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WO2009125697A1 - Moule, procédé pour sa production, et procédé pour produire un substrat comportant un motif fin transféré - Google Patents

Moule, procédé pour sa production, et procédé pour produire un substrat comportant un motif fin transféré Download PDF

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Publication number
WO2009125697A1
WO2009125697A1 PCT/JP2009/056732 JP2009056732W WO2009125697A1 WO 2009125697 A1 WO2009125697 A1 WO 2009125697A1 JP 2009056732 W JP2009056732 W JP 2009056732W WO 2009125697 A1 WO2009125697 A1 WO 2009125697A1
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WO
WIPO (PCT)
Prior art keywords
mold
layer
fluoropolymer
fine pattern
transparent resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2009/056732
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English (en)
Japanese (ja)
Inventor
健太郎 角崎
泰秀 川口
幹彦 佐野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP2010507218A priority Critical patent/JPWO2009125697A1/ja
Publication of WO2009125697A1 publication Critical patent/WO2009125697A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/84—Processes or apparatus specially adapted for manufacturing record carriers
    • G11B5/855—Coating only part of a support with a magnetic layer
    • 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
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B29C33/40—Plastics, e.g. foam or rubber
    • 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
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/42—Moulds or cores; Details thereof or accessories therefor characterised by the shape of the moulding surface, e.g. ribs or grooves
    • 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
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0888—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using transparant moulds

Definitions

  • the present invention relates to a mold, a method for producing the mold, and a method for producing a substrate having a transfer fine pattern made of a cured product of a photocurable resin using the mold.
  • the nanoimprint method is mainly studied as a method for forming a fine pattern with a maximum height of 100 nm or less, such as fine wiring of semiconductor elements, recording media, etc., but MEMS (Micro-Electro-Mechanical-Systems), bio-related As a method for forming a fine pattern in which the maximum height of a member, an optical member or the like exceeds several ⁇ m to several tens of ⁇ m, its application is expected in terms of greatly improving productivity.
  • MEMS Micro-Electro-Mechanical-Systems
  • the following molds have been proposed as molds used in the optical nanoimprint method.
  • Quartz mold (2) a transparent substrate (A), a surface layer (B) having a fine pattern on the surface, a transparent substrate (A), and a surface layer (including a fluorine-containing aliphatic ring structure in the main chain) B) a mold having an intermediate layer (C) existing between (see Patent Document 3).
  • the mold has low releasability, and the accuracy of the transferred fine pattern of the cured product tends to decrease when the mold is separated from the cured product.
  • a method for improving the releasability a method of applying a release agent to the surface of the fine pattern of the mold has been proposed.
  • the fine pattern of the mold cannot be accurately transferred due to the uneven thickness of the applied release agent.
  • the mold (2) Since the surface layer (B) is made of a fluoropolymer, the mold (2) has a high releasability. However, since the mold (2) for the purpose of improving mechanical strength and dimensional stability uses a hard material as the transparent substrate (A), the maximum height is the thickness of the surface layer (B) and the intermediate layer. It is difficult to form a fine pattern exceeding the total thickness of (C) for the following reason.
  • the intermediate layer (C) and the surface layer (B) are formed on the surface of the transparent substrate (A) by coating, the master mold is pressed against the surface layer (B), and the reverse pattern of the master mold is formed. It is manufactured by transferring to the surface layer (B).
  • the maximum height of the reverse pattern of the master mold If the maximum height difference of the concavo-convex structure including distortion (waviness) of the entire master mold exceeds the total thickness, in order to accurately transfer the reverse pattern of the master mold, the total thickness is For the excess, the reverse pattern must be transferred to the transparent substrate (A). However, since the transparent substrate (A) is hard, the reverse pattern cannot be transferred to the transparent substrate (A) for the portion exceeding the total thickness.
  • the present invention provides a mold having a fine pattern with high light transmission and releasability and a relatively large maximum height, a method for manufacturing the mold, and a fine pattern of the mold can be transferred with high accuracy and production efficiency.
  • the mold of the present invention is a mold having a fine pattern for molding a photocurable resin, the following transparent resin layer (A), the following surface layer (B), and the surface of the transparent resin layer (A) And the following intermediate layer (C) present between the transparent resin layer (A) and the surface layer (B), wherein the maximum height of the fine pattern is the surface layer (B) ) And the total thickness of the intermediate layer (C).
  • Transparent resin layer (A) a layer made of a transparent resin having a glass transition temperature equal to or lower than the glass transition temperature of the following fluoropolymer (I) and the following fluoropolymer (II), and forming an intermediate layer (C) Before the intermediate layer (C) is formed, the surface on which the intermediate layer (C) is formed has the functional group (x). After the intermediate layer (C) is formed, the surface on which the intermediate layer (C) is formed A layer having a chemical bond based on the functional group (x) and the following reactive group (y).
  • Surface layer (B) A layer comprising a fluoropolymer (I) having a fluorinated aliphatic ring structure in the main chain and substantially not having the following reactive group (y).
  • Intermediate layer (C) A layer comprising a fluorinated polymer (II) having a fluorinated aliphatic ring structure in the main chain and having a reactive group (y) reactive with the functional group (x).
  • the maximum height of the fine pattern is preferably 1 to 500 ⁇ m.
  • the transparent resin layer (A) is preferably supported by a transparent support (D).
  • the functional group (x) is preferably a hydroxyl group, an amino group or an oxiranyl group, and the reactive group (y) is preferably a carboxyl group.
  • the transparent resin layer (A) is preferably a layer in which a functional group (x) is introduced to the surface by surface treatment.
  • the mold production method of the present invention is a mold production method having a fine pattern for molding a photocurable resin, which is made of the following transparent resin, and has a transparent resin layer (A) having a functional group (x) on the surface. ), A step in which a solution obtained by dissolving the following fluoropolymer (II) in a fluorine-containing solvent is applied and dried to form an intermediate layer (C) comprising the following fluoropolymer (II); On the surface of the intermediate layer (C), a solution in which the following fluoropolymer (I) is dissolved in a fluorine-containing solvent is applied and dried to form a surface layer (B) comprising the following fluoropolymer (I).
  • the reversal pattern of the master mold that exceeds the total thickness of the intermediate layer (C), and at least one of the mold precursor and the master mold is the following fluoropolymer (I) and the following fluoropolymer Pressing in a state where the glass transition temperature is higher than (II), forming a fine pattern over the surface layer (B), the intermediate layer (C) and the transparent resin layer (A) to obtain a mold; Characterized by a step of separating the master mold from Rudo.
  • Transparent resin A transparent resin having a glass transition temperature equal to or lower than the glass transition temperature of the following fluoropolymer (I) and the following fluoropolymer (II).
  • Fluoropolymer (I) Fluoropolymer having a fluorinated aliphatic ring structure in the main chain and substantially not having the following reactive group (y).
  • Fluoropolymer (II) Fluoropolymer having a fluorinated aliphatic ring structure in the main chain and a reactive group (y) reactive with the functional group (x).
  • the method for producing a substrate having a transfer fine pattern according to the present invention comprises a step of placing a photocurable resin on the surface of the substrate and a mold according to the present invention so that the fine pattern of the mold is in contact with the photocurable resin. Then, in the state of pressing the photocurable resin, and in a state where the mold is pressed to the photocurable resin, the photocurable resin is irradiated with light to cure the photocurable resin to obtain a cured product. It has a process and the process of isolate
  • the method for producing a substrate having a transfer fine pattern according to the present invention comprises a step of placing a photocurable resin on the surface of a fine pattern of a mold according to the present invention, and a substrate as the photocurable resin on the surface of the mold. A step of pressing the photocurable resin with light applied to the photocurable resin while the substrate is pressed against the photocurable resin, and curing the photocurable resin to obtain a cured product, and the cured product. And a step of separating the mold from the mold.
  • the method for producing a base material having a transfer fine pattern comprises a step of bringing a base material and the mold of the present invention into close contact or contact so that the fine pattern of the mold is on the base material side, and photocurability
  • the mold production method of the present invention can produce a mold having a fine pattern with high light transmittance and releasability and a relatively large maximum height.
  • the present invention can produce a substrate having a transfer fine pattern having a relatively large maximum height, by using the mold of the present invention, capable of accurately transferring the fine pattern of the mold with high production efficiency. Can do.
