WO2009093661A1 - Process for forming metallic-film pattern - Google Patents

Abstract

A metallic-film (metallic-die) pattern for producing a product of metal processing or a fine part. Also provided is a process for easily forming the pattern. The process for forming the metallic-film pattern is characterized by comprising applying a curable resin composition (4) to a substrate (3) on which a seed film (2) has been deposited, using a mold (5) having a given pattern to transfer the given pattern of the mold (5) to the curable resin composition (4) based on the movement of the mold (5) relative to the substrate (3), curing the curable resin composition (4) having the given pattern of the mold (5) transferred to the curable resin composition (4), detaching the mold (5) from the cured resin (4'), removing the cured resin (4") remaining as a residue in a region (8), forming a metallic film (11) in a region (10), and removing the cured resin (4') remaining on the substrate. Use of a plastic mold and a visible-light-curable resin containing a polymerizable compound having a weight-average molecular weight not higher than a specific value enables the process to more easily yield a metallic-film pattern.

Description

Metal film pattern forming method

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.

There is a LIGA (Lithography Galvanoforming Abforming) process as a technology for manufacturing fine parts. In the LIGA process, 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. This is a technology for mass production of fine parts. (See Patent Document 1)

However, the LIGA process has a problem in forming a desired thick film resist pattern in the lithography process. When performing by X-ray lithography, the stable operation of X-ray apparatus, productivity, and the complexity of mask production are raised. In addition, when performing by UV lithography, the present thick film resist has problems in resolution and peelability.

In recent years, a method of forming a pattern using a thermal imprint method has been studied. 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.

However, in the thermal imprint method using a 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.

On the other hand, in the photoimprint method, 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).

In addition, 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). However, in the case of 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.

JP 2006-73936 A JP-T-2004-504718 JP 2002-539604 A JP 2007-177194 A JP 2007-234153 A

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).
(1) 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.
(2) The metal film pattern forming method as described in (1) above, wherein the curable resin composition is a resin composition that is cured by light.
(3) The method for forming a metal film pattern according to (1) or (2), wherein the metal film is formed by electroforming.
(4) The method for forming a metal film pattern according to any one of (1) to (3), wherein the curable resin composition contains a polymerizable compound and a polymerization initiator.
(5) The method for forming a metal film pattern according to (4), wherein the polymerizable compound is a polymerizable monomer.
(6) The metal film according to (4), wherein the polymerizable compound is a polymerizable polymer having a weight average molecular weight of 5,000 or less, or a polymerizable monomer and a polymerizable polymer having a weight average molecular weight of 5,000 or less. Pattern forming method.
(7) The metal film pattern forming method as described in (6) above, wherein the polymerizable polymer having a weight average molecular weight of 5,000 or less contains urethane acrylate.
(8) The metal film pattern forming method as described in (7) above, wherein the content of urethane acrylate in the curable resin composition is 5 to 99.99 parts by weight.
(9) The method for forming a metal film pattern according to any one of (4) to (8), wherein the polymerization initiator is a visible light polymerization initiator.
(10) The method for forming a metal film pattern according to (9), wherein the visible light polymerization initiator is an acylphosphine oxide compound.
(11) The metal film pattern forming method according to any one of (1) to (10), wherein the mold having the predetermined pattern is a plastic mold.
(12) The metal film pattern forming method according to (11), wherein the plastic mold material is at least one of polyimide, polycarbonate, polypropylene, and polydimethylsiloxane.
(13) The method for forming a metal film pattern according to any one of (1) to (12), wherein the residual cured resin is removed by ashing.
(14) The metal film pattern forming method according to any one of (1) to (13), wherein the seed film is formed of a metal film.
(15) A pattern formed product, which is patterned by the method described in any one of (1) to (14) above.
(16) A processed product comprising the pattern-formed product according to (15).

According to the method of the present invention, a metal film (mold) pattern and a method for forming the pattern can be easily provided. According to 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.

