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WO2009093661A1 - Procédé pour former un motif de film métallique - Google Patents

Procédé pour former un motif de film métallique Download PDF

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Publication number
WO2009093661A1
WO2009093661A1 PCT/JP2009/050983 JP2009050983W WO2009093661A1 WO 2009093661 A1 WO2009093661 A1 WO 2009093661A1 JP 2009050983 W JP2009050983 W JP 2009050983W WO 2009093661 A1 WO2009093661 A1 WO 2009093661A1
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WO
WIPO (PCT)
Prior art keywords
mold
metal film
pattern
resin composition
manufactured
Prior art date
Application number
PCT/JP2009/050983
Other languages
English (en)
Japanese (ja)
Inventor
Masatsugu Komai
Iwao Hotta
Satoshi Moriyama
Original Assignee
Kyowa Hakko Chemical 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 Kyowa Hakko Chemical Co., Ltd. filed Critical Kyowa Hakko Chemical Co., Ltd.
Publication of WO2009093661A1 publication Critical patent/WO2009093661A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • 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
    • B29C33/424—Moulding surfaces provided with means for marking or patterning
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • C25D5/022—Electroplating of selected surface areas using masking means

Definitions

  • the present invention relates to a method of forming a metal film pattern for manufacturing a metal processed product, a fine part, and the like.
  • LIGA Lithography Galvanoforming Abforming
  • a resist pattern similar to the desired part is formed in the lithography process, then a metal film pattern (mold) is formed by electroforming, and the metal film pattern is used to make a metal, resin, or ceramic.
  • the LIGA process has a problem in forming a desired thick film resist pattern in the lithography process.
  • the stable operation of X-ray apparatus, productivity, and the complexity of mask production are raised.
  • the present thick film resist has problems in resolution and peelability.
  • the thermal imprint method is a method in which a thermoplastic resin is heated above its glass transition point, a mold on which a fine pattern is formed is pressed onto the thermoplastic resin, and after cooling, the pattern is formed by peeling from the mold. It is.
  • thermoplastic resin it is difficult to remove the remaining film on the bottom of the recess that causes the plating to grow by electroforming, and the resin after electroforming is removed. It is also difficult to obtain a good metal film pattern.
  • a photocurable resin composition is applied to a substrate, a mold on which a fine pattern is formed is pressed on the photocurable resin, and the resin composition is cured by light irradiation. It is a method of forming a cured resin pattern by peeling from (see, for example, Patent Documents 2 and 3).
  • a quartz mold is generally used as a transparent material that transmits ultraviolet rays in the mold of the optical imprint method (see, for example, Patent Documents 4 and 5).
  • a pattern having a large aspect ratio particularly when forming a deep groove, it is difficult to process quartz and the processing cost is high.
  • An object of the present invention is to provide a simple metal film pattern forming method.
  • the present invention relates to the following (1) to (16).
  • a curable resin composition is applied on a substrate on which a seed film is formed, and the predetermined pattern of the mold is transferred to the curable resin composition by relative movement between the substrate and a mold having a predetermined pattern.
  • the curable resin composition is cured in a state where the predetermined pattern of the mold is transferred to the curable resin composition, the mold is removed from the cured resin, and the residual cured resin in the region where the metal film is formed is removed.
  • a method of forming a metal film pattern comprising forming a metal film in the region and removing the cured resin remaining on the substrate.
  • the plastic mold material is at least one of polyimide, polycarbonate, polypropylene, and polydimethylsiloxane.
  • a metal film (mold) pattern and a method for forming the pattern can be easily provided.
  • the method of the present invention in particular, by using a visible light curable resin composition containing a plastic mold and a polymerizable compound having a specific weight average molecular weight or less, the metal film (mold) can be more easily formed.
  • a pattern can be formed.
  • FIG. 1 is an explanatory diagram for explaining an embodiment of a metal film pattern forming method according to the present invention.
  • BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an explanatory diagram illustrating an embodiment of a mold creation process for creating a plastic mold.
  • BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an explanatory view illustrating one embodiment of a plastic mold production process used in a metal film pattern forming method according to the present invention.
  • FIG. 1 is an explanatory view illustrating an embodiment of a metal film pattern forming method according to the present invention.
  • a seed film 2 is formed on the substrate 1.
  • the substrate 1 is a material made of silicon (Si).
  • the seed film 2 is formed by forming a chromium (Cr) film of about 50 nm and then forming a nickel (Ni) film of about 100 nm on the chromium film.
  • Cr chromium
  • Ni nickel
  • the curable resin composition 4 is applied onto the seed film 2 of the substrate 3, and the plastic mold 5 disposed above the substrate 3 is moved downward as viewed in the figure.
  • a predetermined pattern is formed on the plastic mold 5, and in the present embodiment, the pattern includes a convex portion 6 and a concave portion 7 as an example.
  • the plastic mold 5 which moved to the downward direction bites into the curable resin composition 4 as shown in a process (c).
  • the curable resin composition 4 is irradiated with light and cured.
  • step (d) the plastic mold 5 is moved upward and removed from the cured resin 4 '.
  • a pattern opposite to the concavo-convex pattern of the plastic mold 5 is transferred to the cured resin 4 ′. That is, the convex portion 6 of the plastic mold 5 is transferred to the concave portion 8 of the cured resin 4 ′, and the concave portion 7 of the plastic mold 5 is transferred to the convex portion 9 of the cured resin 4 ′.
  • the convex portion 9 transferred to the cured resin 4 ′ is a region where electroforming is not performed (hereinafter, simply referred to as a non-electroforming region), and conversely, the concave portion 8 is a region where electroforming is performed ( Hereinafter, it may be simply referred to as an electroforming region).
  • a residue 4 ′′ of the cured resin 4 ′ is present at the bottom of the recess 8 which is an electroforming region, and the residual cured resin 4 ′′ is removed in the step (e).
  • the residual cured resin 4 ′′ is removed by performing an oxygen (O 2 ) plasma ashing (hereinafter sometimes simply referred to as an ashing process) with an RIE (Reactive Ion Etching) apparatus.
  • O 2 oxygen
  • RIE Reactive Ion Etching
  • step (f) the electroforming region 10 is subjected to an electroforming process to form a metal film 11.
  • the cured resin 4 ' is removed in the step (g).
  • the removal process of the cured resin 4 ′ is performed by a chemical process or an oxygen (O 2 ) plasma ashing process of an RIE apparatus, and a concave portion 12 is formed at the place where the removal process is performed.
  • steps (a) to (g) a formed product in which a metal film pattern is formed on the substrate is completed.
  • the plastic mold is moved downward to bite into the curable resin composition, but the moving direction is not particularly limited, and the substrate is moved upward to turn the curable resin composition into the mold. You may bite in.
  • Examples of the mold having the predetermined pattern described above include a quartz glass mold (quartz mold) and a plastic mold in consideration of optical imprinting. Among these, a plastic mold is particularly preferable.
  • a hard quartz glass surface has to be processed in order to create a pattern, and there is a limit in processing a complicated pattern or a deep groove pattern.
  • the mold can be processed inexpensively and easily, and a pattern with a complicated shape, a deep groove pattern, or a pattern with an extremely narrow pitch can be easily created.
  • FIG. 2 shows an embodiment of a mold making process when a plastic mold is made.
  • the seed film 22 is formed on the upper surface of the substrate 21 to produce the substrate 20 on which the seed film is formed (hereinafter, the substrate 20 on which the seed film is formed is simply referred to as the substrate 20).
