JP2012116108A - Resin mold - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin mold, excellent in adhesiveness to a base material and in mold releasability from a transfer material resin, and capable of withstanding repeated use.SOLUTION: The resin mold for nano-imprint has a fine irregular structure on a first surface of a film base material having the first surface and a second surface in the opposite side of the first surface. A resin constituting a resin mold is composed of a cured material of a photo-polymerizable compound, and the photo-polymerizable compound contains (meth)acrylate, a fluorinated hyper branched polymer and a photopolymerization initiator.

Description

  The present invention relates to a resin mold having a fine relief structure on the surface. More specifically, the present invention relates to a resin mold containing a fluorinated hyperbranched polymer.

  The use of a member that is precisely controlled in the nano / micrometer size region greatly affects the control function in developing an optical element or biomaterial having a controlled object in the nano / micrometer size region. From the viewpoint of mass production, it is desirable that the technology for developing these elements and materials is a precision processing technology that maintains reproducibility, uniformity, and throughput while maintaining processing accuracy at the nanometer size.

  Known micro-processing techniques include, for example, a method of directly micro-processing using an electron beam and a method of batch drawing on a large area by interference exposure. Recently, fine pattern processing by a step-and-repeat method using a stepper apparatus in semiconductor technology is also known. However, each of them requires a plurality of processing steps and requires high capital investment, and it is difficult to say that the technology is good in terms of production time and cost. In addition, nanometer-size large-area processing cannot be performed by either method.

  One of the processing methods proposed for solving these problems is a nanoimprint method. This is a technique in which a member subjected to fine pattern processing is used as a mold and can be easily transferred and copied to a transfer material with processing accuracy of several nm to several tens of nm. Since it can be carried out at a low cost with a simple process, it is attracting attention as an indispensable precision replication processing technology in the industry. It is classified into thermal nanoimprint, optical nanoimprint, room temperature nanoimprint, soft lithography method, etc., depending on the physical properties of transfer materials and processing processes.

  Among these, the photo nanoimprint method using a photocurable resin is easy to apply to a roll-to-roll method process that can be quickly and repeatedly transferred while maintaining high processing accuracy, and is attractive in terms of processing accuracy and throughput. In the process, since exposure from the transfer material side or the mold side is essential, it is necessary to select a material having a high light transmittance in the ultraviolet / visible wavelength region. In particular, the material on the mold side is mainly limited to quartz, sapphire, and glass molds, and because of its rigid material, there is a problem of lack of versatility in continuous manufacturing techniques and processing processes.

  The following Patent Document 1 discloses a resin mold having transparency and flexibility as an alternative to these rigid molds. However, Patent Document 1 does not describe the adhesion between the disclosed thermoplastic resin mold and the base material.

  On the other hand, considering the cost aspect, from the master having a fine concavo-convex structure on the surface produced by the above-described electron beam drawing or the like, from the resin mold (A) as much as possible, or from the resin mold (A) by the nanoimprint method, A technique for obtaining as many resin molds (B) as possible on which the fine concavo-convex structure of the resin mold (A) is transferred is important. However, Patent Document 1 does not describe the repeated transfer durability of the disclosed thermoplastic resin mold.

JP 2006-198883 A

  The present invention has been made in view of the above-described problems of the prior art, and the problems to be solved by the present invention are excellent in adhesion to a substrate and excellent in releasability from a transfer material resin, And it is providing the resin mold which can endure repeated use.

In order to solve the above-mentioned problems, the present inventors use the easy surface segregation ability of a fluorinated hyperbranched polymer, and determine the fluorine concentration in the vicinity of the surface fine concavo-convex structure in the resin mold. By making it higher than the average fluorine concentration of the resin, the free energy on the resin surface is reduced, it is excellent in releasability from the transfer material resin, and the nano-sized size due to the low resin permeability of the fluorinated hyperbranched polymer A resin mold with excellent releasability that can easily and repeatedly transfer uneven shapes from the resin mold to the resin many times, while at the same time maintaining high free energy near the base material improves adhesion to the base material As a result, the present invention has been completed.
In addition, since the resin mold (B) produced by transferring from the resin mold (A) to the resin can also be transferred to the resin, the cost of the expensive master stamper can be absorbed, and the fluorine type to be used Since the components can be kept low, the resin mold of the present invention is also useful from the environmental aspect.