  • a compound represented by the formula (1) is referred to as a compound (1).
  • the mold of the present invention is a mold having a fine pattern for forming a photocurable resin.
  • FIG. 1 is a cross-sectional view showing an example of the mold of the present invention.
  • the mold 10 is formed on the surface of the transparent resin layer (A) 12, the surface layer (B) 16, and the transparent resin layer (A) 12, and the transparent resin layer (A) 12 and the surface layer (B) 16
  • the intermediate layer (C) 14 existing between the transparent resin layer (A) 12 and the transparent support (D) 17 that supports the transparent resin layer (A) 12 from the back side, and the surface layer (B) 16 and the intermediate layer (C ) 14 and the transparent resin layer (A) 12.
  • the transparent support (D) 17 is not necessarily provided.
  • the convex structure portion in the concavo-convex structure exists in a linear or dot shape on the surface of the mold.
  • the linear convex structure portion may be a straight line, a curved line, or a bent shape. Further, a large number of linear convex structure portions may exist in parallel to form a stripe shape. Examples of the cross-sectional shape of the linear convex structure portion (the cross-sectional shape perpendicular to the longitudinal direction) include a rectangle, a trapezoid, a triangle, and a semicircle.
  • Examples of the shape of the dot-like convex structure include columnar shapes, conical shapes, hemispherical shapes, polyhedral shapes, and the like whose bottom shape is a rectangle, square, rhombus, hexagon, triangle, circle, or the like.
  • the aspect ratio of the convex structure part (height of the convex structure part / width of the base of the convex structure part) is preferably 5 or less. When the aspect ratio is 5 or less, a good fine pattern free from defects such as pinholes can be formed when transferring the reverse pattern of the master mold.
  • the aspect ratio is more preferably 3 or less, and even more preferably 2 or less.
  • the height of the convex structure and the width of the bottom are obtained by profile measurement with a confocal laser microscope.
  • the fine pattern is cut and the cross-section is viewed with a microscope (optical microscope, laser It may be observed and determined with a microscope or an electron microscope.
  • the fine pattern is cut by a known method.
  • a resin embedding process, a cooling process with liquid nitrogen, or the like is performed.
  • the maximum height of the fine pattern exceeds the sum of the thickness of the surface layer (B) and the thickness of the intermediate layer (C).
  • the maximum height of the fine pattern is preferably 500 ⁇ m or less. If the maximum height of the fine pattern is 500 ⁇ m or less, the reverse pattern of the master mold can be uniformly transferred over a wide area.
  • the maximum height of the fine pattern is more preferably 300 ⁇ m or less, and further preferably 100 ⁇ m or less.
  • the lower limit of the maximum height of the fine pattern depends on the total thickness of the surface layer (B) and the intermediate layer (C), but is usually 1 ⁇ m.
  • the maximum height in the present invention is the maximum height defined in JIS B0601, and is the maximum height difference between the highest peak line and the lowest valley line of the concavo-convex structure at the reference length L.
  • the maximum height is determined by profile measurement with a confocal laser microscope. However, if the maximum height is a fine pattern with a steep wall and it is difficult to measure accurately with a confocal laser microscope, the fine pattern is cut and the cross section is observed with a microscope (optical microscope, laser microscope or electron microscope) And you may ask for it.
  • the fine pattern is cut by a known method. However, when there is a possibility that the pattern shape may be lost by cutting, a resin embedding process, a cooling process with liquid nitrogen, or the like is performed.
  • the length of the reference length L is 5 to 20 periods in the case of periodic patterns such as line and space, V-groove, and dot pattern.
  • the length of the reference length L is determined so as to include a portion that becomes the highest point and a portion that becomes the lowest point in the design.
  • the length of the reference length L is large (several mm or more)
  • profile measurement and cross-sectional observation are performed for each location in multiple times, and the maximum height can be obtained by connecting data later.
  • the thicknesses of the surface layer (B) and the intermediate layer (C) are the thicknesses of the surface layer (B) and the intermediate layer (C) in the mold precursor before forming the fine pattern.
  • the transparent resin layer (A) is a layer made of a transparent resin having a glass transition temperature equal to or lower than the glass transition temperature of the fluoropolymer (I) and the fluoropolymer (II), and the intermediate layer (C) is formed. Before the intermediate layer (C) has a functional group (x), and after the intermediate layer (C) is formed, the functional layer (C) is formed on the surface on which the intermediate layer (C) is formed. It is a layer having a chemical bond based on the group (x) and the reactive group (y).
  • the glass transition temperature of the transparent resin is not higher than the glass transition temperature of the fluoropolymer (I) and not higher than the glass transition temperature of the fluoropolymer (II). If the glass transition temperature of the transparent resin is equal to or lower than the glass transition temperature of the fluoropolymer (I) and the fluoropolymer (II), the maximum height of the reverse pattern of the master mold (the distortion (swell) of the entire master mold) The maximum height difference of the concavo-convex structure included) exceeds the sum of the thickness of the surface layer (B) and the thickness of the intermediate layer (C), the transparent resin layer (A) is deformed, and the concavo-convex structure of the reverse pattern In order to follow the distortion (swell) of the entire master mold, the reverse pattern can be accurately transferred.
  • the glass transition temperature of the transparent resin is equal to or lower than the glass transition temperature of the fluoropolymer (I) and the fluoropolymer (II), when the master mold is pressed, the master mold and the surface layer (B) Even if foreign matter is mixed in between, the transparent resin layer (A) is deformed and absorbs the influence of the foreign matter, so that the expensive master mold is not damaged.
  • the glass transition temperature of the transparent resin is preferably 5 ° C. or more, and more preferably 10 ° C. or more lower than the glass transition temperature of the fluoropolymer (I) and the fluoropolymer (II).
  • the glass transition temperature of the transparent resin is preferably 20 ° C. or higher. If the glass transition temperature of transparent resin is 20 degreeC or more, when separating a master mold from a surface layer (B), a transparent resin layer (A) will not deform
  • the glass transition temperature of the transparent resin is more preferably 40 ° C. or higher.
  • the glass transition temperature of the transparent resin is preferably 200 ° C. or lower because it is difficult to synthesize the fluoropolymer (I) and the fluoropolymer (II) having a glass transition temperature exceeding 200 ° C.
  • the glass transition temperature in the present invention is determined according to JIS K7121: 1987 using a differential scanning calorimeter (DSC).
  • the glass transition temperature in this invention means an intermediate point glass transition temperature.
  • Transparent resins include acrylic resin, polystyrene, acrylonitrile butadiene styrene resin (ABS), amorphous polyester, cycloolefin resin (COP), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and ethylene-tetrafluoro.
  • COP cycloolefin resin
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • ethylene-tetrafluoro examples include ethylene copolymer (ETFE), fluoroolefin-alkyl vinyl ether copolymer (FEVE), and silicone resin.
  • the transparent resin is preferably an acrylic resin, amorphous polyester or FEVE from the viewpoints of light transmittance, molding processability and patternability.
  • acrylic resin is polymethyl methacrylate (PMMA).
  • FEVE is Lumiflon (manufactured by Asahi Glass Co., Ltd.). Byron (made by Toyobo Co., Ltd.) is mentioned as an amorphous polyester.
  • the transparent resin is preferably acrylic resin, polystyrene, or COP from the viewpoints of light transmittance, molding processability, patternability, and heat resistance.
  • PMMA is mentioned as an acrylic resin.
  • COP include ZEONEX (manufactured by Nippon Zeon Co., Ltd.).
  • the transparent resin layer (A) (when the transparent support (D) is provided, a laminate of the transparent resin layer (A) and the transparent support (D)) is at least of light in the wavelength region of 300 to 500 nm.
  • the light transmittance is preferably 75% or more, more preferably 85% or more.
  • the photocurable resin can be efficiently cured in the method for producing a substrate having a transfer fine pattern described later.
  • the light transmittance at 436 nm (wavelength of g-line of high-pressure mercury lamp) or 365 nm (wavelength of i-line of high-pressure mercury lamp) is preferably 75% or more, more preferably 85% or more. If the light transmittance at a wavelength of 436 nm or 365 nm is 75% or more, the photocurable resin can be efficiently cured using a high-pressure mercury lamp in the method for producing a substrate having a transfer fine pattern described later.