BRIEF DESCRIPTION OF THE DRAWINGS 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.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate 2 Seed film 3 Substrate with seed film 4 Curing resin 5 Plastic mold 6 Convex part 7 Concave part 8 Concave part 9 Convex part 10 Electroformed region 11 Metal film 21 Substrate 22 Seed film 23 Resist 24 Mask 25 Passing part 26 Non-passing part 27 Concave part 28 Metal film 29 Removal part 30 Mold material 31 Mold 32 Convex part 33 Concave part 34 Concave part 35 Convex part

An example of a metal film pattern forming method according to the present invention will be described in detail with reference to the drawings.
FIG. 1 is an explanatory view illustrating an embodiment of a metal film pattern forming method according to the present invention. In step (a), a seed film 2 is formed on the substrate 1. As an example, the substrate 1 is a material made of silicon (Si). As an example, 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. The formation of the seed film 2 composed of these two layers is completed, and a substrate 3 having the seed film 2 formed on the substrate 1 is created (hereinafter, the substrate 3 having the seed film formed thereon is simply referred to as a substrate 3). ).

Next, in the step (b), 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. And the plastic mold 5 which moved to the downward direction bites into the curable resin composition 4 as shown in a process (c). In a state where the plastic mold 5 has digged into the curable resin composition 4, the curable resin composition 4 is irradiated with light and cured.

After curing, as shown in 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).

However, 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. When all the residual cured resin 4 ″ in the recess 8 is removed, the seed film 2 of the substrate 3 is exposed, and this exposed portion becomes the electroformed region 10.

In step (f), the electroforming region 10 is subjected to an electroforming process to form a metal film 11. After the formation of the 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. As described above, by performing steps (a) to (g), a formed product in which a metal film pattern is formed on the substrate is completed. In this embodiment, 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. In the quartz mold, 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.

Therefore, by using a plastic mold, 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. In the step (a), 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.

As shown in step (b), 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). Then, 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. When these resists are developed, 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). The

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. After the formation of the metal film 28, as shown in the step (e), 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). Through these steps, 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.

(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. Examples of 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)], polydimethylsiloxane, melamine resin, polyester Ether resin, saran resin, fluorine-based resins [for example, Cytop (Asahi Glass Co.), and other plastic materials such like.

Among the 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.

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.

In addition to 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.

For example, when a plastic mold is used, 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.

In the case of using a film-like plastic mold, 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. Further, 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. In addition, 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.

Among the methods for producing the plastic mold, 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. from the glass transition point (Tg) of the plastic, and more preferably set to a temperature of ± 30 ° 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. In the step (a), a mold material 30 is prepared, and a mold release agent is applied to the mold material 30. Thereafter, as shown in step (b), the mold 31 is disposed above the mold material 30. As an example, 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).

Then, 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. After the transfer, as shown in step (d), the mold 31 is removed from the mold 30 to produce a plastic mold 30 ′. In this 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. In this embodiment, 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. Examples of the 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. Examples of the release agent 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.

(Curable resin composition)
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.

(1) Polymerizable compound 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.

When the polymerizable polymer is contained in the curable resin composition in the present invention, the weight average molecular weight of the polymerizable polymer is preferably 500 to 5,000, and more preferably 800 to 2,000. When a polymer having a weight average molecular weight of 500 to 5,000 is used, 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, diacetone acrylamide [DAAM (manufactured by Kyowa Hakko Chemical Co., Ltd.)], N-isopropylacrylamide [NIPAM (manufactured by Kojin Co., Ltd.)], acryloylmorpholine [ACMO (Kojin Co., Ltd.) )), N, N-dimethylacrylamide [DMAA (manufactured by Kojin)], N, N-diethylacrylamide [DEAA (manufactured by Kojin)], N, N-dimethylaminopropylacrylamide [ DMAPAA (manufactured by Kojin Co., Ltd.)]], N-vinylpyrrolidone [for example, Nippon Shokubai Co., Ltd.], N-vinylcaprolactam, N-vinylcarbazole, 4-vinyl-1-cyclohexene, 2-vinyl-1 , 3-dioxolane, 4-vinyl-1,3-dioxolan-2-one, vinylene carbonate, hydroxyethylated β-naphthol Meth) acrylate, vinyl esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrene, alkylstyrenes, halostyrenes, N- vinylpyrrolidone, vinyl chloride, vinylidene chloride and the like. Here, (meth) acrylic acid represents acrylic or methacrylic acid, and (meth) acrylate represents acrylate or methacrylate. The same applies to other derivatives.