That is, the present invention is as follows.
[1] A resin mold for nanoimprinting having a fine concavo-convex structure on a first surface of a film substrate having a first surface and a second surface opposite to the first surface, the resin mold comprising: The constituent resin is composed of a cured product of a photopolymerizable compound, and the photopolymerizable compound contains (meth) acrylate, a fluorinated hyperbranched polymer, and a photopolymerization initiator. Resin mold.

[2] The ratio of the fluorine element concentration (Es) of the surface portion of the fine concavo-convex structure of the resin mold to the average fluorine element concentration (Eb) in the resin constituting the resin mold is represented by the following formula (1):
1 <Es / Eb ≦ 30000 (1)
The resin mold according to [1], wherein

  [3] The resin mold according to [1] or [2], wherein a contact angle with respect to water is 110 ° or more.

  [4] 0.05 parts by weight to 30 parts by weight of a fluorinated hyperbranched polymer and 0.01 parts by weight to 10 parts by weight of a photopolymerization initiator are contained with respect to 100 parts by weight of the (meth) acrylate. The resin mold according to any one of [1] to [3].

  [5] The resin mold according to any one of [1] to [4], wherein the photopolymerizable compound further contains a fluorine-containing (meth) acrylate.

  [6] 0.05 parts by weight to 30 parts by weight of at least fluorinated hyperbranched polymer and 0.1 parts by weight to 50 parts by weight of fluorine-containing (meth) acrylate with respect to 100 parts by weight of (meth) acrylate And the resin mold according to [5] above, containing 0.05 to 30 parts by weight of a photopolymerization initiator.

  [7] The above [1] to [6], wherein the fluorinated hyperbranched polymer contains at least one of a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group as a photopolymerizable group. The resin mold as described.

  [8] The resin mold according to any one of [1] to [7], wherein the fine concavo-convex structure has a structure with a pitch of 10 nm to 500 μm and a height of 10 nm to 10 μm.

  ADVANTAGE OF THE INVENTION According to this invention, the resin mold which is excellent in adhesiveness with a base material, is excellent in releasability with transfer material resin, and can endure repeated use can be provided.

Hereinafter, the present invention will be described in detail. In the present specification, (meth) acrylate means acrylate and / or methacrylate.
The present invention relates to a resin mold for nanoimprinting having a fine concavo-convex structure on a first surface of a film substrate having a first surface and a second surface opposite to the first surface, the resin mold And the photopolymerizable compound contains (meth) acrylate, a fluorinated hyperbranched polymer, and a photopolymerization initiator. The resin mold. The ratio of the fluorine element concentration (Es) of the surface portion of the fine uneven structure of the resin mold to the average fluorine element concentration (Eb) in the resin constituting the resin mold is preferably the following formula (1):
1 <Es / Eb ≦ 30000 (1)
Meet.

  By adding a fluorinated hyperbranched polymer to the photopolymerizable compound constituting the resin mold, the fluorine element concentration near the surface fine uneven structure is made higher than the average fluorine concentration of the resin constituting the resin mold. This reduces the free energy of the resin mold surface, and also suppresses the penetration of the resin used for transfer due to the surface packing effect of the fluorinated hyperbranched polymer, thereby releasing the resin from the transfer material resin. In addition to obtaining a resin mold with excellent releasability and excellent releasability that can easily and repeatedly transfer nanometer-sized concavo-convex shapes from resin to resin, while maintaining high free energy near the substrate Adhesiveness can be improved.

  In the present specification, the term “surface portion of the fine concavo-convex structure of the resin mold” refers to a portion invading in the thickness direction from about 1 to 10% from the surface relative to the thickness of the resin mold, or 2 nm to 20 nm in the thickness direction. It means the part that invaded. The fluorine element concentration (Es) in the surface portion of the resin mold can be quantified by the XPS method described later. The XPS X-ray penetration depth is as shallow as several nm, which is suitable for quantifying the Es value. Another analysis method includes calculating the Es / Eb ratio of the cross section of the cured product by energy dispersive X-ray spectroscopy (TEM-EDX) using a transmission electron microscope.