  • a transparent resin layer (A) When providing a transparent support (D), you may form a transparent resin layer (A) by apply
  • transparent resin is shape
  • the shape of the transparent resin layer (A) (when a transparent support (D) is provided, a laminate of the transparent resin layer (A) and the transparent support (D)) is a flat plate (square shape, disk shape). It may be in the form of a film or a curved surface (lens, cylinder, column, etc.).
  • the transparent resin layer (A) When the shape of the transparent resin layer (A) (when the transparent support (D) is provided, a laminate of the transparent resin layer (A) and the transparent support (D)) is flat, the transparent resin layer (A ) Is preferably 0.4 mm to 20 mm, more preferably 0.5 mm to 15 mm, and still more preferably 0.5 mm to 8 mm. If the thickness of the transparent resin layer (A) is 0.4 mm or more, the mold is difficult to bend and the handleability is good. If the thickness of the transparent resin layer (A) is 20 mm or less, the material is not wasted, and the handleability is good because it does not become heavy.
  • the thickness of the transparent resin layer (A) is preferably in the range of 1 to 10 times the maximum height of the fine pattern. If the thickness of the transparent resin layer (A) is smaller than the maximum height of the fine pattern, the transfer of the fine pattern may be insufficient. When the thickness of the transparent resin layer (A) exceeds 10 times the maximum height of the fine pattern, the dimensional stability of the fine pattern is poor when the glass transition temperature of the transparent resin layer (A) is low (80 ° C. or lower). There is a risk. When the thickness of the transparent resin layer (A) is in the range of 1 to 10 times the maximum height of the fine pattern, it is easy to achieve both good transferability and good dimensional stability. The thickness of the transparent resin layer (A) is more preferably in the range of 1.5 to 6 times the maximum height of the fine pattern.
  • the functional group (x) is preferably a hydroxyl group, an oxiranyl group, or an amino group.
  • the functional group (x) may be a functional group derived from a transparent resin, or may be a functional group imparted to the surface of the transparent resin layer (A) by a surface treatment that introduces the functional group (x). .
  • the latter functional group is preferable because the type and amount of the functional group (x) can be arbitrarily controlled.
  • the surface treatment method for introducing the functional group (x) is a method of surface-treating the transparent resin layer (A) with a silane coupling agent having the functional group (x), or surface treatment of the transparent resin layer (A) by plasma treatment.
  • a method of surface-treating the transparent resin layer (A) by graft polymerization, a method of surface-treating the transparent resin layer (A) by UV ozone treatment, and having a functional group (x) on the transparent resin layer (A) A method of applying a primer is preferred.
  • silane coupling agent having a functional group (x) the following compounds are preferable.
  • Silane coupling agents having an amino group aminopropyltriethoxysilane, aminopropylmethyldiethoxysilane, aminoethyl-aminopropyltrimethoxysilane, aminoethyl-aminopropylmethyldimethoxysilane, and the like.
  • Silane coupling agents having an oxiranyl group glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldimethoxysilane, and the like.
  • part or all of the functional group (x) is part of the reactive group (y) of the fluoropolymer (II). Or form a chemical bond with all.
  • the transparent resin layer (A) in the mold of the present invention has the functional group (x).
  • the transparent resin layer (A) in the mold of the present invention does not have the functional group (x).
  • a chemical bond formed from the functional group (x) and the reactive group (y) exists on the surface of the transparent resin layer (A) after the formation of the intermediate layer (C).
  • the chemical bond is an ester bond when the reactive group (y) is a carboxyl group and the functional group (x) is a hydroxyl group or an oxiranyl group, and the reactive group (y) is a carboxyl group and the functional group (x) is Examples include an amide bond in the case of an amino group. Therefore, in the mold of the present invention, the transparent resin layer (A) and the intermediate layer (C) are firmly bonded via chemical bonds.
  • the surface layer (B) is a layer made of the fluorinated polymer (I) having a fluorinated aliphatic ring structure in the main chain and substantially not having the following reactive group (y).
  • the fluorine-containing polymer (I) having a fluorine-containing aliphatic ring structure in the main chain is an amorphous or non-crystalline polymer. Having a fluorinated aliphatic ring structure in the main chain means that at least one carbon atom constituting the ring of the fluorinated aliphatic ring in the polymer is a carbon atom constituting the main chain of the polymer.
  • the atoms constituting the fluorine-containing aliphatic ring may contain oxygen atoms, nitrogen atoms and the like in addition to carbon atoms.
  • the fluorine-containing aliphatic ring is preferably a fluorine-containing aliphatic ring having 1 to 2 oxygen atoms.
  • the number of atoms constituting the fluorinated aliphatic ring is preferably 4 to 7.
  • the carbon atom constituting the main chain is a polymer obtained by polymerizing a cyclic monomer, it is derived from the carbon atom of a polymerizable double bond and obtained by cyclopolymerizing a diene monomer. In the case of a polymer, it is derived from 4 carbon atoms of 2 polymerizable double bonds.
  • the cyclic monomer is a monomer having a fluorine-containing aliphatic ring and having a polymerizable double bond between carbon atoms constituting the fluorine-containing aliphatic ring, or fluorine-containing aliphatic
  • the diene monomer is a monomer having two polymerizable double bonds.
  • the ratio of the number of fluorine atoms bonded to carbon atoms to the total number of hydrogen atoms bonded to carbon atoms and fluorine atoms bonded to carbon atoms is 80% or more, respectively. Preferably, 100% is particularly preferable.
  • compound (1) or compound (2) is preferable.
  • X 1 represents a fluorine atom or a perfluoroalkoxy group having 1 to 3 carbon atoms
  • R 1 and R 2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms
  • 2 and X 3 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 9 carbon atoms.
  • compound (1) examples include compounds (1-1) to (1-3).
  • compound (2) examples include compounds (2-1) to (2-2).
  • the compound (3) is preferable.
  • Q represents a perfluoroalkylene group having 1 to 3 carbon atoms (which may have an etheric oxygen atom).
  • the etheric oxygen atom may be present at one end of the group or may be present at both ends of the group, and the carbon atom of the group May be present between From the viewpoint of cyclopolymerization, it is preferably present at one end of the group.
  • a fluorinated polymer having one or more monomer units of the following formulas ( ⁇ ) to ( ⁇ ) is obtained by cyclopolymerization of the compound (3).
  • compound (3) include compounds (3-1) to (3-9).
  • the ratio of the monomer units having a fluorinated aliphatic ring structure to the total monomer units (100 mol%) is 20 mol% or more from the viewpoint of the transparency of the fluoropolymer (I). Is preferable, 40 mol% or more is more preferable, and 100 mol% is particularly preferable.
  • the monomer unit having a fluorinated alicyclic structure is a monomer unit formed by polymerization of a cyclic monomer or a monomer unit formed by cyclopolymerization of a diene monomer.
  • Fluoropolymer (I) has substantially no reactive group (y). Having substantially no reactive group (y) means that the content of the reactive group (y) in the fluoropolymer (I) is below the detection limit. Further, it is preferable that the fluoropolymer (I) has substantially no reactive group other than the reactive group (y).
  • the intrinsic viscosity of the fluoropolymer (I) is preferably from 0.1 dL / g to 1.0 dL / g. Intrinsic viscosity correlates with the molecular weight of the fluoropolymer. When the intrinsic viscosity is 0.1 dL / g or more, the fluoropolymer (I) has high mechanical strength, and thus the fine pattern is hardly damaged. If the intrinsic viscosity is 1.0 dL / g or less, the flowability of the fluoropolymer (I) during heating becomes good, and therefore, formation of a fine pattern is facilitated.
  • the intrinsic viscosity of the fluoropolymer (I) is more preferably from 0.15 dL / g to 0.75 dL / g.
  • the intrinsic viscosity in the present invention is an intrinsic viscosity measured at 30 ° C. in perfluoro (2-butyltetrahydrofuran). The viscosity is measured according to JIS Z8803 using an Ubbelohde viscometer (capillary viscometer).
  • the fluoropolymer (I) a highly transparent fluoropolymer is preferable.
  • the light transmittance of light having a wavelength of 300 to 500 nm of the fluoropolymer (I) is preferably 90% or more.
  • the light transmittance is a light transmittance of the fluoropolymer (I) having a thickness of 100 ⁇ m.