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., Ltd.)], dipropylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate [NK ester APG-200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), TPGDA (manufactured by Daicel UC Corporation)], 1,4-butanediol di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate [NK ester HD, A-HD (manufactured by Shin-Nakamura Chemical Co., Ltd.)], tetramethylene glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, bisphenol A di (Meth) acrylate, 2,2′-bis [4-{(meth) acryloxyethoxy} phenyl] propane [NK ester BPE-100 (manufactured by Shin-Nakamura Chemical Co., Ltd.)], 4,4′-bis (2 -(Meth) acryloyloxyethoxy) diphenylpropane, bisphenol A type EO (ethylene oxide) Di (meth) acrylate [NK ester BPE-200, A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd.)], 9,9-bis (3-phenyl-4- (meth) acryloylpolyoxyethoxy) fluorene , Tricyclodecane dimethanol di (meth) acrylate [NK ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.)], cyclohexane dimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, tetraacrylate, pentaerythritol divinyl ether, vinyl (meth) acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, tris (2-acryloylethyl) isocyanurate Divinyl ether, triethylene glycol divinyl ether, 2-hydroxy-1,3-dimethacryloxypropane, ethoxylated cyclohexanedimethanol diacrylate [NK ester A-CHD-4E (manufactured by Shin-Nakamura Chemical Co., Ltd.)], trimethylol Propane tri (meth) acrylate [NK ester TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), TMPTA (manufactured by Daicel UCB Co., Ltd.)] and the like.

Among these, 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.

Examples of the urethane acrylate 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.

Examples of the hydroxyl group-containing polymer include polyester polyols, polyether polyols, polycarbonate polyols and the like. Among these, polyester polyols are preferable.

Examples of the polyester polyol include polyester polyols obtained by reacting one or more dicarboxylic acids with one or more compounds having two or more hydroxyl groups. Examples of the dicarboxylic acid 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. Among these, 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. 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.

Examples of the polyfunctional isocyanate 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.

Examples of chain extenders 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.

For curing the resin composition in the present invention, moisture curing, room temperature curing or the like can be used in combination with photocuring or heat curing. Therefore, in addition to the polymerizable compound, 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 resins, existing UV curable or visible light hardened Mold adhesive [for example, 350, 352, 366, 349, 3201, 3211, 3301, 3311, 3321, 3341, 3102 to 3106 (manufactured by Henkel Loctite Co., Ltd.), 3170B, 3121, 3003, 3042, 3046 (Three Bond ( Co., Ltd.), Clear Luce MA21, OPTOKLEB OPM55 (manufactured by Adale Co., Ltd.), Aronix (manufactured by Toagosei Co., Ltd.)] and existing photosensitive resin [for example, PAK-01 (manufactured by Toyo Gosei Co., Ltd.)] NIP-K (manufactured by Zen Photonics Co., Ltd.) and SU-8 (manufactured by Microchem Co., Ltd.)]. Moreover, according to resin to contain, you may contain a thermal-polymerization initiator, a polymerization accelerator, a moisture polymerization agent, etc.

(2) Polymerization initiator 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.

One type of polymerization initiator may be used alone, or a plurality of types may be used in combination. 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.

Examples of the thermal polymerization initiator include radical polymerization initiators and ionic polymerization initiators, and radical polymerization initiators are preferred. Examples of the radical polymerization initiator include peroxides, azo compounds, persulfates, redox initiators, etc. Among these, peroxides and azo compounds are preferable.

Examples of the azo compound 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.].

Examples of peroxides include hydrogen peroxide, peroxide salts, alkyl peroxides, acyl peroxides, and peroxide esters. Specifically, 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), and the like.

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.). Among these, trichloroacetic acid, aluminum chloride, and boron trifluoride are preferable.

Examples of the anionic polymerization initiator 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. Moreover, the hardening | curing agent used for superposition | polymerization of an epoxy resin can also be used. Examples of the curing agent 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.

Examples of visible light polymerization initiators include acylphosphine oxide compounds, α-aminoalkylphenone compounds, α-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.

Among the above visible light polymerization initiators, acylphosphine oxide compounds are particularly preferable. Examples of 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-dimethoxybenzoyl) -5H-dibenzophosphole 5-oxide, 5- (1-naphthoyl) -5H-dibenzophosphole 5-oxide, 5- ( 2-toluoyl) -5H-dibenzophosphole 5-oxide, 5- (2-thenoyl) -5H-dibenzophosphole 5-oxide, 5- [5- (2'-thienyl) -2-thenoyl] -5H- Examples include dibenzophosphole 5-oxide.

Examples of the bisacylphosphine oxide 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 α-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 (described later).

As the α-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, Isakyua KIP 100F (manufactured by Lamberti Co.), and the like. The α-hydroxyalkylphenone compound is used in combination with a photosensitizer or other photopolymerization initiator.

As the 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.)].