  Furthermore, if the fluorine element concentration (Es) on the surface of the fine concavo-convex structure of the resin mold is higher than the average fluorine element concentration (Eb) in the resin constituting the resin mold, the resin mold surface is transferred due to low free energy. A resin mold that is superior in releasability with resin and has excellent releasability and durability that can repeatedly transfer resin / resin with nanometer-sized unevenness, while at the same time increasing free energy near the base material By maintaining, the adhesiveness with the substrate can be improved.

  In this specification, the term “average fluorine element concentration (Eb) in the resin constituting the resin mold” is calculated from the charged amount or measured by a gas chromatograph mass spectrometer (GC / MS). It means the fluorine element concentration contained in the resin constituting the resin mold. For example, the concentration of elemental fluorine can be identified by subjecting a physically peeled sample of a resin mold composed of a cured product of a photopolymerizable mixture formed on a film to gas chromatography mass spectrometry.

In the present invention, the resin mold having a fine uneven structure on the surface, the ratio of the average fluorine element concentration (Eb) in the resin constituting the resin mold and the fluorine element concentration (Es) of the resin mold surface portion, Preferably, the following formula (1):
1 <Es / Eb ≦ 30000 Formula (1)
By satisfying the above, the above effect can be exhibited.
Furthermore, if it is the range of 1 <Es / Eb <= 20,000, since the usage-amount of a fluorine component can be made low, the range of 3 <= Es / Eb <= 10000 is more preferable. Moreover, in order to improve mold release, it is more preferable that the range is 5 ≦ Es / Eb ≦ 10000, and in order to improve reproducibility in repeated transfer, it is more preferable that the range is 10 ≦ Es / Eb ≦ 10000. . Further, since a high fluorine content layer can be formed on the surface while reducing the amount of fluorine used, the range of 10 ≦ Es / Eb ≦ 8000 is more preferable, and the penetration when transferring from the resin mold to the resin is effectively performed. In order to suppress it, it is more preferable that the range is 20 ≦ Es / Eb ≦ 8000. 20 ≦ Es / Eb ≦ 1000 is more preferable because the surface deterioration of the resin mold at the time of repeated transfer is further suppressed, and if it is in the range of 20 ≦ Es / Eb ≦ 500, high fluorine formed on the resin mold surface. It is further preferable because the thickness of the content layer is increased and the mold release is further improved.

  If the contact angle of water with respect to the resin mold surface is 110 ° or more, filling when transferring from the resin mold to the resin is easy, and if it is 130 ° or more, it is preferable when transferring from the resin mold to the resin. Since it becomes easy to release, it is more preferable, and if it is 140 ° or more, it is more preferable because good reproducibility upon repeated transfer from the resin mold to the resin can be obtained.

  In the resin mold, the fluorine element concentration (Es) on the resin mold surface portion is effectively made higher than the average fluorine element concentration (Eb) in the resin constituting the resin mold, and the resin mold is repeatedly transferred from the resin mold to the resin. From the viewpoint of obtaining good reproducibility, at least from a cured product of a photopolymerizable compound composed of (meth) acrylate, a fluorinated hyperbranched polymer, a photopolymerization initiator, and optionally further comprising a fluorine-containing (meth) acrylate. More preferably, it is configured.

  The fluorinated hyperbranched polymer preferably contains at least one of a vinyl group, an allyl group, an acryloyl group or a methacryloyl group as a photopolymerizable group from the viewpoint of compatibility, and the physical stability of the resin mold is improved. In order to improve, it is more preferable to contain at least one of a vinyl group, an acryloyl group or a methacryloyl group. In order to improve releasability and reproducibility when repeatedly transferring from a resin mold to a resin, an acryloyl group Or it is further more preferable that at least one of the methacryloyl groups is included.

  The method for producing the resin mold is not particularly limited, but a method for producing a resin by photopolymerization or thermal polymerization is common. Also, obtain a resin molded body by transfer by optical nanoimprint from the resin mold, obtain a new resin molded body by optical nanoimprint by regarding the resin molded body as a resin mold, and use the obtained resin molded body as a resin mold Is also possible. Hereinafter, the case of synthesizing by photopolymerization and the case of synthesizing by thermal polymerization will be sequentially described.

