as polycarbonate, polyurethane, polyether sulfone and polytetrafluoroethylene; and the like.
  • the mold may be a replica mold produced by curing a thermosetting resin or a photocurable resin.
  • a step of surface-treating the substrate and / or the mold may be further included.
  • the surface treatment include a treatment of applying a mold release agent containing an organic compound containing a fluorine atom and / or a silicon atom.
  • the method for producing an imprinted molded product includes a step (d) of applying at least one surface treatment selected from the group consisting of plasma irradiation or corona treatment.
  • the surface of the cured layer has a centerline average roughness in a specific range, and slipperiness is imparted.
  • the region to be surface-treated is appropriately selected depending on the pattern shape and application of the imprinted molded product, the device for manufacturing the molded product, the surface treatment device, and the like.
  • the surface treatment region may be at least a part of a region (pattern region) in which an uneven pattern is formed, or may be at least a part of a region (non-pattern region) in which an uneven pattern is not formed.
  • the surface-treated region is preferably a non-patterned region from the viewpoint of imparted slipperiness.
  • the average roughness of the center line is preferably large from the viewpoint of slipperiness, but if it is too large, it may affect the device characteristics and optical characteristics of the parts including the imprinted molded product.
  • the average roughness of the center line is preferably 0.5 nm or more, more preferably 1.0 nm or more.
  • the upper limit of the average roughness of the center line may be, for example, 10 ⁇ m or 1 ⁇ m.
  • the center line average roughness can be set to a specific range by appropriately adjusting the output of the surface treatment device, the treatment time, the hole diameter of the shielding plate described later, and the like.
  • the average roughness of the center line tends to increase by performing the surface treatment under strong conditions such as increasing the output of the surface treatment apparatus or lengthening the treatment time.
  • the average roughness of the center line in the present invention is the average roughness of the center line (Ra) measured by AFM5100N (scanning probe microscope, manufactured by Hitachi High-Technologies Corporation) in accordance with JIS B0601: 1982. In particular, it represents the roughness represented by the following equation 1.
  • L is a reference length on the center line.
  • F (X) is a function representing the surface shape at an arbitrary position X on the center line.
  • the average roughness of the center line in the present invention includes the roughness derived from the shape of the uneven pattern.
  • the average roughness of the center line including the roughness derived from the shape of the uneven pattern is within the above range, even when the imprinted molded product according to one aspect of the present invention comes into contact with the molded product having the uneven pattern. , The unevenness pattern does not mesh with each other, and the slipperiness tends to be improved.
  • the first surface has a centerline average roughness in a specific range, so that slipperiness is imparted.
  • the low slipperiness of the surface may cause a problem that the wound sheet is wrinkled and a defective product is produced.
  • the molded product when the molded product is formed on both sides of the same substrate, it is formed on the front surface of the molded product (first molded product) having the first surface and the back surface of the substrate on which the first molded product is formed. Since the surface of the molded product (second molded product) is in contact with the surface, the low slipperiness of the surface tends to cause a problem of defective products due to wrinkles.
  • the single-wafer manufacturing process in which the substrates on which the molded products are formed are manufactured one by one also includes a step of bringing the surfaces of the molded products into contact with each other for alignment.
  • the low slipperiness of the surface makes it difficult to finely adjust the position.
  • a known gas can be appropriately selected, and examples thereof include oxygen (O 2 ), hydrogen (H 2 ), a rare gas, and a fluorine-containing compound.
  • the noble gas include helium, neon, argon, krypton, xenon and the like.
  • the fluorine-containing compound represents not only fluorine (F 2 ) but also fluorocarbons such as fluoromethane, difluoromethane, trifluoromethane and tetrafluoromethane; boron trifluoride; and compounds such as sulfur hexafluoride.
  • oxygen is preferable from the viewpoint of handleability of the gas used and reactivity with the cured layer.
  • a plurality of types of process gases may be mixed and used. When a plurality of types of process gases containing oxygen are used as the process gas, the oxygen concentration in the process gas is preferably 5 to 99% by volume, more preferably 50 to 95% by volume.
  • Examples of the plasma generation method include known plasma generation methods such as an inductively coupled plasma method, an electron cyclotron resonance method, and a capacitively coupled plasma method. Irradiation of plasma may be performed under reduced pressure such as vacuum, or may be performed under atmospheric pressure.
  • the corona treatment may be performed under reduced pressure such as vacuum, or may be performed under atmospheric pressure.