Examples of the hydrogen abstraction type radical photopolymerization initiator include benzophenone derivatives, thioxanthone derivatives, quinone-amine photopolymerization initiators, and the like.

Examples of the benzophenone derivative 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.

Examples of the benzyl ketal type photopolymerization initiator 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.

Examples of the amine compound 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.)).

Examples of aminobenzoate compounds include ethyl 4-dimethylaminobenzoate [Darocur EBD (manufactured by Ciba Specialty Chemicals), Kayacure EPA (manufactured by Nippon Kayaku)], 2-ethylhexyl = 4-dimethylamino Benzoate [Darocur EHA (manufactured by Ciba Specialty Chemicals)], isoamyl = 4-dimethylaminobenzoate [Kayacure DMBI (manufactured by Ciba Specialty Chemicals)], and the like.

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. 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) acetonitrile [CGI1325 (Ciba Specialte) Chemicals Co., Ltd.)], [2- (Propanolsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene)-(O-tolyl) acetonitrile [CGI103 (Ciba Specialty Chemicals Co., Ltd.) )], [2- (octanesulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene)-(O-tolyl) acetonitrile [CGI108 (manufactured by Ciba Specialty Chemicals)], [2- (4-toluenesulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene)-(O-tolyl) acetonitrile [CGI121 (manufactured by Ciba Specialty Chemicals)] and the like. Can be used in combination with a photosensitizer. Moreover, it is preferable that 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 (600 to 1,000 nm) can be used alone or in combination with other polymerization initiators. For example, a combination of an organic boron compound and a near-infrared absorbing photosensitive dye can be used as a photopolymerization initiator. Specific examples include, for example, tetrabutylammonium butyltriphenylborate [P3B (manufactured by Showa Denko KK)], tetrabutylammonium butyltri (4-tert-butylphenyl) borate [BP3B (manufactured by Showa Denko KK)] And combinations of tetrabutylammonium = butyltri (4-naphthyl) borate [N3B (manufactured by Showa Denko KK)] and near-infrared absorbing dyes [IR-T and IR-13F (manufactured by Showa Denko KK)] can give.

Examples of the photosensitizer include anthracene, phenothiazene, perylene, coumarin derivatives, thiazole derivatives, thioxanthone derivatives, CT complexes (complexes of pyridinium salts and aromatic compounds), and the like.

Examples of the photopolymerization accelerator include aromatic amine compounds, aminobenzoate compounds, thioxanthone derivatives, and the like. Specifically, for example, isoamyl p-dimethylaminobenzoate [KAYACURE DMBI (made by Nippon Kayaku Co., Ltd.)], ethyl p-dimethylaminobenzoate [KAYACURE EPA (made by Nippon Kayaku Co., Ltd.)], etc. can give.

The curable resin composition in the present invention preferably contains the polymerizable compound and a visible light polymerization initiator. In this way, in particular, 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. There is. Moreover, since visible light permeate | transmits the inside of a curable resin composition, sclerosis | 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. When the pattern is a columnar object, the width of the obtained pattern is preferably 10 nm to 100 mm, and the depth is preferably 10 nm to 5 mm.

(3) Solvent The curable resin composition in the present invention may contain a solvent. When the curable resin composition contains 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. . Examples of the solvent include volatile solvents.

Examples of the volatile solvent 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). Butyl acetate, isobutyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc.), alkane solvents (eg hexane, heptane, pentane, isooctane etc.), ether solvents (eg tetrahydrofuran, dioctyl Butyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.), lactone solvents (for example, γ-butyrolactone, etc.), -Bonate solvents (eg, ethylene carbonate, propylene carbonate, etc.), alcohol solvents (eg, butanol, 2-methyl-1-propanol, 4-methyl-2-pentanol, 4-hydroxy-4-methyl-2-pentanone) Hexanol, heptanol, octanol, 3,5,5-trimethylhexanol, etc.), amine solvents (for example, triethylamine, pyridine, triethanolamine, N-methylpyrrolidone, N-methylcaprolactam, etc.). After applying the curable resin composition on the substrate on which the seed film is formed, the solvent contained in the curable resin composition may be removed by heat treatment.

(4) Other Additives 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. As the additive, for example, a polymerization inhibitor can be added for the purpose of improving the stability of the resin or suppressing / adjusting the polymerization. Specifically, hydroquinone, 2,6-di-tert-butyl-p- Examples thereof include polymerization inhibitors such as cresol, p-methoxyphenol, and sterically hindered phenol.

