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WO2006030625A1 - Composition vulcanisable, procédé de fabrication d’une fine structure et procédé de formation de motif - Google Patents

Composition vulcanisable, procédé de fabrication d’une fine structure et procédé de formation de motif Download PDF

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Publication number
WO2006030625A1
WO2006030625A1 PCT/JP2005/015666 JP2005015666W WO2006030625A1 WO 2006030625 A1 WO2006030625 A1 WO 2006030625A1 JP 2005015666 W JP2005015666 W JP 2005015666W WO 2006030625 A1 WO2006030625 A1 WO 2006030625A1
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WIPO (PCT)
Prior art keywords
curable composition
monomer
pattern
mold
fluorine
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PCT/JP2005/015666
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English (en)
Japanese (ja)
Inventor
Yasuhide Kawaguchi
Akihiko Asakawa
Kenji Ishizeki
Takeshi Eriguchi
Kimiaki Kashiwagi
Daisuke Shirakawa
Original Assignee
Asahi Glass Company, Limited
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Publication date
Application filed by Asahi Glass Company, Limited filed Critical Asahi Glass Company, Limited
Publication of WO2006030625A1 publication Critical patent/WO2006030625A1/fr

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18Monomers containing fluorine

Definitions

  • the present invention relates to a curable composition, a fine structure manufacturing method, and a pattern forming method.
  • the present invention relates to a curable composition, a method for producing a fine structure, and a method for forming a pattern.
  • a step of sandwiching and pressing a photocurable composition between the reverse pattern surface of a mold having a reverse pattern of a fine pattern on the surface and a substrate surface, and a photocurable composition by light irradiation Attention is focused on a method for producing a fine structure having a substrate strength in which a fine pattern of the cured product is formed on the surface, in which a step of curing the material to form a cured product and a step of peeling the mold from the cured product are sequentially performed.
  • Patent Document 5 describes a photocurable composition containing a photopolymerization initiator having no fluorine atom and a specific monomer having a fluorine atom.
  • Patent Document 6 describes a photocurable composition containing a photopolymerization initiator having no fluorine atom, and a monomer having a perfluoropolyether structure and a methacryloyl group.
  • Patent Document 1 US Patent No. 5772905
  • Patent Document 2 US Pat. No. 6,482,742
  • Patent Document 3 U.S. Patent No. 6719915
  • Patent Document 4 U.S. Patent No. 6696220
  • Patent Document 5 International Publication No. 04Z104059 Pamphlet
  • Patent Document 6 International Publication No. 05Z030822 Pamphlet
  • the total amount of monomers The actual content of the photopolymerization initiator relative to is 1 to 2% by mass.
  • the content of the photopolymerization initiator is more than 2% by mass, the photocurable composition tends to be non-uniform and the physical properties of the cured product are lowered.
  • An object of the present invention is to provide a curable composition for forming a microstructure and a method for producing the microstructure using the curable composition.
  • the present invention provides the following inventions.
  • a mold having a reverse pattern of a fine pattern is sandwiched between the reverse pattern surface of the mold and the substrate surface, pressed and then cured to form a fine pattern of the cured product on the substrate surface.
  • a curable composition comprising a monomer (A) having a fluorine atom and a polymerization initiator (B) having a fluorine atom.
  • ⁇ 4> The curable composition according to any one of ⁇ 1> to ⁇ 3>, wherein the polymerization initiator (B) is a photopolymerization initiator having a fluorine atom.
  • the curable composition does not have a monomer (A) and a fluorine atom! /, And includes a monomer (C), and the monomer (A) has a total amount of the monomer (A) and monomer (C) content is 50 mass 0/0 or ⁇ 1> of ⁇ rather 4> the curable composition according to any misalignment.
  • the curable composition does not have a monomer (A) and a fluorine atom! /, Includes a monomer (C), and the total amount of fluorine atoms contained in the monomer (A) is the monomer (A).
  • Curable composition strength Including any fluorine-containing surfactant ⁇ 1> to ⁇ 7> The curable composition as described.
  • Curable composition strength The curable composition according to any one of ⁇ 1> to ⁇ 8>, which is substantially free of a solvent.
  • the curable composition is cured by sequentially performing a step of sandwiching and pressing between the substrate and the substrate surface, a step of curing the curable composition to form a cured product, and a step of peeling the mold from the cured product.
  • a method for producing a fine structure characterized in that a fine structure comprising a substrate on which a fine pattern of an object is formed is obtained.
  • the curable composition is formed by sequentially performing a step of sandwiching and pressing between the substrate and the substrate surface, a step of peeling the mold from the curable composition sheet, and a step of curing the curable composition to form a cured product.
  • a method for producing a fine structure comprising obtaining a fine structure comprising a substrate having a fine pattern of a cured product formed on the surface thereof.