<Synthesis by photopolymerization>
For the photopolymerizable compound, it is preferable to use at least (meth) acrylate, a fluorinated hyperbranched polymer, and a photopolymerization initiator. Improvement in reproducibility and release during repeated transfer from resin mold to resin From the viewpoint of improvement, it is more preferable to use (meth) acrylate, a fluorinated hyperbranched polymer, a fluorine-containing (meth) acrylate, and a photopolymerization initiator. By mixing (meth) acrylate and fluorinated hyperbranched polymer together, the fluorine element concentration (Es) on the surface of the resin mold can be easily changed to the average fluorine element concentration (Eb) in the resin constituting the resin mold. Since the resin can be adjusted to be higher and the penetration of the resin during transfer from the resin mold to the resin can be suppressed, the mold release is improved.
Also, by mixing (meth) acrylate, fluorinated hyperbranched polymer, and fluorine-containing (meth) acrylate, surface segregation occurs more effectively, mold release is improved, and from resin mold to resin The durability of the resin mold during repeated transfer is improved.

Hereinafter, each component will be described.
(A) (Meth) acrylate As (meth) acrylate, there is no limitation as long as it is a polymerizable monomer other than (B) fluorinated hyperbranched polymer and (C) fluorine-containing (meth) acrylate described later, A monomer having an acryloyl group or a methacryloyl group, a monomer having a vinyl group, and a monomer having an allyl group are preferable, and a monomer having an acryloyl group or a methacryloyl group is more preferable.

  The polymerizable monomer is preferably a polyfunctional monomer having a plurality of polymerizable groups, and the number of polymerizable groups is preferably an integer of 1 to 4 because of excellent polymerizability. Moreover, when mixing and using 2 or more types of polymerizable monomers, the average number of polymeric groups has 1-3. When a single monomer is used, the number of polymerizable groups may be 3 or more in order to increase the crosslinking point after the polymerization reaction and to obtain physical stability (strength, heat resistance, etc.) of the cured product. preferable. In the case of a monomer having 1 or 2 polymerizable groups, it is preferably used in combination with monomers having different polymerizable numbers.

  Specific examples of the (meth) acrylate monomer include the following compounds: As the monomer having an acryloyl group or a methacryloyl group, (meth) acrylic acid, aromatic (meth) acrylate [phenoxyethyl acrylate, benzyl acrylate etc. ] Hydrocarbon (meth) acrylate [stearyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, allyl acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol di Acrylate, trimethylolpropane triacrylate, pentaaerythritol triacrylate, dipentaerythritol hexaacrylate and the like. ]; Hydrocarbon-based (meth) acrylates containing etheric oxygen atoms [ethoxyethyl acrylate, methoxyethyl acrylate, glycidyl acrylate, tetrahydrofurfryl acrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, polyoxyethylene glycol diacrylate , Tripropylene glycol diacrylate and the like. ]; Hydrocarbon-based (meth) acrylates containing functional groups [2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl vinyl ether, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N-vinyl pyrrolidone, dimethylaminoethyl methacrylate, etc. ]; Silicone acrylate and the like.

  Other examples of (meth) acrylate monomers include EO-modified glycerol tri (meth) acrylate, ECH-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, pentaerythritol triacrylate, EO-modified phosphate triacrylate , Trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, EO modified trimethylolpropane tri (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol Droxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, pentaerythritol ethoxytetra (Meth) acrylate, pentaerythritol tetra (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, di (meth) acrylated isocyanurate, 1,3-butylene glycol di ( (Meth) acrylate, 1,4-butanediol di (meth) acrylate, EO-modified 1,6-hexanediol di (meth) acrylate, E CH-modified 1,6-hexanediol di (meth) acrylate, allyloxy polyethylene glycol acrylate, 1,9-nonanediol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) Acrylate, modified bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, ECH modified hexahydrophthalic acid diacrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate , EO-modified neopentyl glycol diacrylate, PO-modified neopentyl glycol diacrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol, stearin Modified pentaerythritol di (meth) acrylate, ECH modified propylene glycol di (meth) acrylate, ECH modified phthalic acid di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol-tetra Methylene glycol) di (meth) acrylate, polypropylene glycol di (meth) acrylate, silicone di (meth) acrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyester (di) acrylate, polyethylene glycol Di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) a Relate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate, EO-modified tripropylene glycol di (meth) acrylate, divinylethyleneurea, divinylpropyleneurea, 2-ethyl 2-butylpropanediol acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) ) Acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acrylic acid dimer, benzy (Meth) acrylate, butanediol mono (meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, cetyl (meth) acrylate, EO-modified cresol (meth) acrylate, ethoxylated phenyl (meth) acrylate, ethyl (Meth) acrylate, dipropylene glycol (meth) acrylate, isoamyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) Acrylate, dicyclopentanyloxyethyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, methoxydipropylene glycol ( ) Acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methyl (meth) acrylate, methoxytripropylene glycol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxy polyethylene glycol ( (Meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, ECH-modified phenoxy acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, Phenoxytetraethylene glycol (meth) acrylate, phenoxyethyl (meth ) Acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, tert-butyl (meth) acrylate, Examples thereof include tribromophenyl (meth) acrylate, EO-modified tribromophenyl (meth) acrylate, and tridodecyl (meth) acrylate.