  • the seed film 22 is formed by forming a chromium film having a thickness of about 50 nm on the upper surface of the substrate 21 and then forming a nickel film having a thickness of about 100 nm on the chromium film.
  • a resist 23 is arranged on the substrate 20 thus created.
  • a mask 24 is disposed above the resist 23.
  • the mask 24 has a passage portion 25 (for example, a material such as glass) through which light passes and a non-passage portion 26 (for example, a chromium film) through which light does not pass. A formed glass material or the like).
  • a lithography technique when the resist 23 is exposed through the mask 24 by a lithography technique, an exposed resist 23 ′ and an unexposed resist 23 ′′ are formed.
  • a pattern of the unexposed resist 23 ′′ is formed by the concave portion 27 from which the exposed resist 23 ′ is removed and the unexposed resist 23 ′′, as shown in step (c).
  • step (d) When the exposed resist 23 'is completely removed, an electroforming process is performed in step (d).
  • the metal film 28 can be formed in the recess 27 by electroforming.
  • the resist 23 ′′ that is left unexposed is removed.
  • the resist 23 ′′ can be removed by performing a chemical treatment or an RIE treatment (Reactive Ion Etching).
  • RIE treatment Reactive Ion Etching
  • a metal film pattern can be formed on the substrate 20.
  • the resist film thickness and the thickness of the metal film formed by electroforming are adjusted according to the depth of the plastic mold. As the metal material to be electroformed, it is desirable to select a material that can withstand the aspect strength of the pattern and that can realize stress reduction.
  • plastic mold In the present invention, a plastic mold can be preferably used.
  • the material of the plastic mold is not limited as long as the material can hold the pattern.
  • plastic materials include polyethylene, polypropylene, polyvinyl chloride, polymethacrylate, polyamide, polyimide [for example, Upilex S (manufactured by Ube Industries), Aurum film (manufactured by Mitsui Chemicals)], polystyrene, polyfluoride Ethylene, polycarbonate, polyphenylene oxide, polyurethane, polyester [for example, Lumirror (manufactured by Toray Industries, Inc.)], polyethylene terephthalate, polyphenylene isophthalamide, polylactic acid [for example, plamate (manufactured by Dainippon Ink, Inc.), Terramac (unitika )], Polyacrylonitrile, epoxy resin, silicone resin [eg, Sylpot or Sylgard 184 (manufactured by Toray Dow Corning)], polydi
  • plastic materials polypropylene, polymethacrylate, polycarbonate, polyester, polyethylene terephthalate, polystyrene, polyimide, silicon-based resin, and fluorine-based resin are preferable from the viewpoint of peelability from the resin, and more preferably polyimide.
  • polycarbonate, polypropylene and polydimethylsiloxane are preferable from the viewpoint of peelability from the resin, and more preferably polyimide.
  • the mold used in the present invention is preferably colorless and transparent, but may be colored. However, the total light transmittance is preferably at least 10% or more, more preferably 30% or more. Moreover, you may contain fillers, such as UV absorber.
  • the mold is preferably colorless and transparent, but even if it is colored, it can cure the visible light curable resin composition and form a pattern if it transmits at least 10% of visible light.
  • plastic molds for example, in addition to quartz glass, molds of inexpensive glass materials such as soft glass, hard glass, Pyrex (registered trademark) glass, ordinary glass, and frosted glass are also used. A plastic mold is most preferred.
  • the shape of the plastic mold may be any shape as long as pattern formation is possible, and examples thereof include a plate shape, a film shape, an endless belt shape, and a cylindrical shape, preferably An endless belt shape and a cylindrical shape are mentioned.
  • a material obtained by bonding the above plastic material or plastic film with an adhesive or photocuring to give strength may be used as the mold.
  • a plastic plate or a plastic film in which a metal mold is pressed by pressure bonding to form a pattern may be used as a mold as it is.
  • Examples of the method for producing a plastic mold in the present invention include a thermal (nano) imprint method, a hot embossing method, and a direct press method.
  • a method of drawing directly on plastic with an electron beam or ion beam (proton beam, X-ray, etc.), a plastic mold by applying or dripping a curable resin on a metal mold, thermosetting or photocuring A room temperature nanoimprint method using HSQ (hydrogen silsesquioxane polymer), a soft lithography method using PDMS (polydimethylsiloxane), and the like.
  • HSQ hydrogen silsesquioxane polymer
  • PDMS polydimethylsiloxane
  • the thermal (nano) imprint method is preferable. Specifically, it is a method in which an original mold (a material such as metal, silicon, quartz or plastic) is pressed against the surface of a plastic plate or film, and is heated and pressed, and a heating plate under a thermal (nano) imprint apparatus By placing the original mold and the plastic plate or film on the plate and changing the temperature of the upper heating plate and the lower heating plate, a plastic mold having a good shape and good light transmittance can be formed. At that time, the heating temperature of the lower heating plate is preferably set to a temperature of ⁇ 50 ° C.
  • the temperature difference between the upper and lower heating plates is preferably 30 ° C. or higher, and more preferably 50 ° C. or higher.
  • the pressing pressure is preferably 0.2 to 50 MPa, more preferably 1 to 10 MPa.
  • the cooling temperature is preferably cooled to room temperature in two or more stages.
  • FIG. 3 shows an embodiment of a process for producing a plastic mold.
  • a mold material 30 is prepared, and a mold release agent is applied to the mold material 30.
  • the mold 31 is disposed above the mold material 30.
  • the mold 31 can be a mold created according to the embodiment shown in FIG. A convex portion 32 and a concave portion 33 are formed on the mold 31, and a predetermined pattern is formed by these concave and convex portions 32 and 33.
  • the mold 31 is moved downward as seen in the figure, and the convex portions 32 of the mold 31 are digged into the molding material 30 as shown in step (c).
  • the mold 31 is heated in a state where it is bitten into the mold material 30, and the pattern of the mold 31 is transferred to the mold material 30.
  • the mold 31 is removed from the mold 30 to produce a plastic mold 30 ′.
  • the convex portion 32 of the mold 31 is transferred to form a concave portion 34, and further, the concave portion of the mold 31 is transferred to form a convex portion 35.
  • the pattern is uneven.
  • the plastic mold 30 'thus produced can be used in the metal film pattern forming method of the embodiment shown in FIG.
  • the mold is moved downward to bite into the mold material, but the moving direction is not particularly limited, and the mold material is moved upward to bite the mold material into the mold. It may be allowed.
  • the mold (particularly plastic mold) used in the present invention may be coated or vapor-deposited on the release surface with a mold release agent or a release agent in order to improve release properties and release properties.
  • a mold release agent include fluorine-based surface treatment agents [OPTOOL DSX, Durasurf HD-1100, HD-2100 (manufactured by Daikin Industries, Ltd.), NovecEGC-1720 (manufactured by Sumitomo 3M), etc.], gold Mold release agent [barrier serum gamma R (manufactured by Vanatech Co., Ltd.)] and the like.
  • release agent examples include fluorine release agents [Flease (manufactured by Neos Co., Ltd.)], silicone resin, silicone oil, silicone wax, Teflon (registered trademark) dispersant, polyvinyl alcohol, water-soluble emulsion release agent, and the like.
  • fluorine release agents include fluorine release agents [Flease (manufactured by Neos Co., Ltd.)], silicone resin, silicone oil, silicone wax, Teflon (registered trademark) dispersant, polyvinyl alcohol, water-soluble emulsion release agent, and the like.