  • a pattern forming method comprising: a step of curing; and a step of separating a mold from a cured product of the curable composition.
  • a method of forming a pattern comprising:
  • the curable composition of the present invention contains a monomer having a fluorine atom and a polymerization initiator having a fluorine atom having a high compatibility with the monomer, and thus becomes a uniform composition and phase separation. There is no problem. Therefore, a cured product having excellent physical properties such as hardness can be easily formed from the curable composition of the present invention. Further, since the photocurable composition of the present invention and the cured product thereof are excellent in releasability, they can be easily peeled off from the mold and can form a fine pattern with high accuracy. Therefore, it is possible to easily and highly accurately produce a fine structure having a substrate strength on which a fine pattern of a cured product of the curable composition is formed on the surface.
  • acrylic acid and methacrylic acid are collectively referred to as (meth) acrylic acid; (Meth) ataryloyl group.
  • the monomer means a monomer having a polymerizable unsaturated bond-containing group (hereinafter also simply referred to as a polymerizable unsaturated group) or a polymerizable group such as an epoxy group.
  • the monomer is preferably a monomer having a polymerizable unsaturated group.
  • the polymerizable unsaturated group is a vinyl group, a trifluorovinyl group, a allyl group or a (meth) acryloyl group. The group is particularly preferred.
  • the fluorine content of the monomer (A) in the present invention particularly preferably from 40 to 70 weight 0/0, and even preferable instrument 45-65 mass 0/0.
  • the fluorine content is the ratio of the mass of fluorine atoms to the total mass of all atoms constituting the monomer (A).
  • the fluorine content of the monomer (A) is 40% by mass or more, the release property of the cured product is particularly excellent. Further, when the fluorine content of the monomer (A) is 70% by mass or less, the compatibility with the polymerization initiator (B) is further improved, and the curable composition can be easily adjusted uniformly.
  • Monomer (A ) Can use one monomer (A) or two or more monomers (A).
  • Monomer (A) is the following monomer al (where, n is an integer of 1 to 4, X is a hydrogen atom, fluorine atom, a methyl group or a triflate Ruo Russia methyl, R F is 1 carbon atoms 30 represents an n-valent fluorine-containing organic group.) Or the following monomer a2 (where Q represents a divalent organic group having 1 to 10 carbon atoms in which the main chain is composed of 1 to 3 carbon atoms) .).
  • N in the monomer al is preferably 1 or 2.
  • X is preferably a hydrogen atom or a methyl group.
  • the number of carbon atoms in R F is particularly preferably 4-24.
  • R F is a monovalent fluorine-containing organic group.
  • the monovalent fluorine-containing organic group is a group represented by the formula — (CH 2)
  • R F1 which is preferably a polyfluoroalkyl group in which an etheric oxygen atom may be inserted between carbon atoms.
  • Fl is an integer of 1 to 3
  • R F1 is a carbon atom having 4 to 16 carbon atoms, and a polyfluoroalkyl group in which an etheric oxygen atom may be inserted between carbon atoms is particularly preferred.
  • R F is a divalent fluorine-containing organic group.
  • the divalent fluorine-containing organic group is represented by the formula — (CH 2 ) R F2 (CH 2 ) —, which is preferably a polyfluoroalkylene group in which an etheric oxygen atom may be inserted between carbon atoms.
  • f2 and f3 are each an integer of 1 to 3
  • R F2 is a polyfluoroalkylene group in which an etheric oxygen atom may be inserted between a carbon atom and a carbon atom having 4 to 16 carbon atoms.
  • Q in the monomer a2 is a group in which a group force including methylene, dimethylene and trimethylene forces is selected, and a hydrogen atom in the main chain is a fluorine atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, carbon 1 to 6 hydroxyalkyl groups, carbon atoms 1 to 6 carbon atoms with an etheric oxygen atom inserted between carbon atoms, and 1 to 6 carbon atoms with an etheric oxygen atom inserted between carbon atoms 1
  • a hydroxyalkyl group of ⁇ 6 is a group substituted with a selected group, and a group in which one or more hydrogen atoms forming a carbon-hydrogen bond in the group is substituted with a fluorine atom is preferred.
  • monomer al examples include the following compounds.
  • CH 2 C (CH 3 ) COOCH 2 CF (CF 3 ) 0 (CF 2 CF (CF 3 ) 0) 2 (CF 2 ) 3 F
  • CF 2 CFCH (CH 2 C (CF 3 ) 2 OH) CH 2 CH ⁇ CH 2
  • the curable composition of the present invention adjusts the physical properties (hardness, refractive index, transparency, heat resistance, etc.) of the cured product. From this viewpoint, the monomer (C) having no fluorine atom may be contained.
  • Examples of the monomer (C) include the following compounds.
  • Olefin norbornene, norbornagen, butadiene and the like.