  • a process gas may be used. Examples of the process gas include the same gas as the process gas in the plasma irradiation.
  • the surface treatment it is preferable to perform the surface treatment via a shielding plate having a region through which plasma or corona active species can pass.
  • a part of the cured layer may be ashed by the surface treatment and the desired uneven pattern transferred may be deteriorated.
  • the surface treatment only a part of the generated plasma or corona active species reaches the cured layer, so the surface should have a centerline average roughness in a specific range while suppressing deterioration of the desired uneven pattern. Can be done.
  • the above-mentioned average roughness of the center line can also be adjusted by the hole diameter of the shielding plate.
  • performing the surface treatment through the shielding plate means performing the surface treatment in a state where the shielding plate is present between the irradiated object (the cured layer) and the surface treatment apparatus.
  • the corona active species represents an electron, an ionized atom, an ionized molecule, or the like generated by the corona discharge in the corona treatment.
  • the material of the shielding plate metals such as nickel, chromium, titanium, iron, copper, aluminum and stainless steel; non-metals such as glass, quartz and silicon; and polyethylene terephthalate, polyimide, polycarbonate, polycycloolefin, polyethylene and polypropylene, Organic polymers such as polycarbonate, polyurethane, polyether sulfone and polytetrafluoroethylene; and the like.
  • a metal thin film may be formed on the surface of the shield plate.
  • shielding plates are filters such as membrane filters, surface filters and depth filters with a specific maximum pore size; patterns with a hole pattern with a specific maximum pore size and / or a line pattern with a specific lateral width.
  • filters such as membrane filters, surface filters and depth filters with a specific maximum pore size; patterns with a hole pattern with a specific maximum pore size and / or a line pattern with a specific lateral width.
  • the maximum pore diameter is measured by a bubble point method based on JIS K3832, and isopropyl alcohol is used as a test solution for the measurement.
  • the maximum pore diameter of the shielding plate is preferably 0.01 ⁇ m to 10 ⁇ m, more preferably 0.02 ⁇ m to 1 ⁇ m, and even more preferably 0.05 ⁇ m to 0.3 ⁇ m.
  • the shielding plate having the maximum pore diameter examples include PTFE membrane filters T010A, T020A and T050A manufactured by Advantech Toyo Co., Ltd. Further, nanoporous alumina films SmartPor25, SmartPor40, SmartPor180 and the like manufactured by Smart Membranes, and macroporous silicon films MakroPor and the like can also be used as the shielding plate.
  • the hole pattern and / or the line pattern can be produced by a known pattern forming method such as photolithography using a photoresist and imprint lithography using a curable resin.
  • the energy rays used for photolithography are appropriately selected depending on the size of the hole pattern and / or the line pattern. Examples of energy rays used for photolithography include i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), extreme ultraviolet rays (wavelength 13.5 nm), and electron beams.
  • a step (e) of bringing at least a part of the first surface and at least a part of the second surface into contact with each other is further performed.
  • the second surface preferably has a centerline average roughness of 0.5 nm or more.
  • the upper limit of the average roughness of the center line of the second surface may be, for example, 10 ⁇ m or 1 ⁇ m.
  • the first surface is slippery because it has a centerline average roughness in a specific range. Therefore, in the step of contacting at least a part of the first surface and at least a part of the second surface, the surfaces come into smooth contact with each other.
  • the second surface may be the back surface of the substrate (first substrate) on which the molded product (first molded product) having the first surface is formed, or the molded product formed on the back surface of the first substrate. It may be the surface of (second molded product). Further, the second surface may be the surface of a substrate (second substrate) different from the first substrate, or may be the surface of a molded product (third molded product) formed on the second substrate. May be good. In this specification, the "molded product" does not include the "substrate”.
  • the shape of the uneven pattern of the mold, the first surface, and the second surface is appropriately selected depending on the intended use of the imprinted product and the like.
  • the width of the uneven pattern is preferably 0.01 ⁇ m to 100 ⁇ m, more preferably 0.01 ⁇ m to 50 ⁇ m, and even more preferably 0.01 ⁇ m to 30 ⁇ m.
  • the aspect ratio of the uneven pattern is preferably 0.01 to 5.0, more preferably 0.01 to 3.0. By setting the aspect ratio of the uneven pattern to a certain level or less, there is a tendency that the pattern collapse can be suppressed.
  • the first surface and the second surface preferably have a hardness of a certain level or higher.