  • examples include molds.
  • Deposition methods include organic thin film treatment [Nanos (manufactured by T & K Co.)], fluorine coating [manufactured by Asahi Precision Co., Ltd.], chemical growth vapor phase [fluorine-containing diamond-like carbon (F-DLC) composition] Film method] and the like, and organic thin film treatment is preferred.
  • the curable resin composition in the present invention preferably contains a polymerizable compound and a polymerization initiator and can be cured by light or heat.
  • the polymerizable compound is preferably a polymerizable monomer and / or a polymerizable polymer.
  • the polymerizable monomer and the polymerizable polymer have one or more carbon-carbon unsaturated bonds in the molecule.
  • a polymeric compound may be used individually by 1 type, and may be used in combination of multiple types.
  • the content of the polymerizable compound is preferably 5 to 99.99 parts by weight and more preferably 10 to 99.9 parts by weight per 100 parts by weight of the curable resin compound.
  • the weight average molecular weight of the polymerizable polymer is preferably 500 to 5,000, and more preferably 800 to 2,000.
  • the ashing process is facilitated and the working time is shortened.
  • Examples of the polymerizable monomer having one carbon-carbon unsaturated bond in the molecule include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxydiethylene ( (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, 2-hydroxy-1-methylethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, (meth) acrylamide, -Substituted (meth) acrylamide [for example, diace
  • Examples of the polymerizable monomer having two or more carbon-carbon unsaturated bonds in the molecule include ethylene glycol di (meth) acrylate [NK ester 1G (manufactured by Shin-Nakamura Chemical Co., Ltd.)], propylene glycol di (meta) ) Acrylate, diethylene glycol di (meth) acrylate [NK ester 2G (manufactured by Shin-Nakamura Chemical Co., Ltd.)], triethylene glycol di (meth) acrylate [NK ester 3G (manufactured by Shin-Nakamura Chemical Co., Ltd.)], tetraethylene glycol Di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate [NK ester BG (manufactured by Shin-Nakamura Chemical Co., Ltd.)], neopentyl glycol di (meth) acrylate [NK ester NPG, A-NPG (new) Nakamura Chemical Co
  • triethylene glycol di (meth) acrylate triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, 2-hydroxy 1,3-dimethacryloxypropane, diethylene glycol dimethacrylate, ethoxylated cyclohexanedimethanol diacrylate, tripropylene glycol diacrylate [NK ester, APG-200 (manufactured by Shin-Nakamura Chemical Co., Ltd.)] and trimethylolpropane trimethacrylate Is preferred.
  • Examples of the polymerizable polymer include methoxypolyethylene glycol (meth) acrylate, polymethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and epoxy (meth).
  • examples include acrylates, epoxy-modified (meth) acrylates, polyether (meth) acrylates, urethane acrylates, ester (meth) acrylates, bisphenol-modified epoxy (meth) acrylates, and unsaturated polyester resins. Among these, urethane acrylates are preferred.
  • urethane acrylate examples include, for example, urethane obtained by reacting a hydroxyl group-containing polymer with a polyfunctional isocyanate and then reacting with a (meth) acrylate having active hydrogen, and (meth) acrylate having active hydrogen with a polyfunctional isocyanate. Further examples include urethane obtained by reacting a chain extender.
  • polyester polyols examples include polyester polyols, polyether polyols, polycarbonate polyols and the like. Among these, polyester polyols are preferable.
  • polyester polyol examples include polyester polyols obtained by reacting one or more dicarboxylic acids with one or more compounds having two or more hydroxyl groups.
  • dicarboxylic acid examples include adipic acid, glutaric acid, 2,4-diethylglutaric acid, succinic acid, dodecanedioic acid and the like, and among these, adipic acid or glutaric acid is preferable.
  • Examples of the compound having two or more hydroxyl groups include ethylene glycol, propylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,4-diethyl-1 , 5-pentanediol, 1,6-hexanediol, pyrocatechol, resorcinol, pyrogallol, bis (hydroxyphenyl) -2-propane, bis (hydroxyphenyl) methane, polyethylene glycol (2-120 polymer), polyprolene glycol (2-120 polymer), polyneopentyl glycol (2-120 polymer), glycerin, pentaerythritol and the like.
  • polypropylene glycol and bis (hydroxyphenyl) -2-propane are preferable.
  • the polyether polyol is obtained by reacting one or more cyclic ethers (for example, tetrahydrofuran, oxetane, ethylene oxide, propylene oxide, etc.) with one or more compounds having two or more hydroxyl groups.
  • the polyether polyol obtained from tetrahydrofuran and polypropylene glycol is preferable among these.
  • a compound having two or more hydroxyl groups has the same meaning as described above.
  • the polycarbonate polyol is a polycarbonate obtained by reacting one or more of carbonate esters (dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, etc.) with one or more compounds having two or more hydroxyl groups.
  • carbonate esters dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, etc.
  • Polyols are mentioned, and among these, polycarbonate polyols obtained from diethyl carbonate and polypropylene glycol are preferred.
  • a compound having two or more hydroxyl groups has the same meaning as described above.
  • polyfunctional isocyanate examples include ethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, 4,4′-. Examples thereof include diphenylmethane diisocyanate and dicyclohexylmethane diisocyanate. Among these, 2,4-tolylene diisocyanate and xylylene diisocyanate are preferable.
  • Examples of the (meth) acrylate having active hydrogen include (meth) acrylic acid ester having a hydroxyl group. Specific examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2 -Hydroxybutyl (meth) acrylate, 2-hydroxypropyl-3-benzoate (meth) acrylate, 2-hydroxypropyl-3- (4-phenylbenzoate) (meth) acrylate, glycidyl (meth) acrylate, etc. Among these, 2-hydroxyethyl (meth) acrylate or 2-hydroxybutyl (meth) acrylate is preferable.
  • chain extenders examples include polyethylene glycol (2 to 120 polymer), polyprolene glycol (2 to 120 polymer), polyneopentyl glycol (2 to 120 polymer), polycaptolactone (2 to 100 polymer) or Examples thereof include polybutyrolactone (2 to 100 polymer). Among these, 3 to 40 polymer polypropylene glycol or polycaptolactone is preferable.
  • the photocurable resin composition includes an epoxy resin, an oxetane resin, a urethane resin, a polyester resin, a silicone resin (for example, PDMS), a melamine resin, a fluorine resin, a polycarbonate resin, a poly ( (Meth) methyl acrylate resin (for example, PMMA), phenol resin, vinyl chloride resin, vinyl acetate resin, polyethylene resin, polypropylene resin, polyether resin, polyvinyl ether resin, polyimide resin, polyamide resin, polyamine resin, polyvinyl alcohol resin, Cyanoacrylate resins, ABS (acrylonitrile-butadiene-styrene) resins, PET (polyethylene terephthalate) resins, biodegradable plastics (polylactic acid, etc.), other thermoplastic resin
  • the curable resin composition in the present invention preferably contains a thermal polymerization initiator or a photopolymerization initiator as a polymerization initiator. If necessary, a photosensitizer, a photopolymerization accelerator, A solvent and other additives may be contained.
  • the content of the polymerization initiator is preferably in the range of 0.01 to 20% by mass in the curable resin composition.
  • the content of the thermal polymerization initiator is preferably in the range of 0.01 to 20% by mass, preferably in the range of 0.1 to 10% by mass with respect to the total polymerizable compound (solid content). More preferably.