  • Vinylenoetenore cyclohexenoremethinorevininoreatenore, isobutinorevininoreethenore, cyclohexenolevinoreethenore, ethinolevinoreethenore, glycidinorevininoreether, 4-hydroxybutyl vinyl ether, etc.
  • (Meth) acrylic acid and its derivatives (Meth) acrylic acid, funochetyl (meth) atari Rate, benzyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, allyl (meth) acrylate, 1, 3 butane diol di (meth) acrylate 1, 4 Butanediol di (meth) acrylate, 1, 6 hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Oxa (meth) acrylate, ethoxy ethyl (meth) acrylate, methoxy ethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydro
  • Styrene and its derivatives styrene, tert-butoxystyrene, 2-methoxy-4-bi-phenol, tert-butyl-4-butylphenol carbonate, and the like.
  • the content of the monomer (A) with respect to the total amount of the monomer (A) and the monomer (C) is preferably 50% by mass or more. Particularly preferred is 75% by mass or more.
  • the total amount of fluorine atoms contained in the monomer (A) is 30% by mass or more based on the total amount of the monomer (A) and the monomer (C). It is particularly preferable that it is 45% by mass or more.
  • the total amount of the fluorine atoms is preferably 60% by mass or less.
  • Total amount of monomer (A) and monomer (C) in the curable composition of the present invention (when the curable composition of the present invention does not contain monomer (C), the total amount of monomer (A)). ) Is preferably 50% by mass or more, particularly preferably 75% by mass or more.
  • the polymerization initiator (B) in the present invention is preferably a photopolymerization initiator having a fluorine atom or a thermal polymerization initiator having a fluorine atom.
  • the photopolymerization initiator is a fluorine-containing compound that causes a radical reaction or an ionic reaction by light.
  • the photopolymerization initiator is preferably a fluorine-containing organic compound. Since the curing is easy and a fine pattern of the mold can be formed with high accuracy, the curable composition of the present invention polymerizes the monomer (A) by light irradiation. It is preferable to form a cured product.
  • the polymerization initiator (B) is particularly preferably a photopolymerization initiator having a fluorine atom.
  • the fluorine content in the photopolymerization initiator having a fluorine atom is preferably 10 to 70% by mass, particularly preferably 20 to 60% by mass.
  • Examples of the photopolymerization initiator having a fluorine atom include an organic peroxide having a fluorine atom and an acetophone-based compound having a fluorine atom.
  • organic peroxide having a fluorine atom examples include perfluoro (t-butylperoxide) and perfluorobenzoylperoxide.
  • acetophenone-based compound examples include compounds represented by the following formula (pi).
  • A represents a group represented by the formula — C (Z 2 ) (Z 3 ) — or a carbo group.
  • ZZ 2 and Z 3 are each independently an alkyl group having 1 to 20 carbon atoms, a carbon atom, or an ether between carbon atoms.
  • Z 1 represents a C 2-20 polyfluoroalkyl group which may have an etheric oxygen atom between carbon atoms.
  • Examples of the compound represented by the formula (pi) include the following compounds.
  • thermal polymerization initiator (B2) examples include fluorine-containing diacyl peroxide, fluorine-containing peroxydicarbonate, fluorine-containing peroxyester, and fluorine-containing dialkyl peroxide, which are preferably organic peroxides having fluorine atoms. Oxide or fluorine-containing dialle peroxide Is particularly preferred.
  • Fluorine-containing diacyl peroxide includes [C F C (0) 0], [C F C (CH) C (O)
  • C F represents a perfluorophenol group
  • Fluorine-containing peroxyesters include CF CF CH OOC (0) C (CF), (CF)
  • Fluorine-containing dialkyl peroxides include [CF C F C (CF) O] and [(CF) CO].
  • C F represents a perfluoro (1,4-phenylene) group.
  • Examples of the fluorine-containing diaryl peroxide include [CFO] and the like.
  • the curable composition of the present invention comprises a total amount of the monomer (A) and the monomer (C) (if the curable composition of the present invention does not contain the monomer (C), the total amount of the monomer (A).
  • the polymerization initiator (B) is preferably contained in an amount of 0.1 to 16% by mass, more preferably 2 to 14% by mass, and more preferably 3 to 12% by mass. In this case, the polymerization of the monomer (A) proceeds in a high density and in a short time, and a cured product having sufficient physical properties can be easily formed.
  • the curable composition of the present invention preferably contains a fluorine-containing surfactant.
  • the curable composition of the present invention contains a fluorine-containing surfactant
  • the curable composition and the cured product of the curable composition are further improved in releasability and can be smoothly peeled off from the mold.
  • the fluorine-containing surfactant is highly compatible with the monomer (A) and the monomer (C) and further improves the stability of the curable composition.
  • the fluorine content of the fluorine-containing surfactant is preferably 10 to 70% by mass, particularly preferably 20 to 40% by mass.
  • the fluorine-containing surfactant may be water-soluble or fat-soluble.