  • the first surface and the second surface have a certain hardness or more, the first surface and the second surface are not deformed by the contact, and the imparted slipperiness tends to be sufficiently exhibited.
  • the pencil hardness is preferably 6B or more, more preferably 3B or more, and further preferably B or more, respectively.
  • the upper limit of the pencil hardness is not particularly limited, and is appropriately selected according to the intended use of the molded product.
  • the upper limit of the pencil hardness is preferably 6H or less.
  • the pencil hardness represents the hardness measured in accordance with JIS K5600-5-4.
  • One aspect of the present invention includes a step (a) of forming a curable composition layer using a curable composition, the curable composition layer, a mold having an uneven pattern, and the like. (B), a step (c) of curing the curable composition layer to obtain a cured layer having an uneven pattern, and a group consisting of plasma irradiation and corona treatment on at least a part of the cured layer. It comprises the step (d) of applying at least one surface treatment to be selected and converting the surface of the cured layer into the first surface, and the surface treatment makes the centerline average roughness of the first surface 0. It is a pattern forming method of 5 nm or more.
  • the pattern forming method includes a step (d) of applying a surface treatment.
  • a surface treatment By this surface treatment, the surface of the cured layer becomes a first surface having a centerline average roughness in a specific range, and slipperiness is imparted.
  • the curable composition, the mold having the uneven pattern, and the surface treatment are the curable composition in the method for producing the imprinted molded product described above, the mold having the uneven pattern, and the surface treatment, respectively. The same can be mentioned.
  • the average roughness of the center line is preferably 0.5 nm or more, more preferably 1.0 nm or more. Further, the upper limit of the average roughness of the center line may be, for example, 10 ⁇ m or 1 ⁇ m.
  • the surface treatment in the pattern forming method it is preferable to perform the surface treatment via a shielding plate having a region through which plasma or corona active species can pass.
  • a part of the cured layer may be ashed by the surface treatment, and the desired uneven pattern transferred may be deteriorated.
  • the surface treatment via the shielding plate the surface can be made to have the average roughness of the center line in a specific range while suppressing the deterioration of the uneven pattern.
  • the material and the maximum hole diameter of the shielding plate include those similar to the material and the maximum hole diameter of the shielding plate in the above-mentioned method for manufacturing an imprint molded product.
  • the pattern forming method it is preferable to further include a step (e) in which at least a part of the first surface and at least a part of the second surface are brought into contact with each other after the step (d) of applying the surface treatment.
  • the second surface preferably has a centerline average roughness of 0.5 nm or more.
  • the upper limit of the average roughness of the center line of the second surface may be, for example, 10 ⁇ m or 1 ⁇ m.
  • the first surface has a specific centerline average roughness and is therefore slippery. Therefore, in the step of contacting at least a part of the first surface and at least a part of the second surface, the surfaces come into smooth contact with each other.
  • the second surface may be the same as the second surface in the method for manufacturing an imprinted molded product described above.
  • the first surface and the second surface preferably have a hardness of a certain level or higher.
  • the first surface and the second surface have a certain hardness or more, the first surface and the second surface are not deformed by the contact, and the imparted slipperiness tends to be sufficiently exhibited.
  • the hardness of the first surface and the second surface include the same hardness as the hardness of the first surface and the second surface in the method for producing an imprint molded product described above.
  • One aspect of the present invention is a method for manufacturing parts using the above-mentioned pattern forming method.
  • the above pattern forming method can be used as a method for manufacturing parts.
  • slipperiness is imparted to the surface of the cured layer by surface treatment. Therefore, in the method of manufacturing parts, there is a tendency to have an effect of facilitating fine adjustment of the positions of surfaces and an effect of preventing wrinkles when winding a molded product.
  • the optical members include optical elements such as diffraction gratings, beam splitters, mirrors and lenses; optical films such as polarizing films, prism sheets, high refraction films and antireflection films; optical devices such as optical isolators, optical fibers and optical waveguides; And so on.
  • the molded product used for the optical member preferably has a total light transmittance of 70% or more, more preferably 80% or more, and particularly preferably 85% or more.
  • a total light transmittance of 70% or more By setting the total light transmittance of the optical member to a certain level or higher, there is an effect that the loss of light due to absorption when light passes through the optical member can be suppressed.
  • the surface is roughened by a general method
  • the roughness is large and the haze may increase due to the scattering of light on the surface. Therefore, a molded product having such a surface may not be usable as an optical member.