  Examples of the monomer having an allyl group include p-isopropenylphenol, and examples of the monomer having a vinyl group include styrene, α-methylstyrene, acrylonitrile, and vinylcarbazole. The EO modification means ethylene oxide modification, the ECH modification means epichlorohydrin modification, and the PO modification means propylene oxide modification.

(B) Fluorinated hyperbranched polymer Hyperbranched polymer is a dendritic polymer, dendritic polymer, multibranched polymer, multibranched polymer, dendritic polymer, dendritic polymer containing many branched structures in the polymer molecular chain. It is a polymer or the like, and in general, an ABx type compound having one functional group A in one molecule and two or more functional groups B capable of reacting with the functional group A, such as AB2 and AB3, This is a highly branched polymer that is obtained by polymerizing a compound having a polymerization point called an AB * type and a compound having one each of an initiator using a condensation, addition, or insertion reaction. In the AB * type molecule, the functional group A corresponding to the polymerization point reacts with the functional group B * serving as an initiator, and the functional group A disappears after the reaction, but B * remains as B * even after the reaction due to elimination and addition. A compound that remains reactive.

For example, in the case of the AB2 type specifically, when the functional group A is a carboxyl group, the functional group B is an amino group, and in this case, it is a hyperbranched polyamide. In the case of the AB * type, when the functional group A is a styrenic double bond, the functional group B * is a dithiocarbamate group, and in this case, hyperbranched polystyrene is obtained.
The fluorinated hyperbranched polymer according to the present invention is not particularly limited as long as it has a fluorinated group in the hyperbranched polymer structure, that is, the presence of elemental fluorine. The elemental fluorine concentration for the hyperbranched polymer should be greater than 0 atm.% And less than 80 atm.% In order to effectively increase the surface fluorine element concentration of the resin mold above the average fluorine element concentration of the resin constituting the resin mold. From the viewpoint of compatibility, it is more preferably 20 atm.% Or more and 50 atm.% Or less, which suppresses the penetration of the resin when repeatedly transferring from the resin mold to the resin, and improves the durability and release of the resin mold. From the viewpoint, it is more preferably 25 atm.% Or more and 40 atm.% Or less.

  Examples of hyperbranched polymer structures include multi-branched polyurea, multi-branched polyamide, multi-branched polyurethane, multi-branched polyester, multi-branched polyamidoamine, multi-branched polycarbonate, multi-branched polyether, multi-branched poly (ether ketone), multi-branched Examples thereof include polycarbosilane, multibranched polycarbosiloxane, multibranched polycarbosilazene, multibranched poly (propyleneimine), multibranched polyalkylamine, and copolymers thereof. Also edited by Akihiko Okada; “Science and Function of Dendrimers” (2000, published by IPC) p. 79-116, polyphenylene structure, polyester structure, polycarbonate structure, polyether structure, polythioether structure, polyetherketone structure, polyethersulfone structure, polyamide structure, polyetheramide structure, polyamidoamine structure, polyurethane structure, Examples include a polyurea structure, a polysiloxysilane structure, a polycarbosilane structure, a polyethynylene structure, a polyphenylenevinylene structure, a polyaniline structure, a polyacrylate structure, a polymethacrylate structure, a polystyrene structure, and a polyamine structure. Further, as the structure of the hyperbranched polymer, D.I. A. Tomalia, et al., “Angew. Chem. Int. Ed. Engl.”, 29, 138 (1990); , “Advanceds in Polymer Science”, Volume 143, 1 (Springer, New York) (1999); C. Salamone, Ed. , “Polymeric Materials Encyclopedia,” Volume 30, page 49 (CRC Press, New York (1996); Masaaki Enomoto, “Polymer”, Volume 47, page 804 (1998); The structures described are also included.