  • the fluorine-containing surfactant is preferably an ionic fluorine-containing surfactant, a cationic fluorine-containing surfactant, an amphoteric fluorine-containing surfactant, or a non-one fluorine-containing surfactant. . Since the compatibility with the monomer (A) and the monomer (C) is particularly excellent, a nonionic fluorine-containing surfactant is particularly preferable.
  • fluorinated surfactant containing fluorine examples include polyfluoroalkyl carboxylates, polyfluoroalkyl phosphates, polyfluoroalkyl sulfonates, and the like.
  • surfactants include Surflon S-111 (trade name, manufactured by Seimi Chemical Co., Ltd.), Florad FC-143 (trade name, manufactured by 3EM), Megafark F-120 (trade name, Dainippon Ink Industries, Ltd.) Etc.).
  • Cationic fluorine-containing surfactants include aliphatic primary amino acids having a polyfluoroalkyl group, aliphatic secondary amino acids having a polyfluoroalkyl group, and polyfluoroalkylsulfonamidopropyltrimethylammo. -Um salt etc.
  • Specific examples of these surfactants include Surflon S-121 (trade name, manufactured by Seimi Chemical Co., Ltd.), Florad FC-134 (trade name, manufactured by 3EM), Megafark F-150 (trade name, Dainippon) Ink Industries Co., Ltd.).
  • amphoteric fluorine-containing surfactant examples include polyfluoroalkylbetaines.
  • surfactants include Surflon S-132 (trade name, manufactured by Seimi Chemical Co., Ltd.), Florado FX-172 (trade name, manufactured by 3EM), Megafark F-120 (trade name, Dainippon Ink Industries, Ltd.) Etc.).
  • Examples thereof include polymers.
  • Bruno - one fluorine-containing surface active agent is an oligomer comprising a monomer unit based on a monomer having a R F group (mass-average Koryou is 1000 to 8000) is preferred.
  • Monomers having an R F group is particularly preferably a preferable tool Furuoroarukiru (meth) Atari rate that is Furuoro (meth) Atarire over preparative
  • non-ionic fluorine-containing surfactant examples include Surflon S-145 (trade name, manufactured by Seimi Chemical Co., Ltd.), Surflon S-393 (trade name, manufactured by Seimi Chemical Co., Ltd.), Surflon K H-20 (trade name, manufactured by Seimi Chemical Co., Ltd.), Surflon KH-40 (trade name, manufactured by Seimi Chemical Co., Ltd.), Florad FC-170 (trade name, manufactured by 3EM), Florad FC-430 (trade name, 3EM) ), MegaFark F-141 (trade name, manufactured by Dainippon Ink Industries, Ltd.) and the like.
  • the curable composition of the present invention comprises a total amount of the monomer (A) and the monomer (C) (if the curable composition of the present invention does not contain the monomer (C)! It is preferable to contain more than 0.1 to 5% by mass of the fluorine-containing surfactant with respect to the total amount).
  • the curable composition of the present invention may contain a solvent or may contain substantially no solvent. Since the operation of removing the solvent is unnecessary when sandwiched and pressed between the reverse pattern surface of the mold and the substrate surface, the curable composition of the present invention does not substantially contain a solvent. U prefer. Since the curable composition of the present invention has high compatibility between the monomer (A) and the polymerization initiator (B), a uniform composition can be formed without containing a solvent. However, the solvent used in the preparation of the curable composition may be included as a residual solvent. In this case as well, it is preferable that the solvent is distilled off as much as possible. When the curable composition does not substantially contain a solvent, there is also an effect that the volume shrinkage of the curable composition upon curing is small.
  • the curable composition of the present invention is cured after being sandwiched and pressed between the reverse pattern surface of a mold having a reverse pattern of a fine pattern (hereinafter also simply referred to as a mold) and the substrate surface. This is used to form a fine pattern of the cured product on the substrate surface.
  • the curable composition of the present invention may be sandwiched between the reversal pattern surface of the mold and the substrate surface and cured while being pressed, or may be sandwiched between the reversal pattern surface of the mold and the substrate surface. After pressing, the mold may be peeled off to cure the force.
  • the fine pattern formed on the surface of the substrate is formed by an uneven structure made of a cured product of the curable composition.
  • the structure having the uneven structure is referred to as an uneven structure.
  • the concavo-convex structure is made of a cured product of the curable composition, and is disposed on the surface of the base material to form a fine pattern.
  • 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 that is a collective force of independent protrusions.
  • the former is a base material A structure consisting of a cured product layer covering the surface, where the surface of the cured product layer is uneven.
  • the latter refers to a structure in which a large number of protrusions having a cured product force exist independently on the surface of the base material, and an uneven shape is formed together with a concave portion having a base material surface force.
  • the portion (projection) forming the convex structure is made of a cured product of the curable composition.