  • the molded product of one aspect of the present invention since the applied roughness is controlled by plasma irradiation or corona treatment, the increase in haze can be suppressed even though the slipperiness tends to be improved. Tend. Therefore, even when the molded product is used as an optical member, there is an effect that light scattering is suppressed.
  • another aspect of the present invention is a step (a) of forming a curable composition layer using a curable composition and a step (c) of curing the curable composition layer to obtain a cured film. ) And a step (d) of applying at least one surface treatment selected from the group consisting of plasma irradiation and corona treatment to at least a part of the cured film to obtain a treated film.
  • This is a method for manufacturing a treated film in which the average roughness of the center line of the surface of the treated film is 0.5 nm or more.
  • another aspect of the present invention is a step (a) of forming a curable composition layer using a curable composition and a step (c) of curing the curable composition layer to obtain a cured film. ), And a step (d) of applying at least one surface treatment selected from the group consisting of plasma irradiation and corona treatment to at least a part of the cured film to convert the cured film into a treated film.
  • This is a method for treating a cured film in which the average roughness of the center line of the surface of the treated film is 0.5 nm or more by surface treatment.
  • Another aspect of the present invention is a method for manufacturing a part using the above-mentioned method for treating a cured film.
  • the cured film having no uneven pattern can be manufactured by the same method as the method for manufacturing an imprinted product, except that the mold is not used.
  • the composition of the curable composition for forming the cured film the same composition as that of the curable composition in the method for producing an imprint molded product can be mentioned.
  • the surface of the imprinted molded product after curing has a centerline average roughness in a specific range.
  • the surfaces are brought into contact with each other or between the surface and another surface by a roll-to-roll process (e), and the slipperiness is excellent.
  • the step (a) of forming the curable composition layer using the curable composition, the curable composition layer, and the mold having the uneven pattern are brought into contact with each other.
  • the surfaces of the imprinted molded product after curing have the average roughness of the center line in a specific range, so that the surfaces are aligned with each other. Or, it has excellent slipperiness in the step of bringing the surface into contact with another surface by a roll-to-roll process.
  • another aspect of the present invention is a step (a) of forming a curable composition layer using a curable composition, and contacting the curable composition layer with a mold having an uneven pattern.
  • (B) a step (c) of curing the curable composition layer to obtain a cured layer having an uneven pattern, and a roll-to-roll between the surfaces of the cured layers or between the cured layer and another surface.
  • It is a pattern forming method having a step (e) of contacting with a roll, and in the step of contacting with a roll-to-roll, the center line average roughness of the surface of the cured layer is set to 0.5 nm or more.
  • Another aspect of the present invention is a method for manufacturing a part using the method for forming the above pattern.
  • the following polyfunctional monomers, polymerization initiators and monofunctional monomers are mixed to prepare a curable composition sample.
  • the prepared curable composition sample is applied to a PET film (Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.), and a quartz mold (thickness 6.35 mm, recess depth 200 nm, line width 500 nm) line and space pattern is applied thereto. (Made by relief printing company), and exposed with a UV-LED lamp at 20 mW / cm 2 (wavelength 365 nm) for 20 seconds in a nitrogen atmosphere. Next, the obtained cured layer and the quartz mold are released from each other, and the film thickness of the cured layer is measured.
  • the cured layer is irradiated with plasma under the irradiation conditions shown below using a plasma dry cleaner (PDC210, manufactured by Yamato Kagaku Co., Ltd.) to perform surface treatment.
  • PDC210 plasma dry cleaner
  • the film thickness, pencil hardness and centerline average roughness of the cured layer after surface treatment are measured.
  • the film thickness reduction rate is calculated from the film thickness measured before and after the surface treatment. The results are shown in Table 1.
  • the cured layer after plasma irradiation is cut into a size of 1 cm in length and 3 cm in width, and the surfaces of the two obtained cured layers are bonded to each other and rubbed to evaluate slipperiness. A sample with particularly good slipperiness is marked with ⁇ , a sample with good slipperiness is marked with ⁇ , and a sample with poor slipperiness is marked with ⁇ .
  • the total light transmittance and the haze are evaluated as the optical characteristics of the cured layer after plasma irradiation.
  • the total light transmittance and haze are measured by an ultraviolet-visible near-infrared spectrophotometer (V-750, manufactured by JASCO Corporation) using a cured layer obtained by the same method as described above.