The fluorinated hyperbranched polymer according to the present invention is one in which a fluorine element is present at least at a part of the branched branch ends of the hyperbranched polymer, and a polyfluoroalkylene chain and / or a perfluoro (polyoxyalkylene) chain. The thing containing is preferable. A linear perfluoroalkylene group or a perfluorooxyalkylene group having an etheric oxygen atom inserted between carbon atoms and a carbon atom and having a trifluoromethyl group in the side chain is more preferred. Moreover, a linear polyfluoroalkylene chain having a trifluoromethyl group at the molecular side chain or molecular structure terminal and / or a linear perfluoro (polyoxyalkylene) chain is particularly preferred.
The polyfluoroalkylene chain is preferably a polyfluoroalkylene group having 2 to 24 carbon atoms. Moreover, the polyfluoroalkylene group may have a functional group.

The perfluoro (polyoxyalkylene) chain is a group consisting of (CF ₂ CF ₂ O) units, (CF ₂ CF (CF ₃ ) O) units, (CF ₂ CF ₂ CF ₂ O) units and (CF ₂ O) units. It is preferably composed of at least one perfluoro (oxyalkylene) unit selected from: (CF ₂ CF ₂ O) unit, (CF ₂ CF (CF ₃ ) O) unit, or (CF ₂ CF ₂ More preferably, it is composed of (CF ₂ O) units. The perfluoro (polyoxyalkylene) chain is particularly preferably composed of (CF ₂ CF ₂ O) units since the physical properties (heat resistance, acid resistance, etc.) of the fluoropolymer are excellent. The number of perfluoro (oxyalkylene) units is preferably an integer of 2 to 200, more preferably an integer of 2 to 50, because the release property and hardness of the fluoropolymer are high.

  The fluorine element concentration for the fluorinated hyperbranched polymer is more than 0 atm.% And less than 80 atm.% In order to effectively increase the surface fluorine element concentration of the resin mold to the average fluorine element concentration of the resin constituting the resin mold. From the viewpoint of compatibility, it is more preferably 20 atm.% Or more and 50 atm.% Or less. Suppression of resin permeation during repeated transfer from resin mold to resin, durability and release of resin mold. From the viewpoint of mold improvement, it is more preferably 25 atm.% Or more and 40 atm.% Or less.

  Furthermore, at least a part of the branched branch terminal of the fluorinated hyperbranched polymer contains at least one polymerizable group that can participate in a crosslinking reaction by light or heat, from the viewpoint of physical durability of the resin mold. Is more preferable. Examples of the photopolymerizable group include acryloyl group, methacryloyl group, acryloxy group, methacryloxy group, vinyl group, epoxy group, allyl group, and oxetanyl group. From the viewpoint of compatibility, acryloyl group, methacryloyl group, acryloxy group, methacryloxy group, and vinyl group are preferable. From the viewpoint of physical stability of the resin mold, acryloyl group, methacryloyl group, acryloxy group, methacryloxy group, and vinyl group are more preferable. An acryloxy group and a methacryloxy group are more preferable from the viewpoint of improving mold release of the resin mold accompanying repeated transfer. Moreover, you may have the cationically polymerizable group represented by the epoxy group and the oxetanyl group. Furthermore, you may have a hydrolyzable silyl group represented by the alkoxy silyl group and the acyloxy silyl group as a thermally polymerizable group.

The fluorinated hyperbranched polymer preferably contains at least one of a vinyl group, an allyl group, an acryloyl group or a methacryloyl group as a photopolymerizable group from the viewpoint of compatibility, and the physical stability of the resin mold is improved. In order to improve, it is more preferable to contain at least one of a vinyl group, an acryloyl group or a methacryloyl group. In order to improve releasability and reproducibility when repeatedly transferring from a resin mold to a resin, an acryloyl group Or it is further more preferable that at least 1 of a methacryloyl group is included.
The polymerizable groups may be the same or different and may contain, for example, at least one polymerizable group selected from the group consisting of a radical polymerizable group, a cationic polymerizable group, and a hydrolyzable silyl group.