  • the uneven structure is those
  • It has a structure that has two structures at different positions on the substrate surface.
  • the fine pattern is formed by this uneven structure.
  • the portion of the concavo-convex structure or the protrusion (hereinafter, both are referred to as the convex structure) exists in the form of lines or dots on the surface of the cured product layer or the substrate, and the shape of the lines or points is not particularly limited. .
  • the linear convex structure is not limited to a straight line, and may be a curved line or a bent shape. Also, many of the lines exist in parallel and form stripes!
  • the cross-sectional shape of the linear convex structure (the cross-sectional shape perpendicular to the direction in which the line extends) is not particularly limited, and examples thereof include a rectangle, a trapezoid, a triangle, and a semicircle.
  • the shape of the dotted convex structure is not particularly limited.
  • columnar or pyramidal shapes, hemispherical shapes, polyhedral shapes, etc. whose bottom surface shape is rectangular, square, rhombus, hexagon, triangle, circle or the like.
  • the average of the width of the linear convex structure portion (referring to the width of the bottom portion) is preferably from lnm to 100 m, particularly preferably from 10 ⁇ m to 10m.
  • the average length of the bottom surface of the point-like convex structure is preferably 1 ⁇ to 100 / ⁇ m, particularly preferably 1011111 to 10111.
  • the length of the bottom surface of this point-shaped convex structure means the length in the direction perpendicular to the extending direction when the point extends in a shape close to a line, and otherwise the length of the bottom surface shape.
  • the average height of the linear and dotted convex structures is preferably from 1 nm to 100 ⁇ m, particularly preferably from 10 nm to 10 ⁇ m.
  • the average distance between adjacent convex structures is preferably from lnm to 500 m, particularly preferably from 10 nm to 50 m.
  • these minimum dimensions in the convex structure are preferably 500 m or less, particularly preferably 50 m or less.
  • the lower limit is preferably lnm. This minimum dimension means the minimum of the width, length and height of the convex structure.
  • the substrate may be a planar substrate or a curved substrate.
  • the substrate include substrates made of inorganic materials such as silicon wafer, glass, quartz glass, and metals; substrates made of organic materials such as fluorine resin, silicone resin, acrylic resin, and polycarbonate resin.
  • surface You may use the base material which improved the adhesiveness with a curable composition by process (A silane coupling process, a silazane process, etc.).
  • the mold has a reverse pattern of the fine pattern.
  • An inverted pattern is a pattern in which the concavo-convex structure in the fine pattern is reversed (that is, the concave is convex and the convex is concave).
  • the shape of the reverse pattern in the mold has a concavo-convex structure corresponding to the fine pattern. That is, the shape of the convex structure portion of the fine pattern is the shape of the concave structure portion in the reverse pattern.
  • the shape and dimensions of the concave structure of the reverse pattern correspond to the shape and dimensions of the fine pattern.
  • the depth of the concave structure portion of the reverse pattern (corresponding to the height of the convex structure portion of the fine pattern) may be different from the height of the convex structure portion of the fine pattern.
  • the minimum dimension in the concave structure of the inverted pattern is preferably 500 / zm or less, particularly preferably 50 / zm or less.
  • the lower limit is lnm, U.
  • Examples of the mold include a mold made of a non-translucent material such as a silicon wafer, SiC, My strength, and the like; a mold made of a translucent material such as glass, polydimethylsiloxane, and transparent fluorine resin.
  • a base material made of a light-transmitting material or a mold made of a light-transmitting material.
  • the present invention provides a curable composition containing a monomer (A) and a polymerization initiator (B) between a reverse pattern surface of a mold having a reverse pattern of a fine pattern and a substrate surface.
  • Step of sandwiching and pressing hereinafter referred to as step 1), step of forming a cured product by curing the curable composition (hereinafter referred to as step 2), step of peeling the mold from the cured product (hereinafter referred to as step) 3) is sequentially performed, and a method for producing a fine structure (hereinafter also simply referred to as a fine structure) comprising a base material on which a fine pattern of a cured product of the curable composition is formed on the surface is provided.
  • the curable composition is preferably the curable composition of the present invention.
  • step 1 includes the following step 11, the following step 12, and the following step 13.
  • Step 11 A step of placing the curable composition on the surface of the substrate and then pressing the substrate and the mold so that the curable composition is in contact with the pattern surface of the mold.
  • Step 12 A step of placing the curable composition on the pattern surface of the mold and then pressing the substrate and the mold so that the surface of the substrate is in contact with the curable composition.
  • Step 13 Combining the base material and the mold to form a gap between the surface of the base material and the pattern surface of the mold, and then filling the void with a curable composition, A step of sandwiching and pressing the curable composition between the materials.
  • the arrangement of the curable composition in step 11 and step 12 is potting method, spin coating method, roll coating method, casting method, dip coating method, die coating method, Langmuir jet method, vacuum deposition method, etc. It is preferable to coat the substrate surface with the curable composition using the above method.