  • thermal polymerization initiator examples include radical polymerization initiators and ionic polymerization initiators, and radical polymerization initiators are preferred.
  • radical polymerization initiator examples include peroxides, azo compounds, persulfates, redox initiators, etc. Among these, peroxides and azo compounds are preferable.
  • azo compound examples include 2,2′-azobis (2-methylpropionitrile) (AIBN), 2,2′-azobis (2-methylbutyronitrile) (AMBN), dimethyl 2,2′-azobis. (2-methylpropionate) [V-601: manufactured by Wako Pure Chemical Industries, Ltd.].
  • peroxides examples include hydrogen peroxide, peroxide salts, alkyl peroxides, acyl peroxides, and peroxide esters.
  • peroxides include hydrogen peroxide, peroxide salts, alkyl peroxides, acyl peroxides, and peroxide esters.
  • di-tert-butyl oxide perbutyl D: NOF Corporation
  • Tert-butyl oxyneodecanate Perbutyl ND: manufactured by NOF Corporation
  • tert-butyl oxypivalate Perbutyl PV: manufactured by NOF Corporation
  • Examples of the ionic polymerization initiator include a cationic polymerization initiator and an anionic polymerization initiator.
  • Examples of cationic polymerization initiators include proton acids (sulfuric acid, perchloric acid, trichloroacetic acid, etc.), Friedel-Craft type catalysts (aluminum chloride, ferric chloride, boron trifluoride, titanium tetrachloride, etc.), stable cations And catalysts (triphenylhexachloroantimonate, triethyloxonium tetrafluoroborate, etc.).
  • trichloroacetic acid, aluminum chloride, and boron trifluoride are preferable.
  • anionic polymerization initiator examples include alkali metals (sodium, lithium, etc.), Grignard reagents, alkyl lithium, electron donating organic compounds (amines, alkali compounds, etc.) and the like. Among these, lithium and amine are preferable.
  • polymerization of an epoxy resin can also be used.
  • the curing agent examples include amine-based curing agents, acid anhydride curing agents, phenol-based curing agents, imidazole-based curing accelerators, and among these, amine-based and acid anhydride-based curing agents are preferable.
  • Examples of the photopolymerization initiator used in the present invention include a photopolymerization initiator having photosensitivity at 200 to 1,000 nm, and among them, a photopolymerization initiator having photosensitivity at 365 to 600 nm is preferable. A visible light polymerization initiator having photosensitivity at 400 to 600 nm is more preferable.
  • visible light polymerization initiators examples include acylphosphine oxide compounds, ⁇ -aminoalkylphenone compounds, ⁇ -hydroxyalkylphenone compounds, titanocene photopolymerization initiators, hydrogen abstraction type radical photopolymerization initiators, and oxime ester types.
  • examples include photopolymerization initiators, cationic photopolymerization initiators, and acid generators.
  • acylphosphine oxide compounds are particularly preferable.
  • the acyl phosphine oxide compound include monoacyl phosphine oxide and bisacyl phosphine oxide.
  • Examples of the monoacylphosphine oxide include 2,4,6-trimethylbenzoyldiphenylphosphine oxide [Lucirin TPO (manufactured by BASF Corporation)], 2,6-dichlorobenzoyldiphenylphosphine oxide, 3-chloro-2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, 5- (4-pentyloxybenzoyl) -5H-dibenzophosphole 5-oxide, 5- (4-hexylbenzoyl) -5H -Dibenzophosphole 5-oxide, 5- (2,4,6-trimethylbenzoyl) -5H-dibenzophosphole 5-oxide, 5- (4-toluoyl) -5H-dibenzophosphole 5-oxide, 5- ( p-anisoy -5H-dibenzophosphole 5-oxide, 5- (2,6-dimethoxybenz
  • bisacylphosphine oxide examples include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide [BAPO: Irgacure 819 (manufactured by Ciba Specialty Chemicals)], bis (2,4,6-trimethyl).
  • Benzoyl) -4-methylphenylphosphine oxide bis (2,4,6-trimethylbenzoyl) -2,4-dimethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,6-diisopropylphenylphosphine Oxide, bis (2,4,6-trimethylbenzoyl) -4-isopropyl-2,6-dimethylphenylphosphine oxide, bis (2,6-dimethylbenzoyl) phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) ) -2,5-Di Chill phenyl phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide and the like.
  • Examples of the ⁇ -aminoalkylphenone compound include 2-methyl-1- [4 (methylthio) phenyl] -2-morpholinopropan-1-one [Irgacure 907 (manufactured by Ciba Specialty Chemicals)], 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone [Irgacure 369 or 1300 (manufactured by Ciba Specialty Chemicals)], 2-dimethylamino-2- (4-methylbenzyl ) -1- (4-morpholinophenyl) -1-butanone [Irgacure 379 (manufactured by Ciba Specialty Chemicals)], 3,6-bis (2-methyl-2-morpholinopropionyl) -9-octylcarbazole [Adekaoptomer N-1414 manufactured by ADEKA Co., Ltd.] It can be used in combination with a tontone derivative (
  • ⁇ -hydroxyalkylphenone compound for example, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl] -2-methylpropan-1-one [Irgacure 127 ( Ciba Specialty Chemicals)], 1-hydroxycyclohexyl phenyl ketone [Irgacure 184 (Ciba Specialty Chemicals)], 2-hydroxy-2-methyl-1-phenylpropan-1-one [Darocur 1173 (manufactured by Ciba Specialty Chemicals)], 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one [Irgacure 2959 (Ciba ⁇ Specialty Chemicals), oligo [2-hydroxy-2 Methyl-1- [4- (1-methylvinyl) phenyl] propane [Isakyua KIP 0.99, Isakyua KIP EM, Irg
  • titanocene type photopolymerization initiator for example, bis (5-2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium [ Irgacure 784 (manufactured by Ciba Specialty Chemicals Co., Ltd.)].
  • hydrogen abstraction type radical photopolymerization initiator examples include benzophenone derivatives, thioxanthone derivatives, quinone-amine photopolymerization initiators, and the like.
  • benzophenone derivative examples include 4- (4-methylphenylthio) phenyl ketone [Kayacure BMS (manufactured by Nippon Kayaku Co., Ltd.)] and the like.
  • Examples of the thioxanthone derivative include 2,4-diethylthioxanthone [Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)], 2-chlorothioxanthone [Kayacure CTX (manufactured by Nippon Kayaku Co., Ltd.)], isopropylthioxanthone [ Isacure ITX (Lamberti Co., Ltd.)] and the like.
  • Examples of the quinone-amine photopolymerization initiator include a combination of a quinone compound or a benzyl ketal photopolymerization initiator and an amine compound or an aminobenzoate compound, and these have a polymerization initiation function.
  • Examples of the quinone compound include camphorquinone, ethyl anthraquinone [Kayacure 2-EAQ (manufactured by Nippon Kayaku Co., Ltd.)], benzyl [BENZIL (manufactured by Kurokin Kasei Co., Ltd.), S-113 (Shinko Giken Co., Ltd.). )] Etc.
  • benzyl ketal type photopolymerization initiator examples include benzyl dimethyl ketal [DMPA: Irgacure 651 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Isacur KB1 (manufactured by Lamberti Co., Ltd.)], and benzoin [Seiko All Z (Seiko Co., Ltd.). Chemical Co., Ltd.)], benzoin ethyl ether [Sequol BEE (Seiko Chemical Co., Ltd.)] and the like.