  • V-750 ultraviolet-visible near-infrared spectrophotometer
  • the smaller the haze (%) value the smaller the scattering of light transmitted through the cured layer, indicating that the optical characteristics are excellent.
  • the film thickness is measured using a film thickness meter Surfcom 920B (manufactured by Tokyo Seimitsu Co., Ltd.).
  • T1 represents the film thickness of the cured layer before the surface treatment
  • T2 represents the film thickness of the cured layer after the surface treatment.
  • plasma irradiation was not performed. Therefore, the film thickness reduction rate has not been calculated.
  • shielding plate A PTFE membrane filter T010A (maximum pore diameter 0.1 ⁇ m) (manufactured by Advantech Toyo Co., Ltd.)
  • Shielding plate B PTFE membrane filter T020A (maximum pore diameter 0.2 ⁇ m) (manufactured by Advantech Toyo Co., Ltd.)
  • Shielding plate C PTFE membrane filter T050A (maximum pore diameter 0.5 ⁇ m) (manufactured by Advantech Toyo Co., Ltd.)
  • the imprinted molded product subjected to the surface treatment has improved slipperiness as compared with the imprinted molded product not subjected to the surface treatment. Further, it can be seen that by using the shielding plate during the surface treatment, the slipperiness is improved and the film thickness reduction of the molded product is suppressed. Furthermore, it can be seen that the total light transmittance and haze of the imprint molded product hardly change depending on the surface treatment. Even if the curable composition has a composition other than the curable composition sample, the slipperiness tends to be improved by setting the average roughness of the center line of the surface to 0.5 nm or more by the surface treatment. ..
  • the slipperiness of the surface is improved by setting the surface of the molded product to a predetermined centerline average roughness. It tends to have an effect of facilitating alignment and an effect of preventing wrinkles when winding the molded product.
  • the total light transmittance and haze of the imprint molded product hardly change depending on the surface treatment. Therefore, it is useful for manufacturing parts such as optical members.

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Abstract

La présente invention concerne un procédé de fabrication d'un produit moulé par impression, comprenant : une étape (a) de formation d'une couche de composition durcissable à l'aide d'une composition durcissable ; une étape (b) consistant à amener la couche de composition durcissable en contact avec un moule ayant un motif irrégulier ; une étape (c) de durcissement de la couche de composition durcissable pour obtenir une couche durcie ayant un motif irrégulier ; et une étape (d) consistant à effectuer au moins un traitement de surface choisi dans le groupe constitué par un traitement par rayonnement plasma ou un traitement corona sur au moins une partie de la couche durcie pour obtenir un produit moulé par impression ayant une première surface, une rugosité moyenne de ligne centrale de la première surface étant d'au moins 0,5 nm par le traitement de surface.
PCT/JP2021/041619 2020-12-11 2021-11-11 Procédé de fabrication de produit moulé par impression, procédé de formation de motif et procédé de fabrication de pièces WO2022124002A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007051218A (ja) * 2005-08-18 2007-03-01 Tateyama Machine Kk プラズマエッチング方法
JP2008094088A (ja) * 2006-10-12 2008-04-24 Samsung Electro Mech Co Ltd インプリンティング用スタンパーの製造方法
JP2010113772A (ja) * 2008-11-07 2010-05-20 Konica Minolta Opto Inc 転写型及び情報記録媒体用基板製造方法
WO2011118238A1 (fr) * 2010-03-23 2011-09-29 リンテック株式会社 Procédé de formation de surface irrégulière utilisant un processus de gravure par plasma et élément d'électrode
JP2012091463A (ja) * 2010-10-28 2012-05-17 Nitta Corp インプリント用モールドおよびその製造方法、並びに微細構造の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007051218A (ja) * 2005-08-18 2007-03-01 Tateyama Machine Kk プラズマエッチング方法
JP2008094088A (ja) * 2006-10-12 2008-04-24 Samsung Electro Mech Co Ltd インプリンティング用スタンパーの製造方法
JP2010113772A (ja) * 2008-11-07 2010-05-20 Konica Minolta Opto Inc 転写型及び情報記録媒体用基板製造方法
WO2011118238A1 (fr) * 2010-03-23 2011-09-29 リンテック株式会社 Procédé de formation de surface irrégulière utilisant un processus de gravure par plasma et élément d'électrode
JP2012091463A (ja) * 2010-10-28 2012-05-17 Nitta Corp インプリント用モールドおよびその製造方法、並びに微細構造の製造方法

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