  • the curable composition may be coated on the entire surface of the substrate or only on a part of the substrate.
  • the pressing pressure (gauge pressure) when pressing the base material and the mold is more than 0 to 10MPa force girls, 0.1 to 5MPa force girls! / ⁇ .
  • step 13 as a method of filling the void with the curable yarn and the composition, a method of sucking the curable composition into the void by capillarity can be mentioned.
  • Curing of the curable composition in step 2 is preferably performed by light irradiation when the curable composition is photocurable, and by heating when the curable composition is thermosetting. That's right. Curing of the curable composition by light irradiation is performed by light irradiation from the mold side when using a translucent material mold, and light from the base material side when using a light transmitting material base material. It is preferable to do it according to the irradiation method. It is preferable that the light has a wavelength of 200 to 400 nm! In this case, the temperature of the system is preferably 0-60 ° C! /.
  • the curable composition containing the monomer (A) and the polymerization initiator (B) is sandwiched between the substrate surface and the reverse pattern surface of the mold having the reverse pattern of the fine pattern.
  • Step 4 a step of peeling the mold from the curable composition (hereinafter referred to as step 5), and a step of curing the curable composition to form a cured product (hereinafter referred to as step 5).
  • step 6 a step of curing the curable composition to form a cured product.
  • the curable composition is preferably the curable composition of the present invention.
  • Step 4 include the same embodiments as the specific embodiments of Step 1 (Step 11, Step 12, Step 13, and the like below).
  • Curing of the curable composition in step 6 is performed when the curable composition is photocurable. Is preferably carried out by irradiation with light and when the curable composition is thermosetting. Curing of the curable composition by light irradiation is performed by light irradiation from the mold side when using a translucent material mold, and light from the base material side when using a light transmitting material base material. It is preferable to do it according to the irradiation method. It is preferable that the light has a wavelength of 200 to 400 nm! In this case, the temperature of the system is preferably 0-60 ° C! /.
  • the fine structure obtained by the production method of the present invention has a fine structure in which fine protrusions made of a cured product of the curable composition of the present invention form a fine pattern and are arranged on the substrate surface. It is.
  • the microstructure is excellent in physical properties such as heat resistance, chemical resistance, releasability, and optical properties (transparency and low refractive index).
  • the microstructure obtained by the manufacturing method of the present invention includes an optical element such as a microlens array, an optical waveguide, optical switching, a Fresnel zone plate, a binary element, a blaze element, and a photo-tus crystal; AR (Anti Reflection It is useful as a coating member, biochip, TAS (Micro-Total Analysis Systems) chip, microreactor chip, recording medium, display material, catalyst carrier, filter, sensor member, and the like.
  • an optical element such as a microlens array, an optical waveguide, optical switching, a Fresnel zone plate, a binary element, a blaze element, and a photo-tus crystal
  • AR Anti Reflection It is useful as a coating member, biochip, TAS (Micro-Total Analysis Systems) chip, microreactor chip, recording medium, display material, catalyst carrier, filter, sensor member, and the like.
  • Preferred embodiments of the present invention include the following pattern forming method 1 and the following pattern forming method 2.
  • a step in which a substrate and a mold having a pattern formed on the surface are brought close to or in contact with each other so that the pattern is on the substrate side, a polymerizable compound having a fluorine content of 40 to 70% by mass, and light having fluorine atoms A curable composition containing a polymerization initiator, a substrate and a mold And a step of curing the curable composition by light irradiation in a state where the substrate and the mold are close to or in contact with each other, and a step of separating the mold from the cured product of the curable composition. Pattern formation method.
  • the minimum dimension of the pattern in the pattern forming method 1 and the pattern forming method 2 is preferably 50 m or less.
  • Fluorine content force 0-70 wt% of the polymerizable I ⁇ comprises, is preferably the full Tsu-containing amount is 40 to 70 mass 0/0 of the monomer (A)! /,.
  • Monomer A 3 can also be a mixture force of different compounds of number m.) (Fluorine content about 54.2%) and Z or Monomer A 4 below (Fluorine content about 38.2%) It was.
  • CH 2 C (CH 3 ) COOCH 2 CH 2 (CF2) 6 F (A 1 )
  • initiator B 1 perfluorobenzoyl peroxide (hereinafter referred to as initiator B 1 intends Toi.) was used.
  • initiator D 1 photopolymerization initiator having no fluorine atom
  • initiator D 1 photopolymerization initiator having no fluorine atom
  • fluorine-containing surfactant a non-one fluorine-containing surfactant (trade name: Surflon S-39 3 manufactured by Seimi Chemical Co., Ltd.), which is an oligomer of polyfluoroalkyl (meth) acrylate, was used. .