In addition, 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. In addition, 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. Examples of 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.

As the light stabilizer, commercially available products can be used as appropriate, for example, 2- (5-methyl-2-hydroxyphenyl) benzotriazole [TINUVIN P (manufactured by Ciba Specialty Chemicals)] 2- (2-hydroxy-3,5-di-tert-amylphenyl) -2H-benzotriazole [TINUVIN 328 (manufactured by Ciba Specialty Chemicals)], isooctyl = 3- (3-2H-benzotriazole -2-yl) -5-tert-butyl-4-hydroxyphenylpropionate [TINUVIN 384 (manufactured by Ciba Specialty Chemicals)], 2- [4- (2-hydroxy-3-dodecyloxypropyl) oxy } -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, , 5-triazine [TINUVIN400 (manufactured by Ciba Specialty Chemicals)], 2- [hydroxy-3,5-di (1,1-dimethylbenzyl) phenyl] -2H-benzotriazole [TINUVIN900 (Ciba Specialty) Chemical Co., Ltd.)], 2- [2-hydroxy-3-dimethylbenzyl-5- (1,1,3,3-tetramethylbutyl) phenyl] -2H-benzotriazole [TINUVIN 928 (Ciba Specialty) Chemical Co., Ltd.)], acrylic ester copolymer containing a sterically hindered amine light stabilizer [New Coat UVA, Vana Resin (Shin Nakamura Chemical Co., Ltd.)] and the like.

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. Examples of 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. Examples of the release agent 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.

On the other hand, in order to improve the adhesion and adhesion between the curable resin composition and the seed film in the present invention, 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.

Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane [KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)], γ-glycidoxypropylmethyldiethoxysilane [KBM-402 (Shin-Etsu Chemical). Industrial Co., Ltd.)], γ-glycidoxypropyltriethoxysilane [KBE-402 (Shin-Etsu Chemical Co., Ltd.)], vinyltrimethoxysilane [KBM-1003 (Shin-Etsu Chemical Co., Ltd.)] Vinyltriethoxysilane [KBE-1003 (manufactured by Shin-Etsu Chemical Co., Ltd.)], p-styryltrimethoxysilane [KBM-1403 (manufactured by Shin-Etsu Chemical Co., Ltd.)], γ-methacryloxypropyltrimethoxysilane [ KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)], γ-methacryloxypropylmethyldimethoxysilane [KBM-502 (Shin-Etsu Chemical Co., Ltd.)], γ-methacryloxypropyltriethoxysilane [KBE-503 (Shin-Etsu Chemical Co., Ltd.)], γ-methacryloxypropylmethyldiethoxysilane [KBE-503 (Shin-Etsu Chemical) Industrial Co., Ltd.)], γ-acryloxypropyltrimethoxysilane [KBM-5103 (Shin-Etsu Chemical Co., Ltd.)], γ-aminopropyltrimethoxysilane [KBM-903 (Shin-Etsu Chemical Co., Ltd.) )], Γ-aminopropyltriethoxysilane [KBE-903 (manufactured by Shin-Etsu Chemical Co., Ltd.)], γ-mercaptopropyltrimethoxysilane [KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)], γ-mercapto And propylmethyldimethoxysilane [KBM-802 (manufactured by Shin-Etsu Chemical Co., Ltd.)].

In addition, in order to alleviate shrinkage when the curable resin composition in the present invention is cured, 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. Further, for the purpose of suppressing curing shrinkage, an acyl group such as an acetyl group may be introduced into the hydroxyl group of the contained compound.

Furthermore, 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. Examples of 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.

Examples of 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. Examples of 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.). By containing the filler, a curable resin composition excellent in antibacterial properties, sterilization properties, antifouling properties, deodorizing properties, deodorizing properties, purifying properties and the like can be obtained.

(light source)
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.

Specific examples of 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. For example, 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. For example, 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.

It is preferable to provide 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.

(substrate)
For 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. Examples of 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. Examples of the method for providing the seed film on the substrate include sputtering.

When the seed film is provided, 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.

(Formation of metal film)
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 μm 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, and 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, in the case of 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 , and the copper cyanide plating bath is 1 to 3 A. It is preferable to carry out at a current density of / dm ² .

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.