  • DMPA benzyl dimethyl ketal
  • Irgacure 651 manufactured by Ciba Specialty Chemicals Co., Ltd.
  • Isacur KB1 manufactured by Lamberti Co., Ltd.
  • benzoin Seiko All Z (Seiko Co., Ltd.). Chemical Co., Ltd.)]
  • benzoin ethyl ether Sequol BEE (Seiko Chemical Co.,
  • amine compound examples include 4,4′-bis (dimethylamino) benzophenone (Michler ketone), 4,4′-bis (diethylamino) benzophenone [S-112, manufactured by Shinko Giken Co., Ltd., High Cure ABP (Kawaguchi Pharmaceutical ( And 10-butyl-2-chloroacridone (NBCA (manufactured by Kurokin Kasei Co., Ltd.)).
  • Darocur EBD manufactured by Ciba Specialty Chemicals
  • Kayacure EPA manufactured by Nippon Kayaku
  • 2-ethylhexyl 4-dimethylamino Benzoate
  • isoamyl 4-dimethylaminobenzoate
  • Kayacure DMBI manufactured by Ciba Specialty Chemicals
  • Examples of the oxime ester type photopolymerization initiator include 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzoyloxime) [Irgacure OXE01 (manufactured by Ciba Specialty Chemicals Co., Ltd.) )], 1- [9- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- [9- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O -Acetyloxime) [CGI242 (Ciba Specialty Chemicals Co., Ltd.)] and the like.
  • Examples of the cationic photopolymerization initiator include aromatic sulfonium salts [Syracure UVI-697, UVI-6922 (manufactured by Dow Chemical Co., Ltd.), SP-150, SP-152, SP-170, SP-172 (( ADEKA) and DTS-102, DTS-103, DTS-105, NDS-103, NDS-105, NDS-155, MNPS-109 (manufactured by Midori Chemical Co., Ltd.)], iodonium salts [for example, UV9380 ( GE Toshiba Silicone Co., Ltd.), Irgacure 250 (Ciba Specialty Chemicals Co., Ltd.), BBI-102, BBI-103 (Midori Chemical Co., Ltd.)] and the like.
  • aromatic sulfonium salts for example, UV9380 ( GE Toshiba Silicone Co., Ltd.), Irgacure 250 (Ciba Specialty Chemicals Co., Ltd.),
  • the cationic photopolymerization initiator is preferably mixed with an epoxy resin, an oxetane resin, a vinyl ether compound, a novolac resin, a phenol resin, a (meth) acrylic acid resin, or the like when used.
  • Examples of the acid generator include 2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine [TFE-triazine (Sanwa Chemical Co., Ltd.). ))], 2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine [TME-triazine (Sanwa Chemical Co., Ltd.) ))], 2- [2- (3,4-dimethoxyphenyl) ethenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine [TAZ-113 (Midori Chemical Co., Ltd.) Dimethoxytriazine (manufactured by Sanwa Chemical Co., Ltd.)], (5-octanesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl
  • an acid generator mixes an epoxy resin, an oxetane resin, a vinyl ether compound, a novolac resin, a phenol resin, a (meth) acrylic acid resin, etc. in use.
  • a photopolymerization initiator having photosensitivity in the (near) infrared region can be used alone or in combination with other polymerization initiators.
  • a combination of an organic boron compound and a near-infrared absorbing photosensitive dye can be used as a photopolymerization initiator.
  • tetrabutylammonium butyltriphenylborate [P3B (manufactured by Showa Denko KK)], tetrabutylammonium butyltri (4-tert-butylphenyl) borate [BP3B (manufactured by Showa Denko KK)]
  • BP3B tetrabutylammonium butyltri (4-tert-butylphenyl) borate
  • IR-T and IR-13F near-infrared absorbing dyes
  • photosensitizer examples include anthracene, phenothiazene, perylene, coumarin derivatives, thiazole derivatives, thioxanthone derivatives, CT complexes (complexes of pyridinium salts and aromatic compounds), and the like.
  • photopolymerization accelerator examples include aromatic amine compounds, aminobenzoate compounds, thioxanthone derivatives, and the like.
  • aromatic amine compounds aminobenzoate compounds
  • thioxanthone derivatives examples include isoamyl p-dimethylaminobenzoate [KAYACURE DMBI (made by Nippon Kayaku Co., Ltd.)]
  • ethyl p-dimethylaminobenzoate [KAYACURE EPA (made by Nippon Kayaku Co., Ltd.)]
  • the curable resin composition in the present invention preferably contains the polymerizable compound and a visible light polymerization initiator.
  • a visible light polymerization initiator for example, it can be cured to a deep portion by light in the visible light wavelength range (400 to 800 nm), and can be photocured even when it contains a substance that lowers transparency such as a filler.
  • visible light permeate transmits the inside of a curable resin composition
  • hardenability is uniform and can give rectangularity faithful to a mold.
  • a preferred form of the pattern forming method of the present invention is to use a plastic mold. Thereby, it can be photocured to the deep part of the visible light curable resin composition, and pattern formation of a thick film or a high columnar object (pattern with a high aspect ratio) becomes possible.
  • the pattern is a columnar object
  • the width of the obtained pattern is preferably 10 nm to 100 mm
  • the depth is preferably 10 nm to 5 mm.
  • the curable resin composition in the present invention may contain a solvent.
  • the content of the solvent in the curable resin composition is preferably 0.1 to 90% by mass, and more preferably 1 to 30% by mass.
  • the solvent include volatile solvents.
  • volatile solvent examples include ketone solvents (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), aromatic solvents (for example, toluene, xylene, cumene, anisole, etc.), ester solvents (for example, ethyl acetate).
  • ketone solvents for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.
  • aromatic solvents for example, toluene, xylene, cumene, anisole, etc.
  • ester solvents for example, ethyl acetate
  • the curable resin composition in the present invention can contain a known additive as appropriate depending on the application.
  • the content of the additive in the curable resin composition is preferably in the range of 0.01 to 5% by mass.
  • a polymerization inhibitor can be added for the purpose of improving the stability of the resin or suppressing / adjusting the polymerization.
  • hydroquinone, 2,6-di-tert-butyl-p- Examples thereof include polymerization inhibitors such as cresol, p-methoxyphenol, and sterically hindered phenol.
  • the curable resin composition in the present invention can contain a copper compound, a phosphorus compound, a quaternary ammonium compound, a hydroxylamine derivative and the like in order to increase the shelf life in a dark room.
  • paraffin or similar wax-like substances that move to the surface at the start of polymerization can be included to reduce the damage caused by oxygen during curing.
  • the curable resin composition in the present invention can also contain a light stabilizer.
  • the light stabilizer include UV absorbers, UV absorption polymers, and photodegradation prevention polymers. Specific examples include benzotriazole, benzophenone, hydroxyphenyl-s-triazine, oxalanilide compounds, and the like. can give.
  • the curable resin composition according to the present invention includes a fluorescent brightening agent, a filler, a pigment, a dye, a wetting agent, a dispersant, an antioxidant, a lubricant, a corrosion inhibitor, an antialgae, and an antifouling agent, depending on the purpose.
  • An antistatic agent, a flow control agent, and the like can be appropriately contained.
  • the curable resin composition in the present invention may contain a mold release agent or a release agent in order to improve the peelability and releasability, and the surface of the curable resin composition applied on the substrate is the above-mentioned.
  • a mold release agent or the release agent may be applied or dispersed.