  • the main wavelength light at 1.5 kHz to 2. OkHz is 255 nm, 315 nm and 36
  • a 5 nm high-pressure mercury lamp (irradiation intensity: 63 mjZcm 2 ) was used.
  • the ratio of the photopolymerization initiator to the total amount of monomers in each photocurable composition Total is expressed in% as the initiator content.
  • Photocurable composition 1 (0.8 L) was dropped onto the silicon wafer to form a layer made of photocurable composition 1 on the silicon wafer.
  • a quartz mold having a concave structure with a width of 1 ⁇ m, a depth of 260 nm, and a length of 10 m is sandwiched between the layer of the silicon wafer and a pressure of 0.5 MPa at 25 ° C (gauge Pressure).
  • the photocurable composition 1 was cured by irradiating a light source from the mold side for 30 seconds.
  • the mold is peeled off from the silicon wafer, and the cured product of the photocurable composition 1 is a fine structure having a convex structure (a convex structure having a width of 0.99 m and a height of 258 nm) in which the concave structure of the mold is inverted.
  • a microstructure comprising a silicon wafer with a pattern formed on the surface was obtained.
  • a photocurable composition 2 (initiator content: 4.2%) was obtained by filtration using a filter. Except for using photocurable composition 2 in place of photocurable composition 1, in the same manner as in Example 1, the cured structure of photocurable composition 2 has a convex structure (width 0 A convex structure with a height of 99 ⁇ m and a height of 259 nm was obtained.
  • Photocurable composition and production example of microstructure (Part 4) 0.90 g of monomer A 2 and 0.10 g of initiator B 1 were mixed and dissolved, and then filtered through a filter with a pore size of 0.45 m to obtain a photocurable composition 4 (initiator content 11 1%). Except for using photocurable composition 4 instead of photocurable composition 1, in the same manner as in Example 1, the cured product of photocurable composition 4 has a fine structure having a convex structure in which the concave structure of the mold is inverted. A fine structure comprising silicon wells having a turn formed on the surface was obtained.
  • the pore size is 0.45 m. Filtration through a filter gave a photocurable composition (initiator content: 0.5%).
  • the photocurable composition was cured in the same manner as in Example 1 except that the photocurable composition was used instead of the photocurable composition 1. In order to sufficiently cure the photocurable composition, a light source was used. 300 seconds of irradiation needed
  • the manufacturing method of the present invention includes an optical element (microlens array, optical waveguide, optical switching, Fresnel zone plate, binary optical element, blaze optical element, photo-tus crystal, etc.), AR coat member, biochip, ⁇ S. It can be used for manufacturing methods for chips, microreactor chips, recording media, display materials, catalyst carriers, filters, sensor members, etc., and fine processing methods in semiconductor device manufacturing processes. It should be noted that the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2004-269803, filed on September 16, 2004, are hereby incorporated herein by reference. As it is incorporated.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L’invention porte sur une composition vulcanisable ; un procédé de fabrication d’une fine structure ; et un procédé de formation de motif. La composition vulcanisable est une composition devant s’utiliser avec un moule dont le motif est l’inverse d’un fin motif. La composition est prise en sandwich entre le côté de motif inversé du moule et une surface de substrat, comprimée, et ensuite vulcanisée pour constituer un fin motif d’un objet vulcanisé à la surface du substrat. La composition comprend comme ingrédients essentiels un monomère fluoré (A) et un initiateur de polymérisation fluoré (B). Le procédé de fabrication de fine structure et le procédé de formation de motif comprennent, dans l’ordre suivant, une phase dans laquelle la composition vulcanisable est prise en sandwich entre ce côté de moule dont le motif est l’inverse d’un fin motif et une surface de substrat, avant compression, une phase dans laquelle la composition vulcanisable est cuite pour constituer un objet vulcanisé, et une phase dans laquelle l’objet vulcanisé est libéré du moule.