  In the hyperbranched polymer according to the present invention, the weight average molecular weight Mw measured in terms of polystyrene by gel permeation chromatography is preferably 500 or more and 5,500,000 or less from the viewpoint of compatibility. From the viewpoint of stability, it is more preferably from 1,000 to 1,500,000, and from the viewpoint of effective surface segregation property of the fluorinated hyperbranched polymer, from 1,500 to 650,000. More preferably it is. In order to improve the compatibility, a diluting solvent may be used. As a dilution solvent, the solvent whose boiling point of a single solvent is 40 to 180 degreeC is preferable, 60 to 180 degreeC is more preferable, and 60 to 140 degreeC is further more preferable. Two or more kinds of diluents may be used. The solvent content may be at least an amount that can be dispersed in the curable resin composition, preferably more than 0 parts by weight to 50 parts by weight with respect to 100 parts by weight of the curable composition, and limit the amount of residual solvent after drying. Considering removal, more than 0 parts by weight to 10 parts by weight is more preferable.

(C) Fluorine-containing (meth) acrylate The fluorine-containing (meth) acrylate is not particularly limited as long as it is a (meth) acrylate containing a fluorine element in the molecule, but a polyfluoroalkylene chain and / or perfluoro (polyoxyalkylene) ) Chain and a polymerizable group, preferably a linear perfluoroalkylene group or a perfluorooxyalkylene group having an etheric oxygen atom inserted between carbon atoms and carbon atoms and having a trifluoromethyl group in the side chain Is more preferable. Further, a linear polyfluoroalkylene chain having a trifluoromethyl group at the molecular side chain or molecular structure terminal and / or a linear perfluoro (polyoxyalkylene) chain is particularly preferred.

The polyfluoroalkylene chain is preferably a polyfluoroalkylene group having 2 to 24 carbon atoms. Moreover, the polyfluoroalkylene group may have a functional group.
The perfluoro (polyoxyalkylene) chain is composed of (CF ₂ CF ₂ O) units, (CF ₂ CF (CF ₃ ) O) units, (CF ₂ CF ₂ CF ₂ O) units, and (CF ₂ O) units. It is preferably composed of at least one perfluoro (oxyalkylene) unit selected from the group, and is a (CF ₂ CF ₂ O) unit, (CF ₂ CF (CF ₃ ) O) unit, or (CF ₂ CF it is more preferably composed of ₂ CF ₂ O) units. The perfluoro (polyoxyalkylene) chain is particularly preferably composed of (CF ₂ CF ₂ O) units since the physical properties (heat resistance, acid resistance, etc.) of the fluoropolymer are excellent. The number of perfluoro (oxyalkylene) units is preferably an integer of 2 to 200, more preferably an integer of 2 to 50, because the release property and hardness of the fluoropolymer are high.

  As the polymerizable group, a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an epoxy group, a dichitacene group, a cyano group or an isocyanate group is preferable, and a vinyl group, an acryloyl group or a methacryloyl group is more preferable. More preferred is an acryloyl group or a methacryloyl group.

The number of polymerizable groups is preferably an integer of 1 to 4 and more preferably an integer of 1 to 3 because of excellent polymerizability. When using 2 or more types of compounds, as for the average number of polymeric groups, 1-3 are preferable.
When the fluorine-containing (meth) acrylate has a functional group, it has excellent adhesion to the transparent substrate. Examples of the functional group include a carboxyl group, a sulfonic acid group, a functional group having an ester bond, a functional group having an amide bond, a hydroxyl group, an amino group, a cyano group, a urethane group, an isocyanate group, and a functional group having an isocyanuric acid derivative. It is done. In particular, it preferably contains at least one functional group having a carboxyl group, a urethane group, or an isocyanuric acid derivative. The isocyanuric acid derivatives include those having an isocyanuric acid skeleton in which at least one hydrogen atom bonded to a nitrogen atom is substituted with another group.