  • the mold release agent include fluorine-based surface treatment agents [for example, OPTOOL DSX, Durasurf HD-1100, HD-2100 (manufactured by Daikin Industries, Ltd.), Novec EGC-1720 (manufactured by Sumitomo 3M Limited)], Mold release agent [Barrier Serum Gamma R (manufactured by Vanatech Co., Ltd.)] and the like.
  • release agent examples include fluorine-based acrylic compounds [V-3F, V-4F, V-8F (manufactured by Osaka Organic Chemical Co., Ltd.)], fluorine-based mold release agents [Flease (manufactured by Neos Corporation)].
  • Etc. silicone resin, silicone oil, silicone wax, Teflon (registered trademark) dispersant, polyvinyl alcohol, water-soluble emulsion release agent and the like.
  • a silane coupling agent for example, a silane coupling agent, a hydroxyl group-containing (meth) acrylate, a chelating agent, a metal trapping agent, an epoxy compound,
  • a treatment agent such as a sulfur-containing compound may be contained in the curable resin composition, and the treatment agent may be applied or dispersed on the surface of the seed film.
  • silane coupling agent examples include ⁇ -glycidoxypropyltrimethoxysilane [KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)], ⁇ -glycidoxypropylmethyldiethoxysilane [KBM-402 (Shin-Etsu Chemical).
  • a ring-opening polymerizable monomer such as an epoxy compound, an oxetane compound, or a tetrahydropyran derivative is polymerized with the ring-opening polymerizable monomer.
  • the curable resin composition may contain a cationic photopolymerization initiator or a curing agent (for example, amines, carboxylic acids, acid anhydrides, thiol compounds, etc.) that can be initiated.
  • an acyl group such as an acetyl group may be introduced into the hydroxyl group of the contained compound.
  • a colorless transparent filler in order to relieve shrinkage when the curable resin composition is cured, a colorless transparent filler, a colored filler, a glossy filler, and the like may be included.
  • the colorless and transparent filler include silica gel, functional silica gel (functional group-modified silica gel), glass (glass beads, glass pieces, etc.), titanium oxide, plastic particles (for example, polystyrene particles, polyacryl particles, polycarbonate particles, PET particles, etc.), dental filling resins, water, aqueous solutions, sugars, organic solvents, inorganic solids, ionic liquids and the like.
  • coloring fillers include pigments, dyes, opaque plastic particles, papers, ceramics, latex, emulsion, carbon black (charcoal), pebbles, sand, soil, concrete, asphalt, minerals, fertilizers, petals, seeds, Examples include pollen, soap, protein, magnetic powder, iron sand, fat, hair, skin, and smoke.
  • glossy fillers include metal grains and metal pieces (eg, gold, silver, copper, iron, lead, tin, aluminum, chromium, nickel, zinc, mercury, arsenic, sodium, potassium, etc.), alloys (For example, tin, bronze, brass, anodized, amalgam, etc.), metal oxides (for example, rust, patina, etc.), silicon wafer pieces, mirror pieces and the like.
  • Others include, for example, dispersion aids, fillers (eg talc, gypsum, silica, rutile, carbon black, zinc oxide, iron oxide), bulking agents, matting agents, antifoaming agents, fluorescent agents, phosphorescent agents, Luminous agent, conductive agent, metal particles (for example, gold particles, silver particles, copper particles), color materials, antibacterial agents (for example, titanium oxide, antibacterial organic compounds, etc.), photocatalysts, reaction catalysts, solid acids, ion exchange Examples thereof include resins, paints, water-based paints, powder paints, other auxiliaries commonly used in surface coating technology, nanoparticles of the other auxiliaries, and the like. *
  • the curable resin composition according to the present invention may contain a filler that functions as a photocatalyst (for example, titanium oxide, silver, etc.).
  • a filler that functions as a photocatalyst (for example, titanium oxide, silver, etc.).
  • a curable resin composition excellent in antibacterial properties, sterilization properties, antifouling properties, deodorizing properties, deodorizing properties, purifying properties and the like can be obtained.
  • Examples of the light used for curing the curable resin composition in the present invention include ultraviolet light, visible light, near infrared light, and the like.
  • Examples of light sources that can emit such light include incandescent lamps, fluorescent lamps, sunlight, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halogen lamps, lasers, and light-emitting diodes (LEDs). ) Etc.
  • lasers and LEDs include light and small semiconductor lasers and LEDs that can irradiate light in a certain region within a range of 360 to 600 nm.
  • a semiconductor violet laser, a semiconductor blue violet laser, a semiconductor blue laser, and a blue LED are preferable.
  • Infrared and near infrared lasers can also be used. The use of visible light or infrared light has advantages in that it is safer than a method using ultraviolet light harmful to the human body, and a shielding device for preventing human exposure is unnecessary.
  • a commercially available light source can be appropriately used.
  • a semiconductor laser violet (400-415 nm): NDHV220APAE1, blue violet (440-450 nm): NDHVB510APAE1, blue (468-478 nm): NDHA500APAE1 (day Manufactured by Asia Chemical Industry Co., Ltd.)]
  • blue LED [(460-490 nm): NSPB300A, NSPB310A, NSPB320BS, NSPB500S, NSPB510S, NSPB513, NSPB518S, NSPB520S, NSPBF50S (manufactured by Nichia Corporation)]
  • blue green LED [(470-530 nm): NSPE800S (manufactured by Nichia Corporation)] and the like.
  • a reflecting plate or a shielding plate around the light source so that the irradiation light from the light source is condensed and applied to the pattern transfer portion and is not irradiated onto the uncured resin before transfer. Further, it is preferable to provide a shielding plate or a shielding device so that irradiation light and room light do not strike the resin before transfer.
  • the substrate to which the curable resin composition is applied in the present invention it is preferable to use a material that can be electroformed or to provide a seed film on the substrate so that the electroforming can be performed.
  • the material that can be electroformed or the metal of the seed film include nickel, tin, zinc, gold, silver, and copper. Among these, nickel and copper are preferable.
  • the method for providing the seed film on the substrate include sputtering.
  • examples of the substrate material include glass, silicon, oxide film-coated glass (ITO: indium titanium oxide-coated glass, etc.), metals (aluminum, gold, silver, copper, iron, true nickel). , Tin, zinc, brass plate, tin plate, etc.), plastic (polycarbonate, acrylic, PET (polyethylene terephthalate), ABS (acrylonitrile and copolymer of butadiene and styrene) resin plate, etc.), film (polyimide, vinyl chloride, polystyrene, saran) Resin film etc.), porcelain (ceramics, ceramics, tiles, etc.) can be used.
  • ITO indium titanium oxide-coated glass, etc.
  • metals aluminum, gold, silver, copper, iron, true nickel
  • Tin zinc, brass plate, tin plate, etc.
  • plastic polycarbonate, acrylic, PET (polyethylene terephthalate), ABS (acrylonitrile and copolymer of butadiene and
  • Examples of the metal of the metal film to be formed include copper, nickel, chromium, zinc, tin, gold, silver, and platinum group metals. Among these, copper, nickel, and gold are preferable, and copper and nickel are more preferable. .
  • Examples of the method for forming the metal film include electroforming (electroplating), displacement plating, electroless plating, and the like.
  • the electroforming process is a method of forming a metal film by reducing metal ions contained in a plating bath with electricity.
  • Displacement plating is a method of forming a metal film by inserting a metal having a higher ionization tendency than the metal ions contained in the plating bath into the plating bath and reducing the metal ions contained in the plating bath due to the difference in ionization tendency.