  • the glass transition temperature of the fluoropolymer (I) is preferably 20 ° C. or higher.
  • the surface layer (B) is not deformed when the master mold is separated from the surface layer (B), and the dimensional accuracy of the fine pattern is good.
  • the shape of the fluoropolymer (I) is maintained, and the dimensional accuracy of the pattern is improved.
  • the glass transition temperature of the fluoropolymer (I) is more preferably 40 ° C. or higher, and further preferably 70 ° C. or higher.
  • the glass transition temperature of the fluorinated polymer (I) is preferably 200 ° C. or less, more preferably 150 ° C. or less, from the viewpoint that the synthesis of the fluorinated polymer (I) having a glass transition temperature exceeding 200 ° C. is difficult.
  • Fluoropolymer (I) can be obtained according to a known method. For example, after obtaining a fluorine-containing polymer (P) having a fluorine-containing aliphatic ring structure in the main chain or a fluorine-containing polymer (II) having a reactive group (y) by the method described later, the fluorine-containing polymer By bringing the polymer (P) or the fluoropolymer (II) into contact with a fluorine gas, the fluoropolymer (I) substantially free of the reactive group (y) can be obtained.
  • the thickness of the surface layer (B) is preferably 0.2 ⁇ m or more. When the thickness of the surface layer (B) is 0.2 ⁇ m or more, when transferring the reverse pattern of the master mold, defects such as pinholes do not occur and a good fine pattern can be formed.
  • the thickness of the surface layer (B) is more preferably 0.5 ⁇ m or more, and further preferably 1 ⁇ m or more.
  • the thickness of the surface layer (B) is preferably 15 ⁇ m or less. If the thickness of the surface layer (B) is 15 ⁇ m or less, a film having a uniform thickness can be formed by coating.
  • the thickness of the surface layer (B) is more preferably 10 ⁇ m or less, and further preferably 5 ⁇ m or less.
  • the thickness of the surface layer (B) is the thickness of the surface layer (B) in the mold precursor before forming the fine pattern.
  • the intermediate layer (C) is a layer comprising a fluorinated polymer (II) having a fluorinated aliphatic ring structure in the main chain and having a reactive group (y) reactive with the functional group (x). is there.
  • the fluorine-containing polymer (II) having a fluorine-containing aliphatic ring structure in the main chain is an amorphous or non-crystalline polymer.
  • the fluoropolymer (II) is the same polymer as the fluoropolymer (I) except that it has a reactive group (y).
  • the monomer unit having a fluorine-containing aliphatic ring structure in the fluorine-containing polymer (I) and the monomer unit having a fluorine-containing aliphatic ring structure in the fluorine-containing polymer (II) are the intermediate layer (C) and the surface layer (B ) Are more strongly bonded and the durability of the mold is excellent, and the same monomer unit is preferable.
  • the ratio of the monomer units having a fluorinated aliphatic ring structure to the total monomer units (100 mol%) is 20 mol% or more from the viewpoint of the transparency of the fluoropolymer (I). Is preferable, 40 mol% or more is more preferable, and 100 mol% is particularly preferable.
  • the fluoropolymer (II) has a reactive group (y).
  • the kind of reactive group (y) is suitably selected according to the kind of functional group (x).
  • the reactive group (y) is preferably a carboxyl group, a hydroxyl group, a silanol group, or a derivative thereof.
  • a carboxyl group is particularly preferable because it has a high reactivity with an oxiranyl group or an amino group and can easily form a strong bond.
  • the functional group (x) is a hydroxyl group, a silanol group or an alkoxysilane group having 1 to 4 carbon atoms is preferable because a strong bond can be easily formed.
  • the presence or absence of the reactive group (y) is preferably confirmed by an infrared spectrum. If necessary, it is preferably quantified as the number of reactive groups per 10 6 carbon atoms using the method described in JP-A-60-240713.
  • the intrinsic viscosity of the fluoropolymer (II) is preferably 0.1 dL / g to 1.0 dL / g. Intrinsic viscosity correlates with the molecular weight of the fluoropolymer. When the intrinsic viscosity is 0.1 dL / g to 1.0 dL / g, the affinity with the fluorine-containing polymer (I) is high, and the surface layer (B) and the intermediate layer (C) are good. Adhesion can be obtained.
  • the intrinsic viscosity of the fluoropolymer (II) is more preferably from 0.15 dL / g to 0.75 dL / g.
  • the fluoropolymer (II) a highly transparent fluoropolymer is preferable.
  • the light transmittance of light having a wavelength of 300 to 500 nm of the fluoropolymer (II) is preferably 90% or more.
  • the light transmittance is the light transmittance of a fluoropolymer (II) having a thickness of 100 ⁇ m.
  • Fluoropolymer (II) can be obtained according to a known method.
  • the fluoropolymer (II) in which the reactive group (y) is a carboxyl group is obtained by polymerizing a diene monomer or a cyclic monomer in the presence of a hydrocarbon radical polymerization initiator.
  • the fluorine-containing polymer (P) having a fluorine-containing aliphatic ring structure is obtained, and the fluorine-containing polymer (P) is then heat-treated in an oxygen gas atmosphere and further immersed in water.
  • the fluorine-containing polymer (II) in which the reactive group (y) is a silanol group is the carboxyl group of the fluorine-containing polymer (II) having a carboxyl group as in the method described in JP-A-4-226177. Is esterified to form a carboxylic acid methyl ester, and the carboxylic acid methyl ester is further reacted with a silane coupling agent having an amino group or an oxiranyl group to form an amide bond.
  • the fluorine-containing polymer (II) in which the reactive group (y) is a hydroxyl group can be obtained by reducing the carboxyl group of the fluorine-containing polymer having a carboxyl group.
  • the thickness of the intermediate layer (C) is preferably 5 nm to 2000 nm. If the thickness of the intermediate layer (C) is 5 nm or more, a uniform film can be formed and high adhesion can be obtained. If the thickness of the intermediate layer (C) is 2000 nm or less, there is little waste of material.
  • the thickness of the intermediate layer (C) is more preferably 10 nm to 1000 nm, further preferably 20 to 500 nm.
  • the thickness of the intermediate layer (C) is the thickness of the intermediate layer (C) in the mold precursor before forming the fine pattern.
  • Transparent support (D) The transparent resin layer (A) is preferably supported by the transparent support (D). If the transparent resin layer (A) is supported by the transparent support (D), the warping of the transparent resin layer (A) can be suppressed when transferring the reverse pattern of the master mold, and the material of the transparent resin layer (A) The choice of transparent resin that can be selected as is increased.
  • the heat distortion temperature of the transparent support (D) is preferably 100 ° C. or higher, more preferably 120 ° C. or higher.
  • the heat distortion temperature of the transparent support (D) is 100 ° C. or higher, it can be heated while maintaining the shape of the transparent resin layer (A), and the workability is excellent. Further, when transferring the reverse pattern of the master mold, the reverse pattern can be transferred with good dimensional stability.
  • the upper limit of the heat distortion temperature of the transparent support (D) is not particularly defined. You may use the transparent support body (D) whose heat-deformation temperature exceeds 300 degreeC like inorganic materials, such as glass.
  • the heat distortion temperature in the present invention is measured under a load condition of 1.82 MPa according to ASTM D648.
  • transparent support As a material of the transparent support (D), inorganic materials (quartz, glass, translucent ceramics, etc.). ) And transparent resins (polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), fluorene polyester, COP, polyarylate (PAR), aromatic polyetheretherketone (PEEK), aromatic polyethersulfone (PES), wholly aromatic polyketone, fluorine resin, silicone resin, acrylic resin, epoxy resin, phenol resin, etc.). Quartz, glass, PC, and COP are preferable from the viewpoint of light transmittance, molding processability, and heat resistance.
  • Step M1 On the surface side of the transparent resin layer (A) having a functional group (x) on the surface, a solution obtained by dissolving the fluorinated polymer (II) in a fluorinated solvent is applied, and then the fluorinated solvent Is removed by drying, and an intermediate layer (C) made of the fluoropolymer (II) is formed on the surface side of the transparent resin layer (A) having a functional group (x) on the surface.