PCT/JP2005/015666 2004-09-16 2005-08-29 Composition vulcanisable, procédé de fabrication d’une fine structure et procédé de formation de motif WO2006030625A1 (fr)

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JP2004-269803 2004-09-16

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JP2006310566A (ja) * 2005-04-28 2006-11-09 Asahi Glass Co Ltd 加工基板の製造方法
JP2006310565A (ja) * 2005-04-28 2006-11-09 Asahi Glass Co Ltd 加工基板の製造方法
WO2007116972A1 (fr) * 2006-04-07 2007-10-18 Asahi Glass Company, Limited Polariseur a grille de fil et son procede de production
JP2008105414A (ja) * 2006-09-27 2008-05-08 Fujifilm Corp 光ナノインプリントリソグラフィ用硬化性組成物およびそれを用いたパターン形成方法
WO2008155928A1 (fr) * 2007-06-20 2008-12-24 Asahi Glass Company, Limited Composition photodurcissable et procédé de production d'un objet moulé présentant un motif fin en surface
WO2010064609A1 (fr) * 2008-12-05 2010-06-10 旭硝子株式会社 Composition pouvant durcir à la lumière et procédé de fabrication d'un corps moulé ayant un fin motif de surface
JP2010157613A (ja) * 2008-12-26 2010-07-15 Toyo Gosei Kogyo Kk パターン形成用光硬化性組成物及びパターン形成方法
US9040090B2 (en) 2003-12-19 2015-05-26 The University Of North Carolina At Chapel Hill Isolated and fixed micro and nano structures and methods thereof
JP2020030313A (ja) * 2018-08-22 2020-02-27 シャープ株式会社 防汚性フィルムの製造方法

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JP2004123831A (ja) * 2002-09-30 2004-04-22 Dainippon Printing Co Ltd 光硬化性樹脂組成物、微細凹凸パターン転写箔、光学物品、スタンパー及び微細凹凸パターンの形成方法
JP2004163490A (ja) * 2002-11-11 2004-06-10 Nippon Sheet Glass Co Ltd 光学素子及びその製造方法
JP2004191919A (ja) * 2002-07-12 2004-07-08 Dainippon Printing Co Ltd 体積型ホログラム記録用感光性組成物、体積型ホログラム記録用感光性媒体、及び体積型ホログラム
JP2004250627A (ja) * 2003-02-21 2004-09-09 Asahi Glass Co Ltd フルオロポリマーの製造方法

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JP2002332275A (ja) * 2001-03-08 2002-11-22 Ausimont Spa 重合開始剤としてのペルフルオロジアシルペルオキシド
JP2004191919A (ja) * 2002-07-12 2004-07-08 Dainippon Printing Co Ltd 体積型ホログラム記録用感光性組成物、体積型ホログラム記録用感光性媒体、及び体積型ホログラム
JP2004123831A (ja) * 2002-09-30 2004-04-22 Dainippon Printing Co Ltd 光硬化性樹脂組成物、微細凹凸パターン転写箔、光学物品、スタンパー及び微細凹凸パターンの形成方法
JP2004163490A (ja) * 2002-11-11 2004-06-10 Nippon Sheet Glass Co Ltd 光学素子及びその製造方法
JP2004250627A (ja) * 2003-02-21 2004-09-09 Asahi Glass Co Ltd フルオロポリマーの製造方法

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9902818B2 (en) 2003-12-19 2018-02-27 The University Of North Carolina At Chapel Hill Isolated and fixed micro and nano structures and methods thereof
US9040090B2 (en) 2003-12-19 2015-05-26 The University Of North Carolina At Chapel Hill Isolated and fixed micro and nano structures and methods thereof
JP2006310565A (ja) * 2005-04-28 2006-11-09 Asahi Glass Co Ltd 加工基板の製造方法
JP2006310566A (ja) * 2005-04-28 2006-11-09 Asahi Glass Co Ltd 加工基板の製造方法
JP5182644B2 (ja) * 2006-04-07 2013-04-17 旭硝子株式会社 ワイヤグリッド型偏光子およびその製造方法
WO2007116972A1 (fr) * 2006-04-07 2007-10-18 Asahi Glass Company, Limited Polariseur a grille de fil et son procede de production
US20090052030A1 (en) * 2006-04-07 2009-02-26 Asahi Glass Company, Limited Wire-grid polarizer and process for producing the same
EP2023169A4 (fr) * 2006-04-07 2011-03-16 Asahi Glass Co Ltd Polariseur a grille de fil et son procede de production
JP2008105414A (ja) * 2006-09-27 2008-05-08 Fujifilm Corp 光ナノインプリントリソグラフィ用硬化性組成物およびそれを用いたパターン形成方法
WO2008155928A1 (fr) * 2007-06-20 2008-12-24 Asahi Glass Company, Limited Composition photodurcissable et procédé de production d'un objet moulé présentant un motif fin en surface
US8163813B2 (en) 2007-06-20 2012-04-24 Asahi Glass Company, Limited Photocurable composition and method for producing molded product with fine pattern
US8703837B2 (en) 2008-12-05 2014-04-22 Asahi Glass Company, Limited Photocurable composition and process for producing molded product having fine pattern on its surface
JP5594147B2 (ja) * 2008-12-05 2014-09-24 旭硝子株式会社 光硬化性組成物および表面に微細パターンを有する成形体の製造方法
WO2010064609A1 (fr) * 2008-12-05 2010-06-10 旭硝子株式会社 Composition pouvant durcir à la lumière et procédé de fabrication d'un corps moulé ayant un fin motif de surface
JP2010157613A (ja) * 2008-12-26 2010-07-15 Toyo Gosei Kogyo Kk パターン形成用光硬化性組成物及びパターン形成方法
JP2020030313A (ja) * 2018-08-22 2020-02-27 シャープ株式会社 防汚性フィルムの製造方法

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