  • Electroless plating is a method of forming a metal film by reducing metal ions in a plating bath with a reducing agent. Among these, electroforming treatment is preferable because a film thickness of 10 ⁇ m or more can be formed.
  • Examples of plating baths used for forming a nickel metal film by electroforming include nickel plating baths (Watt baths) mainly composed of nickel sulfate, nickel chloride and boron, nickel sulfamate, nickel chloride and boron. And a sulfamate salt bath containing as a main component. In any of the above plating baths, it is preferably performed at a pH of 2.5 to 5.0.
  • the Watt bath is preferably performed at 40 to 65 ° C
  • the sulfamate bath is preferably performed at 25 to 65 ° C
  • the low stress plating is preferably performed at 50 to 65 ° C.
  • Watts bath is preferably carried out at a current density of 2 ⁇ 4A / dm 2
  • sulfamate bath is preferably carried out at a current density of 2 ⁇ 90A / dm 2.
  • Examples of the plating bath used when forming a copper metal film by electroforming include, for example, a copper sulfate plating bath mainly composed of copper sulfate and sulfuric acid, cuprous cyanide and sodium cyanide as the main components.
  • Examples thereof include a copper cyanide plating bath, a copper pyrophosphate plating bath mainly composed of copper pyrophosphate and potassium pyrophosphate.
  • the copper sulfate plating bath is preferably performed at 15 to 35 ° C., and the copper cyanide plating bath and the copper pyrophosphate copper plating bath are preferably performed at 40 to 65 ° C.
  • the copper cyanide plating bath is preferably carried out at a pH of 11 to 13, and the copper pyrophosphate plating bath is preferably carried out at a pH of 8.0 to 9.0.
  • the copper sulfate plating bath is preferably performed at a current density of 1 to 6 A / dm 2
  • the copper cyanide plating bath is preferably performed at a current density of 1 to 4 A / dm 2
  • the copper cyanide plating bath is 1 to 3 A. It is preferable to carry out at a current density of / dm 2 .
  • the metal film As a pretreatment when forming the metal film, it may be degreased and cleaned by solvent cleaning such as trichlorethylene or alkali immersion such as caustic soda or sodium carbonate composition, and an insulating film in the region where the metal film is formed, for example, an oxide film In order to remove, etc., it may be washed with sulfuric acid, hydrochloric acid, hydrofluoric acid or the like.
  • the residual cured resin and the cured resin after forming the metal film can be removed by physical or chemical methods. Specifically, ashing (oxygen plasma ashing), solvent (for example, , N-methylpyrrolidone, ⁇ -butyrolactone, propylene glycol methyl ether, propylene glycol methyl ether acetate, cyclohexanone, etc.), an alkali developing method, etc., among which ashing is preferred.
  • ashing oxygen plasma ashing
  • solvent for example, N-methylpyrrolidone, ⁇ -butyrolactone, propylene glycol methyl ether, propylene glycol methyl ether acetate, cyclohexanone, etc.
  • alkali developing method etc.
  • the pattern formed product obtained by the pattern forming method of the present invention can be used by changing its form into a processed product such as a film, a fiber (fiber), or a three-dimensional structure by a physical or chemical method.
  • the pattern formed product obtained by the pattern forming method of the present invention or the processed product including the pattern formed product is, for example, a semiconductor chip material, a printed electronic circuit material, a micro component material, a molecular device material, a micro machine material, a printing plate, a printing Mask manufacturing material, mold manufacturing material, optical recording material, organ duplication material, Gibbs material, design design material, design design material, small device model creation material, simulation model creation material, FPD ( Flat panel display materials, LCD (liquid crystal display) materials, optical circuit materials, optical communication materials, optical waveguides, optical fibers, solar cell materials, optical switches, optical circuit materials, stereolithography materials, optical detector materials, optical morphologies Material, cell culture material (cell culture sheet), plant culture material, LED (light emission) Iodine), organic EL materials, inkjet printer materials, printing plates, biochips, DNA chips, microchannels, diagnostic kits, fingerprint authentication devices, fingerprint replication devices, specimen preparation materials, organ specimen preparation materials, automobile parts, It can be used for ship parts, aircraft parts, space materials
  • a desired pattern can be formed on the substrate using the pattern formed product obtained by the pattern forming method of the present invention.
  • the pattern formed product in which the desired pattern is formed on the substrate or the processed product including the pattern formed product include a semiconductor chip material, an antireflection film, an optical waveguide, a polarizing plate, a microchannel, a cell culture sheet, and a biochip. Can be used for
  • PFO-E was produced by the method described in JP-A-2005-225793.
  • BAPO Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide: Irgacure 819 [manufactured by Ciba Specialty Chemicals]
  • MAPO 2,4,6-trimethylbenzoyldiphenylphosphine oxide: Lucirin TPO [manufactured by BASF Corp.]
  • PFO-E 5- (4-pentyloxybenzoyl) -5H-dibenzophosphole 5-oxide
  • DETX 2,4-diethylthioxanthone: Kayacure DETX-S [manufactured by Nippon Kayaku Co., Ltd.]
  • TITANO Bis (5-2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl)
  • urethane acrylate NK oligo UA-4200 ⁇ used in resin compositions 1-5, weight average molecular weight 1,300 [manufactured by Shin-Nakamura Chemical Co., Ltd.] ⁇ : NK oligo UA-122P ⁇ used in resin composition 6 , Weight average molecular weight 1,100 [manufactured by Negami Kogyo Co., Ltd.] ⁇ : Art Resin UN-904 ⁇ used in resin composition 7, weight average molecular weight 4,900 [manufactured by Negami Kogyo Co., Ltd.] ⁇ ⁇ NVP: N-vinylpyrrolidone [manufactured by Nippon Shokubai Co., Ltd.] TMPTA: trimethylolpropane triacrylate: NK ester A-TMPT [manufactured by Shin-Nakamura Chemical Co., Ltd.] A-DCP: Tricyclo
  • Plastic mold A plastic mold was molded by the following method, and the molded product was used.
  • PP mold Polypropylene plate [2.5 ⁇ 2.5 cm, thickness 1 mm, with UV absorber, made by Nippon Test Panel Co., Ltd.], nickel mold (2.5 ⁇ 2.5 cm, pattern area 0.5 ⁇ 1.0 cm, pattern: L & S: width 80 nm to 20 ⁇ m, aspect ratio 0.1 to 2, spacing ratio 1: 1 to 1:10) is pressed to form a thermal (nano) imprint apparatus [TP-32937-0401: Maruni Co., Ltd.] was used to transfer the pattern (temperature: upper plate 130 ° C .: lower plate 30 ° C., press pressure 5 Mpa, holding time 5 minutes) to produce a plastic mold.
  • PI mold polyimide film [Aurum film, 2.5 ⁇ 2.5 cm, thickness 300 ⁇ m, manufactured by Mitsui Chemicals, Inc.] using the same nickel mold as described above, using a thermal (nano) imprinting device, Pattern transfer (temperature: upper plate 220 ° C .: lower plate 180 ° C., press pressure 10 MPa, holding time 5 minutes) was performed to produce a plastic mold.
  • PDMS mold polydimethylsiloxane (Silpot 184 (manufactured by Toray Dow Corning Co., Ltd.)): The main agent and the catalyst are mixed at a weight ratio of 10: 1, and the resulting resin is placed on the nickel mold pattern in a range of 0.1 to 1 g was dropped and heated in an oven at 100 ° C. for 1 hour to peel off the PDMS to produce a PDMS mold.