  • Step M2 A solution in which the fluorinated polymer (I) is dissolved in a fluorinated solvent is applied to the surface side of the intermediate layer (C), and then the fluorinated solvent is removed by drying, so that the intermediate layer (C ) To form a surface layer (B) made of the fluoropolymer (I) to obtain a mold precursor.
  • Step M3 From the surface layer (B) side of the mold precursor, a fine pattern inversion pattern is provided on the surface, and the maximum height of the inversion pattern is the thickness of the surface layer (B) and the thickness of the intermediate layer (C).
  • Step M4 A step of separating the master mold from the mold after cooling the mold and the master mold to below the glass transition temperature of the fluoropolymer (I) and the fluoropolymer (II).
  • the drying in the step M1 is a chemical bond between part or all of the functional groups (x) of the transparent resin layer (A) and part or all of the reactive groups (y) of the fluoropolymer (II). Is performed at a temperature capable of forming The drying temperature is usually 100 ° C. or higher.
  • the drying temperature in the step M2 is preferably not less than the glass transition temperature of the fluoropolymer (II) and not less than the glass transition temperature of the fluoropolymer (I). By drying at this temperature, the intermediate layer (C) and the surface layer (B) are bonded with high strength.
  • step M3 at least one of the mold precursor and the master mold is heated to a temperature equal to or higher than the glass transition temperature of the fluoropolymer (I) and the fluoropolymer (II). If the heating temperature is equal to or higher than the glass transition temperature of the fluoropolymer (I) and the fluoropolymer (II), the reverse pattern of the master mold can be accurately transferred.
  • the heating temperature is preferably 10 ° C. or more higher than the glass transition temperature of the fluoropolymer (I) and the fluoropolymer (II).
  • the heating temperature is preferably 250 ° C. or lower, and more preferably 220 ° C. or lower.
  • the heating temperature of the mold precursor and the master mold is lower than the glass transition temperature of the fluoropolymer (I) and the fluoropolymer (II) in the step M3, the heating temperature is the transparent resin layer ( If the glass transition temperature is equal to or higher than the glass transition temperature of A), the pattern can be transferred, but the pattern shape may not be accurately transferred, there may be a region where the pattern is not transferred, or the surface of the pattern may be roughened.
  • the heating temperature of the mold precursor and the master mold is lower than the glass transition temperature of the transparent resin layer (A), the pattern is not transferred.
  • the mold of the present invention described above is a laminate of a transparent resin layer (A), an intermediate layer (C) made of a fluoropolymer (II), and a surface layer (B) made of a fluoropolymer (I). Therefore, it has high light transmittance. Moreover, since the mold of this invention is a layer which a surface layer (B) consists of a fluoropolymer (I), it has the mold release property of the grade which can shape
  • the glass transition temperature of the transparent resin constituting the transparent resin layer (A) is not higher than the glass transition temperatures of the fluoropolymer (I) and the fluoropolymer (II). Therefore, the maximum height of the fine pattern (the maximum height difference of the concavo-convex structure including the distortion (waviness) of the entire mold) exceeds the sum of the thickness of the surface layer (B) and the thickness of the intermediate layer (C).
  • the transparent resin layer (A) is deformed and can follow the concavo-convex structure of the reverse pattern, the distortion (swell) of the entire master mold, etc., so that the surface layer (B), intermediate layer A fine pattern can be accurately formed across (C) and the transparent resin layer (A). Furthermore, even if foreign particles are mixed between the master mold and the surface layer (B) when the master mold is pressed, the transparent resin layer (A) is deformed, so that the expensive master mold is not damaged.
  • A-1) A step of disposing the photocurable resin 20 on the surface of the substrate 30.
  • A-2) A step of pressing the mold 10 against the photocurable resin 20 so that the fine pattern 18 of the mold 10 contacts the photocurable resin 20 as shown in FIG.
  • A-3) A step of irradiating the photocurable resin 20 with light while the mold 10 is pressed against the photocurable resin 20 to cure the photocurable resin 20 to obtain a cured product.
  • A-4) A step of separating the mold 10 from the cured product.
  • Method (b) A method comprising the following steps (b-1) to (b-4).
  • B-1) A step of disposing the photocurable resin 20 on the surface of the fine pattern 18 of the mold 10.
  • B-2 A step of pressing the substrate 30 against the photocurable resin 20 on the surface of the mold 10 as shown in FIG.
  • B-3) A step of irradiating the photocurable resin 20 with light while the substrate 30 is pressed against the photocurable resin 20 to cure the photocurable resin 20 to obtain a cured product.
  • B-4) A step of separating the mold 10 from the cured product.
  • Method (c) A method comprising the following steps (c-1) to (c-4).
  • C-1) A step of bringing the base material 30 and the mold 10 close to or in contact with each other so that the fine pattern 18 of the mold 10 is on the base material 30 side.
  • C-2) A step of filling the photocurable resin 20 between the base material 30 and the mold 10 as shown in FIG.
  • C-3) A step of irradiating the photocurable resin 20 with light in a state where the base material 30 and the mold 10 are close to or in contact with each other to cure the photocurable resin 20 to obtain a cured product.
  • C-4) A step of separating the mold 10 from the cured product.
  • the photocurable resin is a resin that is cured by light irradiation to form a cured product.
  • the photocurable resin containing a polymeric compound and a photoinitiator is preferable.
  • the polymerizable compound include compounds having a polymerizable group, such as a polymerizable monomer, a polymerizable oligomer, and a polymerizable polymer.
  • the photopolymerization initiator is a photopolymerization initiator that causes radical reaction or ionic reaction by light.
  • the light irradiation is usually performed from the mold 10 side.
  • light irradiation may be performed from the base material 30 side.
  • the wavelength of the light in light irradiation should just be a wavelength range with which the mold of this invention has high light transmittance.
  • the wavelength of light in the light irradiation is particularly preferably g-line (wavelength 436 nm) or i-line (wavelength 365 nm) of a high-pressure mercury lamp from the viewpoint that a general photocurable resin can be cured at a low temperature.
  • the transparent resin layer (A) is inferior in light resistance to quartz or glass
  • the light in light irradiation preferably does not contain light having a wavelength of less than 300 nm, and more preferably does not contain light having a wavelength of less than 350 nm.
  • the temperature of the system in each step of the methods (a) to (c) is preferably not higher than the glass transition temperature of the fluoropolymer (I).
  • the substrate having a transfer fine pattern produced by the production method of the present invention has a transfer fine pattern made of a cured product of a photocurable resin on the surface of the substrate.
  • the transferred fine pattern is a fine pattern obtained by inverting the fine pattern of the mold of the present invention.
  • the transfer fine pattern is preferably a structure having a concavo-convex structure (hereinafter also referred to as a concavo-convex structure) made of a cured product of a photocurable resin.
  • the concavo-convex structure may have a layer structure composed of a continuous body having a concavo-convex shape on the surface, or may have a structure composed of an independent set of protrusions.
  • the former consists of a layer of a cured product of a photocurable resin that covers the surface of the substrate, and the surface of the cured product layer of the photocurable resin has a concavo-convex shape.
  • the latter refers to a structure in which a large number of protrusions made of a cured product of a photocurable resin are present independently on the surface of the base material and form an uneven shape together with a concave portion made of the surface of the base material.
  • the convex structure (projection) is made of a cured product of a photocurable resin.
  • the concavo-convex structure may have a structure having these two structures together at different positions on the surface of the substrate.
  • Examples of the substrate having a transfer fine pattern include semiconductor elements, recording media, MEMS, bio-related members, optical members, and the like.
  • Specific examples of the MEMS, bio-related member, and optical member include the following.
  • the fine pattern of the mold can be transferred with high accuracy and production efficiency, and a transfer fine pattern having a relatively large maximum height can be formed.
  • the intrinsic viscosity of the fluorinated polymer was measured in perfluoro (2-butyltetrahydrofuran) at 30 ° C. using a glass Ubbelohde tube.
  • the infrared absorption spectrum of the fluorine-containing polymer was measured using a Fourier transform infrared spectrometer (Nicolet, 20DXC).
  • Glass-transition temperature The glass transition temperature of the transparent resin and the fluoropolymer was measured using a differential scanning calorimeter (manufactured by Bruker AXS Co., Ltd., DSC3100) at a temperature rising rate of 20 ° C./min. The glass transition temperature was measured according to JIS K7121: 1987, and the midpoint glass transition temperature was taken as the glass transition temperature.