(Removal of cured resin)
In the pattern forming method of the present invention, 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, γ-butyrolactone, propylene glycol methyl ether, propylene glycol methyl ether acetate, cyclohexanone, etc.), an alkali developing method, etc., among which ashing is preferred. After these treatments, chemical methods such as washing with water, alkaline aqueous solution [eg, 10-50% tetramethylammonium hydroxide (TMAH) aqueous solution, 1-50% sodium hydroxide aqueous solution], acidic aqueous solution are further provided. , Washing with alcohol, water-soluble compounds, etc., or physical methods such as dry ice washing, hot air, cold air or brush washing may be applied.

(Pattern formation and processed product including the pattern formation)
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, etc.

Also, a desired pattern can be formed on the substrate using the pattern formed product obtained by the pattern forming method of the present invention. Examples of 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

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

<Examples 1 to 10>
(1) Preparation of curable resin composition With the composition shown in Table 1, each component was mixed in a yellow room. The mixture was filtered through a membrane filter (0.45 μm, 25N, GL Sciences) to obtain resin compositions 1 to 8.

(Visible light polymerization initiator)
The visible light polymerization initiators shown below were used. 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) -phenyl) titanium: Irgacure 784 [Ciba Specialty Chemical Manufactured by]

(Polymerizable compound)
The following compounds were used as the polymerizable compound.
UA: 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: Tricyclodecane dimethanol diacrylate: NK ester A-DCP {Molecular weight 304 [manufactured by Shin-Nakamura Chemical Co., Ltd.]}

(2) 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 μm, 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 μm, 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.

(3) A nickel seed film (0.1 μm) was formed by sputtering on a substrate / silicon wafer (2 inch) substrate on which a seed film was formed.

(4) 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 μm.

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.

(5) 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.), and 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>
(6) Formation of nickel metal film pattern
The cured resin pattern formed product having a thickness of about 20 μm 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). By carrying out an electroforming process at a current density of ² for 2.5 hours, a nickel plating having a thickness of 15 μm was grown in the concave portion of the pattern. Next, using the RIE apparatus described above, 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.), and the ashing process is performed for 50 minutes. The remaining cured resin was completely removed to obtain a metal film pattern.

As can be seen from Table 1, 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.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on January 25, 2008 (Japanese Patent Application No. 2008-014934), the contents of which are incorporated herein by reference.

According to the present invention, 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. 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, it is possible to more easily form a metal film (mold) pattern. Become.

Claims (16)

1. A curable resin composition is applied onto a substrate on which a seed film is formed, and a 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, and the mold The curable resin composition is cured in a state where the predetermined pattern 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 to be formed is removed. A method for forming a metal film pattern, comprising forming a metal film and removing the cured resin remaining on the substrate.
2. The metal film pattern forming method according to claim 1, wherein the curable resin composition is a resin composition that is cured by light.
3. The metal film pattern forming method according to claim 1, wherein the metal film is formed by electroforming.
4. The metal film pattern forming method according to any one of claims 1 to 3, wherein the curable resin composition contains a polymerizable compound and a polymerization initiator.
5. The metal film pattern forming method according to claim 4, wherein the polymerizable compound is a polymerizable monomer.
6. The metal film pattern forming method according to claim 4, wherein the polymerizable compound is a polymerizable polymer having a weight average molecular weight of 5,000 or less, or a polymerizable monomer and a polymerizable polymer having a weight average molecular weight of 5,000 or less.
7. The metal film pattern forming method according to claim 6, wherein the polymerizable polymer having a weight average molecular weight of 5,000 or less contains urethane acrylate.
8. The method for forming a metal film pattern according to claim 7, wherein the content of urethane acrylate in the curable resin composition is 5 to 99.99 parts by weight.
9. The metal film pattern forming method according to any one of claims 4 to 8, wherein the polymerization initiator is a visible light polymerization initiator.
10. The method for forming a metal film pattern according to claim 9, wherein the visible light polymerization initiator is an acylphosphine oxide compound.
11. 11. The method for forming a metal film pattern according to claim 1, wherein the mold having the predetermined pattern is a plastic mold.
12. The method for forming a metal film pattern according to claim 11, wherein the material of the plastic mold is at least one of polyimide, polycarbonate, polypropylene, and polydimethylsiloxane.
13. 13. The method for forming a metal film pattern according to claim 1, wherein the residual cured resin is removed by an ashing process.
14. The metal film pattern forming method according to any one of claims 1 to 13, wherein the seed film is formed of a metal film.
15. A pattern formed product, wherein a pattern is formed by the method according to any one of claims 1 to 14.
16. A processed product comprising the pattern formed product according to claim 15.

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