  • a nickel seed film (0.1 ⁇ m) was formed by sputtering on a substrate / silicon wafer (2 inch) substrate on which a seed film was formed.
  • Photoimprint A cured resin pattern was formed by the following procedure. 2 to 3 ml of the resin composition 1 to 8 is dropped on the substrate on which the seed film is formed, and the resin composition is covered with a plastic mold (PP mold, PI mold, or PDMS mold), and an optical imprint apparatus [Marni The pattern was obtained by curing with light irradiation at room temperature. As shown in Table 2, the pattern of each Example was obtained using the resin composition and the plastic mold. The film thickness of the convex portions of the pattern was 20 to 40 ⁇ m.
  • the pattern formation conditions were as follows. 1. Press pressure: Press at 0.5 MPa for 30 seconds 2. Depressurization: Next, depressurize using a vacuum pump and hold for 15 seconds. Light irradiation: 15 seconds [ultra-high pressure mercury lamp, the light quantity 100 mJ / cm 2 at 365 nm] 4). Pressure release: Up to normal pressure 5. The mold was removed from the cured resin to obtain the pattern.
  • Ashing treatment RIE-10N manufactured by Samco International Laboratory was used as the RIE apparatus.
  • the RF (Radio Frequency) output is 125 W
  • the pressure in the etching chamber is 40 Pa
  • the oxygen gas flow rate is 45 ml / min (at atmospheric pressure and 0 ° C.)
  • the ashing process is performed for 10 minutes. Residual cured resin was removed.
  • Table 2 shows the results of film thickness reduction with respect to RF output.
  • the thickness of the film reduction represents a decrease in the film thickness of the convex portion of the pattern due to the ashing process.
  • the thickness of the film reduction was measured using a stylus profilometer [DEKTAK3 VEECOSLOAN TECHNOLOGY Co., Ltd.].
  • Example 11 Formation of nickel metal film pattern
  • the cured resin pattern formed product having a thickness of about 20 ⁇ m obtained in Example 1 was subjected to 10 A / dm using a sulfamate bath (aqueous solution of nickel sulfamate, nickel chloride and boric acid, 40 ° C., pH 4.2).
  • a sulfamate bath aqueous solution of nickel sulfamate, nickel chloride and boric acid, 40 ° C., pH 4.2.
  • the RF output is 135 W
  • the pressure in the etching chamber is 40 Pa
  • the oxygen gas flow rate is 45 ml / min (at atmospheric pressure and 0 ° C.)
  • the ashing process is performed for 50 minutes. The remaining cured resin was completely removed to obtain a metal film pattern.
  • a curable resin composition containing a polymerizable monomer or / and a polymerizable polymer having a weight average molecular weight of 5,000 or less is effective in removing the cured resin by ashing treatment. It was. Further, from the results of Example 11, it was found that a metal film pattern can be created using a plastic mold and a visible light curable resin in a method combining the imprint technique and the electroforming technique.
  • a pattern of a metal film (mold) and a method for forming the same for manufacturing a metal processed product, a fine part, and the like are simply provided.
  • a visible light curable resin composition containing a plastic mold and a polymerizable compound having a specific weight average molecular weight or less it is possible to more easily form a metal film (mold) pattern.

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  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

L'invention concerne un motif de film métallique (matrice métallique) pour produire un produit de traitement du métal ou une pièce fine. L'invention concerne également un procédé pour former facilement le motif. Le procédé pour former le motif de film métallique est caractérisé en ce qu'il comprend l'application d'une composition de résine durcissable (4) sur un substrat (3) sur lequel un film de germination (2) a été déposé; l'utilisation d'un moule (5) avec un motif donné devant être transféré sur la composition en résine durcissable (4) d'après le mouvement du moule (5) par rapport au substrat (3); le durcissement de la composition en résine durcissable (4), le motif donné du moule (5) étant transféré sur la composition en résine durcissable (4); le détachement du moule (5) de la résine réticulée (4'); la suppression des résidus de résine durcie (4') dans une zone (8); la formation d'un film métallique (11) dans une zone (10); et la suppression des résidus de résine durcie (4') sur le substrat. L'utilisation d'un moule en plastique et d'une résine durcissant à la lumière visible et contenant un composé polymérisable dont le poids moléculaire moyen n'excède pas une valeur spécifique permet d'obtenir plus facilement un motif de film métallique.
PCT/JP2009/050983 2008-01-25 2009-01-22 Procédé pour former un motif de film métallique WO2009093661A1 (fr)

Applications Claiming Priority (2)

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JP2008014934A JP2011067950A (ja) 2008-01-25 2008-01-25 金属膜のパターン形成方法
JP2008-014934 2008-01-25

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WO2009093661A1 true WO2009093661A1 (fr) 2009-07-30

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JP2011159924A (ja) * 2010-02-03 2011-08-18 Fujifilm Corp 微細パターン製造方法
US8563216B2 (en) 2010-07-23 2013-10-22 Shin-Etsu Chemical Co., Ltd. Substrate to be processed having laminated thereon resist film for electron beam and organic conductive film, method for manufacturing the same, and resist patterning process
JP2018080309A (ja) * 2016-11-18 2018-05-24 株式会社ダイセル レプリカモールド形成用樹脂組成物、レプリカモールド、及び前記レプリカモールドを用いたパターン形成方法

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WO2012160769A1 (fr) * 2011-05-24 2012-11-29 コニカミノルタアドバンストレイヤー株式会社 Procédé de fabrication d'un article moulé en résine
JP2013229532A (ja) * 2012-04-27 2013-11-07 Hitachi Ltd 微細構造転写装置および微細構造転写方法
JP6090707B2 (ja) * 2012-12-28 2017-03-08 川崎化成工業株式会社 ラジカル重合増感剤
JP6443849B2 (ja) * 2013-05-09 2018-12-26 東洋合成工業株式会社 樹脂、樹脂の製造方法及び部品
JP2016044222A (ja) * 2014-08-21 2016-04-04 日立化成株式会社 接着剤組成物及び接続構造体
JP6211546B2 (ja) * 2015-01-07 2017-10-11 富士フイルム株式会社 金属基板の製造方法
KR101907337B1 (ko) * 2015-04-29 2018-10-11 쓰리엠 이노베이티브 프로퍼티즈 캄파니 팽윤성 필름 형성 조성물 및 그것을 사용한 나노임프린트 리소그래피의 방법
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JP5301648B2 (ja) * 2009-02-27 2013-09-25 三井化学株式会社 転写体およびその製造方法
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JP2011159881A (ja) * 2010-02-02 2011-08-18 Fujifilm Corp インプリント用硬化性組成物、パターン形成方法およびパターン
JP2011159924A (ja) * 2010-02-03 2011-08-18 Fujifilm Corp 微細パターン製造方法
US8563216B2 (en) 2010-07-23 2013-10-22 Shin-Etsu Chemical Co., Ltd. Substrate to be processed having laminated thereon resist film for electron beam and organic conductive film, method for manufacturing the same, and resist patterning process
JP2018080309A (ja) * 2016-11-18 2018-05-24 株式会社ダイセル レプリカモールド形成用樹脂組成物、レプリカモールド、及び前記レプリカモールドを用いたパターン形成方法
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EP3543294A4 (fr) * 2016-11-18 2020-07-15 Daicel Corporation Composition de résine pour former un moule de réplique, moule de réplique et procédé de formation de motif utilisant ledit moule de réplique

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