  • the heat distortion temperature of the transparent resin was measured by ASTM D648 using a heat distortion tester (manufactured by Yasuda Seiki Seisakusho, HD-PC) under a load of 1.82 MPa.
  • the film of the transparent resin layer (A) or the laminate of the transparent resin layer (A) and the transparent support (D) has a 436 nm transmittance and a 365 nm transmittance, and a fluoropolymer film having a wavelength of 300 to 500 nm.
  • the light transmittance of light was measured using a spectrophotometer (manufactured by Hitachi High-Technology Corporation, U-4100).
  • the thicknesses of the surface layer (B) and the intermediate layer (C) were measured using an optical interference film thickness measuring device (C10178, manufactured by Hamamatsu Photonics).
  • the refractive indexes of the fluoropolymer (I-1), the fluoropolymer (II-1) and the fluoropolymer (II-2) were each 1.34.
  • the maximum height of the fine pattern formed on the mold was obtained by profile measurement using a confocal laser microscope (manufactured by Keyence Corporation, VK-9500).
  • V-groove pattern the profile in the direction perpendicular to the groove was measured, and in the case of the cylindrical pattern, the profile on a line passing through the center of the cylinder was measured.
  • color ultra-depth observation is performed under the conditions of a lens magnification of 50 times, an optical zoom of 1 time, and a measurement pitch of 0.05 ⁇ m, and after performing surface tilt correction (automatic), a profile in a range of 200 ⁇ m in length is obtained.
  • the maximum height difference between the highest peak line and the lowest valley line of the concavo-convex structure was obtained.
  • Example 1 Production of fluorinated polymer (P-1): To an autoclave (made of pressure-resistant glass), 100 g of compound (3-3), 0.5 g of methanol, and 0.7 g of compound (4-1) were added, and compound (3-3) was added by suspension polymerization. Polymerization was performed to obtain a fluoropolymer (P-1).
  • the fluorine-containing polymer (P-1) is a polymer comprising monomer units represented by the following formula ( ⁇ -1).
  • the intrinsic viscosity of the fluoropolymer (P-1) was 0.34 dL / g.
  • the glass transition temperature of the fluoropolymer (P-1) was 108 ° C.
  • fluoropolymer (I-1) Production of a fluoropolymer having a monomer unit represented by the above formula ( ⁇ -1) and having a terminal —CF 3 (hereinafter referred to as fluoropolymer (I-1)):
  • the fluoropolymer (P-1) was placed in an autoclave (made of nickel, internal volume 1 L), and the interior of the autoclave was replaced with nitrogen gas three times, and then the pressure was reduced to 4.0 kPa (absolute pressure). After introducing fluorine gas diluted to 14% by volume with nitrogen gas into the autoclave up to 101.3 kPa, the internal temperature of the autoclave was maintained at 230 ° C. for 6 hours.
  • the contents of the autoclave were recovered to obtain a fluoropolymer (I-1).
  • a fluoropolymer (I-1) As a result of measuring the infrared absorption spectrum of the fluoropolymer (I-1), no peak due to the carboxyl group was confirmed.
  • the fluoropolymer (I-1) was processed into a film having a thickness of 100 ⁇ m, and the light transmittance of light having a wavelength of 300 to 500 nm was measured and found to be 95% or more.
  • the glass transition temperature of the fluoropolymer (I-1) was 108 ° C.
  • the intrinsic viscosity of the fluoropolymer (I-1) was 0.33 dL / g.
  • solution composition 1 containing the fluoropolymer (I-1): A perfluorotributylamine solution containing 9% by mass of the fluoropolymer (I-1) was prepared, and the solution was filtered through a membrane filter (pore size: 0.2 ⁇ m, manufactured by PTFE) to obtain a solution composition 1.
  • a membrane filter pore size: 0.2 ⁇ m, manufactured by PTFE
  • the fluoropolymer (P-1) was heat-treated at 300 ° C. for 1 hour in a hot-air circulating oven under atmospheric pressure, then immersed in ultrapure water at 110 ° C. for 1 week, and then vacuum dried. It was dried in the machine at 100 ° C. for 24 hours to obtain a fluoropolymer (II-1).
  • the fluoropolymer (II-1) was processed into a film having a thickness of 100 ⁇ m, and the light transmittance of light having a wavelength of 300 to 500 nm was measured. As a result, it was 93% or more.
  • the glass transition temperature of the fluoropolymer (II-1) was 108 ° C.
  • the intrinsic viscosity of the fluoropolymer (II-1) was 0.34 dL / g.
  • solution composition 2 containing the fluoropolymer (II-1): A perfluorotributylamine solution containing 1% by mass of the fluoropolymer (II-1) was prepared, and the solution was filtered through a membrane filter (pore size: 0.2 ⁇ m, manufactured by PTFE) to obtain a solution composition 2.
  • a membrane filter pore size: 0.2 ⁇ m, manufactured by PTFE
  • Example 4 Mold production: A PC sheet (length 40 mm ⁇ width 40 mm ⁇ thickness 0.5 mm) was prepared as the transparent resin layer (A). Table 1 shows the physical properties of the transparent resin layer (A).
  • a primer having an oxiranyl group (manufactured by Shin-Etsu Chemical Co., Ltd., FS-10) was diluted 20 times with a mixed solvent of butyl acetate / 2-propanol (5/9 mass ratio) to obtain a primer coating solution.
  • the primer coating solution is applied to the surface of the transparent resin layer (A) using a spin coating method, and heated and dried at 100 ° C. for 30 minutes in a nitrogen stream to introduce oxiranyl groups to the surface of the transparent resin layer (A). Surface treatment was performed.
  • the solution composition 2 is applied to the surface-treated surface of the transparent resin layer (A) by using a spin coating method, followed by heating and drying at 110 ° C. for 2 hours, so that the perfluorotributylamine in the solution composition 2 is obtained. Volatilized.
  • the intermediate layer (C) (C) comprising the fluoropolymer (II-1) is obtained by chemically bonding the oxiranyl group on the surface of the transparent resin layer (A) and the carboxyl group of the fluoropolymer (II-1). (Thickness: 0.1 ⁇ m) was formed.
  • the solution composition 1 is applied to the surface of the intermediate layer (C) by using a spin coating method, and heated and dried at 110 ° C. for 4 hours to volatilize perfluorotributylamine in the solution composition 1, A surface layer (B) was formed to obtain a mold precursor.
  • the sum of the thickness of the surface layer (B) and the thickness of the intermediate layer (C) was 1.3 ⁇ m.
  • a nickel master mold having a fine pattern composed of V-grooves having a depth (maximum height) of 10 ⁇ m, a pitch of 20 ⁇ m, and an angle of slope of 45 degrees on the surface was prepared.
  • the master mold was heated to 160 ° C. and pressure-bonded at 3 MPa (absolute pressure) for 2 minutes from the surface layer (B) side of the mold precursor.
  • the master mold is separated from the mold precursor, and is composed of a transparent resin layer (A), an intermediate layer (C), and a surface layer (B).
  • a mold in which a fine pattern was formed over (B) and the intermediate layer (C) was obtained.
  • the maximum height of the fine pattern was 9.8 ⁇ m. Some warpage was observed in the mold.
  • the transparent resin layer (A) was exposed at the valley bottom of the fine pattern of the mold.
  • a photocurable resin (NIF-A-1 manufactured by Asahi Glass Co., Ltd.) was applied to the surface of the fine pattern of the mold, and a silicon wafer was pressed from above onto the photocurable resin.
  • the photocurable resin was cured by irradiating with ultraviolet rays (wavelength: 365 nm, illuminance: 50 mW / cm 2 ) for 30 seconds from the mold side. Next, an attempt was made to separate the mold, but it was not possible to separate the mold and the silicon wafer because they were bonded.
  • Example 5 Mold production: A PMMA sheet (length 40 mm ⁇ width 40 mm ⁇ thickness 1.8 mm) was prepared as the transparent resin layer (A). Table 1 shows the physical properties of the transparent resin layer (A). A transparent resin layer (A), an intermediate layer (C), and a transparent resin layer (A) were prepared in the same manner as in Example 4 except that a PMMA sheet was used instead of the PC sheet as the transparent resin layer (A) and the heating temperature of the master mold was 130 ° C. A mold comprising a surface layer (B) and having a fine pattern formed over the surface layer (B) and the intermediate layer (C) was obtained. The maximum height of the fine pattern was 9.8 ⁇ m. Some warpage was observed in the mold. Moreover, the transparent resin layer (A) was exposed at the valley bottom of the fine pattern of the mold.
  • a photocurable resin (NIF-A-1 manufactured by Asahi Glass Co., Ltd.) was applied to the surface of the fine pattern of the mold, and a silicon wafer was pressed from above onto the photocurable resin.
  • the photocurable resin was cured by irradiating with ultraviolet rays (wavelength: 365 nm, illuminance: 50 mW / cm 2 ) for 30 seconds from the mold side. Next, an attempt was made to separate the mold, but it was not possible to separate the mold and the silicon wafer because they were bonded.
  • Example 6 Mold production: As the transparent resin layer (A), a PMMA sheet (length 40 mm ⁇ width 40 mm ⁇ thickness 1.8 mm) having a glass transition temperature lower than that of the PMMA sheet used in Example 5 was prepared. Table 2 shows the physical properties of the transparent resin layer (A).
  • a transparent resin layer (A), an intermediate layer (C), and a transparent resin layer (A) were prepared in the same manner as in Example 4 except that a PMMA sheet was used instead of the PC sheet as the transparent resin layer (A) and the heating temperature of the master mold was 120 ° C.
  • a mold comprising a surface layer (B) and having a fine pattern formed on the surface layer (B), the intermediate layer (C) and the transparent resin layer (A) was obtained. The maximum height of the fine pattern was 10.0 ⁇ m. Some warpage was observed in the mold.
  • a photocurable resin (NIF-A-1 manufactured by Asahi Glass Co., Ltd.) was applied to the surface of the fine pattern of the mold, and a silicon wafer was pressed from above onto the photocurable resin.
  • the photocurable resin was cured by irradiating with ultraviolet rays (wavelength: 365 nm, illuminance: 50 mW / cm 2 ) for 30 seconds from the mold side.
  • the mold and the silicon wafer were separated, and a silicon wafer having a transfer fine pattern made of a cured product of a photocurable resin on the surface was obtained.
  • VK-9500 manufactured by Keyence Corporation
  • Example 7 Mold production: A transparent resin FEVE (manufactured by Asahi Glass Co., Ltd., Lumiflon LF710F) was dissolved in toluene so as to be 30% by mass to obtain a coating solution. Using an applicator, the coating solution is applied to a transparent support (D) (soda lime glass plate, thickness: 1.30 mm, heat distortion temperature: 300 ° C. or higher) and dried at 100 ° C. for 2 hours to form a transparent resin Layer (A) was formed. It was 30 micrometers when the thickness of the transparent resin layer (A) was measured with the micrometer. Table 2 shows the physical properties of the transparent resin layer (A) and the transparent support (D).
  • a transparent support (D) was used in the same manner as in Example 4 except that a glass plate on which a transparent resin layer (A) made of FEVE was formed was used instead of the PC sheet, and the heating temperature of the master mold was 120 ° C. And a transparent resin layer (A), an intermediate layer (C), and a surface layer (B), and a mold having a fine pattern formed on the surface layer (B), the intermediate layer (C), and the transparent resin layer (A). Obtained. The maximum height of the fine pattern was 9.9 ⁇ m. A laser microscope image of the mold is shown in FIG. No warpage was observed in the mold.
  • a silicon wafer having a transfer fine pattern made of a cured product of a photocurable resin on the surface was obtained in the same manner as in Example 6 except that the mold of Example 7 was used instead of the mold of Example 6.
  • the transferred fine pattern was observed with a laser microscope, the fine pattern of the master mold was reproduced.
  • Example 8 Mold production: A transparent resin FEVE (manufactured by Asahi Glass Co., Ltd., Lumiflon LF710F) was dissolved in toluene so as to be 30% by mass to obtain a coating solution. Using an applicator, the coating solution is applied to a transparent support (D) (soda lime glass plate, thickness: 1.30 mm, heat distortion temperature: 300 ° C. or higher) and dried at 100 ° C. for 2 hours to form a transparent resin Layer (A) was formed. It was 30 micrometers when the thickness of the transparent resin layer (A) was measured with the micrometer. Table 2 shows the physical properties of the transparent resin layer (A) and the transparent support (D).
  • the surface of the transparent resin layer (A) was previously hydrophilized (nitrogen plasma treatment).
  • the hydrophilic treatment was performed using a reactive ion etching apparatus (RIE-10NR, manufactured by Samco Corporation) under the conditions of a nitrogen flow rate: 20 sccm, a pressure: 4 Pa, an output: 80 W, and a treatment time: 1 minute.
  • RIE-10NR reactive ion etching apparatus
  • An ethanol solution containing 0.5% by mass of a silane coupling agent having an amino group (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) and 5% by mass of water is applied to the surface of the transparent resin layer (A) by spin coating. It applied using. Surface treatment for introducing the amino group derived from the silane coupling agent to the surface of the transparent resin layer (A) by washing the transparent resin layer (A) with water and then drying by heating in a nitrogen stream at 100 ° C. for 30 minutes. Went.
  • the solution composition 2 is applied to the surface-treated surface of the transparent resin layer (A) by using a spin coating method, followed by heating and drying at 110 ° C. for 2 hours, so that the perfluorotributylamine in the solution composition 2 is obtained. Volatilized. At the same time, the amino group on the surface of the transparent resin layer (A) and the carboxyl group of the fluoropolymer (II-1) are chemically bonded to form an intermediate layer (C) composed of the fluoropolymer (II-1) ( Thickness: 0.10 ⁇ m) was formed.
  • the solution composition 1 is applied to the surface of the intermediate layer (C) by using a spin coating method, and heated and dried at 110 ° C. for 4 hours to volatilize perfluorotributylamine in the solution composition 1, A surface layer (B) was formed to obtain a mold precursor.
  • the sum of the thickness of the surface layer (B) and the thickness of the intermediate layer (C) was 1.25 ⁇ m.
  • a fine pattern is formed in the same manner as in Example 4 except that the mold precursor is used, and includes a transparent resin layer (A), an intermediate layer (C), and a surface layer (B).
  • a mold having a fine pattern formed over the intermediate layer (C) and the transparent resin layer (A) was obtained.
  • the maximum height of the fine pattern was 10.0 ⁇ m. No warpage was observed in the mold.
  • a silicon wafer having a transfer fine pattern made of a cured product of a photocurable resin on the surface was obtained in the same manner as in Example 6 except that the mold of Example 8 was used instead of the mold of Example 6.
  • the transferred fine pattern was observed with a laser microscope, the fine pattern of the master mold was reproduced.
  • Example 9 Mold production: Except that the oxiranyl group was not introduced into the surface of the transparent resin layer (A), the same procedure as in Example 7 was conducted. When separating the master mold from the mold, the transparent resin layer (A) and the intermediate layer (C) Peeling occurred between.
  • Example 10 Mold production: When the intermediate layer (C) was formed, except that the solution composition 1 was used in place of the solution composition 2, it was performed in the same manner as in Example 8. When separating the master mold from the mold, a transparent resin was used. Peeling occurred between the layer (A) and the intermediate layer (C).
  • Example 11 A polymer comprising monomer units represented by the above formula ( ⁇ -1) and having a terminal reactive group (y) (silanol group (alkoxysilane group)) (hereinafter referred to as “fluorinated polymer”)).
  • fluorinated polymer hereinafter referred to as “fluorinated polymer”.
  • the system was replaced with nitrogen, and the mixture was stirred at room temperature for 3 hours to obtain a fluoropolymer (II-2).
  • the fluoropolymer (II-2) was processed into a film having a thickness of 100 ⁇ m, and the light transmittance of light having a wavelength of 300 to 500 nm was measured and found to be 92% or more.
  • the glass transition temperature of the fluoropolymer (II-2) was 108 ° C.
  • the intrinsic viscosity of the fluoropolymer (II-2) was 0.32 dL / g.
  • solution composition 3 A perfluorotributylamine solution containing 1% by mass of the fluoropolymer (II-2) was prepared. The solution was filtered through a membrane filter (pore size: 0.2 ⁇ m, made of PTFE) to obtain a solution composition 3.
  • Example 12 Mold production: Amorphous polyester (byron 200, manufactured by Toyobo Co., Ltd.), which is a transparent resin, was dissolved in cyclohexanone so as to be 30% by mass to obtain a coating solution. Using an applicator, the coating solution is applied to a transparent support (D) (soda lime glass plate, thickness: 1.30 mm, heat distortion temperature: 300 ° C. or higher) and dried at 150 ° C. for 2 hours to form a transparent resin Layer (A) was formed. It was 30 micrometers when the thickness of the transparent resin layer (A) was measured with the micrometer. Table 2 shows the physical properties of the transparent resin layer (A) and the transparent support (D).
  • the surface of the transparent resin layer (A) was previously hydrophilized (oxygen plasma treatment).
  • the hydrophilic treatment was performed using a reactive ion etching apparatus (RIE-10NR, manufactured by Samco) under the conditions of oxygen flow rate: 50 sccm, pressure: 10 Pa, output: 100 W, treatment time: 10 seconds.
  • RIE-10NR reactive ion etching apparatus
  • the solution composition 3 is applied to the surface-treated surface of the transparent resin layer (A) by using a spin coating method, and is heated and dried at 110 ° C. for 2 hours, so that the perfluorotributylamine in the solution composition 3 is obtained. Volatilized.
  • the hydroxyl group on the surface of the transparent resin layer (A) and the silanol group of the fluoropolymer (II-2) are chemically bonded to form an intermediate layer (C) (thickness of the fluoropolymer (II-2)). : 0.1 ⁇ m).
  • the solution composition 1 is applied to the surface of the intermediate layer (C) by using a spin coating method, and heated and dried at 110 ° C. for 4 hours to volatilize perfluorotributylamine in the solution composition 1, A surface layer (B) was formed to obtain a mold precursor.
  • the sum of the thickness of the surface layer (B) and the thickness of the intermediate layer (C) was 1.2 ⁇ m.
  • a fine pattern is formed in the same manner as in Example 4 except that the mold precursor is used, and includes a transparent resin layer (A), an intermediate layer (C), and a surface layer (B).
  • a mold having a fine pattern formed over the intermediate layer (C) and the transparent resin layer (A) was obtained.
  • the maximum height of the fine pattern was 9.7 ⁇ m. No warpage was observed in the mold.
  • Example 13 Mold production: Amorphous polyester (byron 300, manufactured by Toyobo Co., Ltd.), which is a transparent resin, was dissolved in cyclohexanone so as to be 30% by mass to obtain a coating solution. Using an applicator, the coating solution is applied to a transparent support (D) (soda lime glass plate, thickness: 1.30 mm, heat distortion temperature: 300 ° C. or higher) and dried at 150 ° C. for 2 hours to form a transparent resin Layer (A) was formed. It was 30 micrometers when the thickness of the transparent resin layer (A) was measured with the micrometer. Table 2 shows the physical properties of the transparent resin layer (A) and the transparent support (D).
  • a mold was obtained. The maximum height of the fine pattern was 10.1 ⁇ m. No warpage was observed in the mold.
  • Example 14 Mold production: Example 7 except that instead of the master mold of Example 1, a silicon mold having a fine pattern in which cylindrical holes having a diameter of 5 ⁇ m and a depth (maximum height): 5 ⁇ m are arranged in a grid at intervals of 10 ⁇ m was used. In the same manner, the transparent support (D), the transparent resin layer (A), the intermediate layer (C), and the surface layer (B) are formed. The surface layer (B), the intermediate layer (C), and the transparent resin layer ( A mold having a fine pattern formed over A) was obtained. The maximum height of the fine pattern was 5.1 ⁇ m. No warpage was observed in the mold.
  • Example 15 Mold production: Except that the heating temperature of the master mold was set to 40 ° C., the same process as in Example 7 was performed. As a result, the fine pattern of the master mold was not transferred onto the surface of the mold.
  • the mold of the present invention is useful as a mold for optical nanoimprint using a photocurable resin.
  • a base material having a transfer fine pattern obtained by using the mold of the present invention is useful as a semiconductor element, a recording medium, a MEMS, a bio-related member, an optical member, and the like.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Thermal Sciences (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Micromachines (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

L'invention porte sur un moule qui a une transmission de la lumière élevée et une aptitude au démoulage élevée, et qui a un motif fin dont la hauteur maximale est relativement grande. L'invention porte également sur un procédé pour produire le moule ; et sur un procédé pour produire un substrat avec un motif fin transféré à l'aide du moule. Le moule (10) comprend une couche de résine transparente (A) (12) constituée par une résine transparente et comportant des liaisons chimiques fondées sur un groupe fonctionnel (x) à sa surface, sur le côté couche intermédiaire (C), une couche intermédiaire (C) (14) comprenant un polymère fluoré (II) dont le squelette a une structure alicyclique fluorée et qui comporte un groupe réactif (y) pouvant réagir avec le groupe fonctionnel (x), et une couche de surface (B) (16) comprenant un polymère fluoré (I) dont le squelette a une structure alicyclique fluorée et qui ne comporte pas le groupe réactif (y), la résine transparente ayant une température de transition vitreuse qui n'est pas supérieure aux températures de transition vitreuse du polymère fluoré (I) et du polymère fluoré (II). Le motif fin a une hauteur maximale dépassant la somme de l'épaisseur de la couche de surface (B) et de l'épaisseur de la couche intermédiaire (C).
PCT/JP2009/056732 2008-04-08 2009-03-31 Moule, procédé pour sa production, et procédé pour produire un substrat comportant un motif fin transféré Ceased WO2009125697A1 (fr)

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JP2011159824A (ja) * 2010-02-01 2011-08-18 Sumitomo Electric Ind Ltd ナノインプリント法による樹脂パターン形成方法及び回折格子の形成方法
JP2013219230A (ja) * 2012-04-10 2013-10-24 Dainippon Printing Co Ltd ナノインプリント方法及びナノインプリント装置
JP5794387B2 (ja) * 2012-04-10 2015-10-14 ダイキン工業株式会社 インプリント用樹脂モールド材料組成物
WO2021033538A1 (fr) * 2019-08-21 2021-02-25 Ａｇｃ株式会社 Substrat électronique, procédé de fabrication de substrat électronique et instrument électronique

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JP2007245702A (ja) * 2006-02-20 2007-09-27 Asahi Glass Co Ltd テンプレートおよび転写微細パターンを有する処理基材の製造方法
JP2007266384A (ja) * 2006-03-29 2007-10-11 Toppan Printing Co Ltd インプリント用モールド及びその製造方法
JP2007320071A (ja) * 2006-05-30 2007-12-13 Asahi Glass Co Ltd テンプレートおよび転写微細パターンを有する処理基材の製造方法
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WO2006059580A1 (fr) * 2004-11-30 2006-06-08 Asahi Glass Company, Limited Moule et procédé de fabrication de substrats ayant des micromotifs transférés sur ceux-ci
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JP2007266384A (ja) * 2006-03-29 2007-10-11 Toppan Printing Co Ltd インプリント用モールド及びその製造方法
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WO2011052369A1 (fr) * 2009-10-29 2011-05-05 Dic株式会社 Composition pour disques optiques qui peut durcir aux uv et disque optique
JP4748377B2 (ja) * 2009-10-29 2011-08-17 Ｄｉｃ株式会社 光ディスク用紫外線硬化型組成物および光ディスク
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JP2011159824A (ja) * 2010-02-01 2011-08-18 Sumitomo Electric Ind Ltd ナノインプリント法による樹脂パターン形成方法及び回折格子の形成方法
JP2013219230A (ja) * 2012-04-10 2013-10-24 Dainippon Printing Co Ltd ナノインプリント方法及びナノインプリント装置
JP5794387B2 (ja) * 2012-04-10 2015-10-14 ダイキン工業株式会社 インプリント用樹脂モールド材料組成物
WO2021033538A1 (fr) * 2019-08-21 2021-02-25 Ａｇｃ株式会社 Substrat électronique, procédé de fabrication de substrat électronique et instrument électronique
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JP7515240B2 (ja) 2019-08-21 2024-07-12 Ａｇｃセイミケミカル株式会社 電子基板、電子基板の製造方法及び電子機器

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