Specific examples of the fluorine-containing (meth) acrylate include the following compounds: CH ₂ ═CHCOO (CH ₂ ) ₂ (CF ₂ ) ₁₀ F, CH ₂ ═CHCOO (CH ₂ ) ₂ (CF ₂ ) ₈ F CH ₂ = CHCOO (CH ₂ ) ₂ (CF ₂ ) ₆ F, CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₂ (CF ₂ ) ₁₀ F, CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₂ (CF ₂ ) ₈ F, CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₂ (CF ₂ ) ₆ F, CH ₂ = CHCOOCH ₂ (CF ₂ ) ₆ F, CH ₂ = C (CH ₃ ) _{COOCH 2 (CF 2) 6 F} , CH 2 = CHCOOCH 2 (CF 2) 7 F, CH 2 = C (CH 3) COOCH 2 (CF 2) 7 F, CH 2 = CHCOOCH 2 CF 2 CF 2 H _{CH 2 = CHCOOCH 2 (CF 2} CF 2) 2 H, CH 2 = CHCOOCH 2 (CF 2 CF 2) 4 H, CH 2 = C (CH 3) COOCH 2 (CF 2 CF 2) H, CH 2 = C _{(CH 3) COOCH 2 (CF} 2 CF 2) 2 H, CH 2 = C (CH 3) COOCH 2 (CF 2 CF 2) 4 H, CH 2 = CHCOOCH 2 CF 2 OCF 2 CF 2 OCF 3, CH 2 _{= CHCOOCH 2 CF 2 O (CF} 2 CF 2 O) 3 CF 3, CH 2 = C (CH 3) COOCH 2 CF 2 OCF 2 CF 2 OCF 3, CH 2 = C (CH 3) COOCH 2 CF 2 O ( _{CF 2 CF 2 O) 3 CF} 3, CH 2 = CHCOOCH 2 CF (CF 3) OCF 2 CF (CF 3) O (CF 2) 3 F, CH 2 = _{CHCOOCH 2 CF (CF 3) O} (CF 2 CF (CF 3) O) 2 (CF 2) 3 F, CH 2 = C (CH 3) COOCH 2 CF (CF 3) OCF 2 CF (CF 3) O ( _{CF 2) 3 F, CH 2} = C (CH 3) COOCH 2 CF (CF 3) O (CF 2 CF (CF 3) O) 2 (CF 2) 3 F, CH 2 = CFCOOCH 2 CH (OH) CH ₂ (CF ₂ ) ₆ CF (CF ₃ ) ₂ , CH ₂ = CFCOOOCH ₂ CH (CH ₂ OH) CH ₂ (CF ₂ ) ₆ CF (CF ₃ ) ₂ , CH ₂ = CFCOOCH ₂ CH (OH) CH ₂ ( _{CF 2) 10 F, CH 2} = CFCOOCH 2 CH (OH) CH 2 (CF 2) 10 F, CH 2 = CHCOOCH 2 CH 2 (CF 2 CF 2) 3 CH 2 CH 2 OCO _{H = CH 2, CH 2 =} C (CH 3) COOCH 2 CH 2 (CF 2 CF 2) 3 CH 2 CH 2 OCOC (CH 3) = CH 2, CH 2 = CHCOOCH 2 CyFCH 2 OCOCH = CH 2, CH ₂ = C (CH ₃ ) COOCH ₂ CyFCH ₂ OCOC (CH ₃ ) = fluoro (meth) acrylate such as CH ₂ (where CyF represents perfluoro (1,4-cyclohexylene group)). ), CF ₂ = CFCF ₂ CF = CF ₂ , CF ₂ = CFOCF ₂ CF = CF ₂ , CF ₂ = CFOCF ₂ CF ₂ CF = CF ₂ , CF ₂ = CFOCF (CF ₃ ) CF ₂ CF = CF ₂ , CF _{2 = CFOCF 2 CF (CF 3} ) CF = CF 2, CF 2 = CFOCF 2 OCF = CF 2, CF 2 = CFOCF 2 CF (CF 3) OCF 2 CF = CF 2, CF 2 = CFCF 2 C (OH) (CF ₃ ) CH ₂ CH═CH ₂ , CF ₂ = CFCF ₂ C (OH) (CF ₃ ) CH═CH ₂ , CF ₂ = CFCF ₂ C (CF ₃ ) (OCH ₂ OCH ₃ ) CH ₂ CH═CH ₂ , fluorodiene such as CF ₂ ═CFCH ₂ C (C (CF ₃ ) ₂ OH) (CF ₃ ) CH ₂ CH═CH ₂ .

  A fluorine-containing (meth) acrylate may be used individually by 1 type, and may use 2 or more types together. Further, it can be used in combination with surface modifiers such as abrasion resistance, scratch resistance, fingerprint adhesion prevention, antifouling property, leveling property and water / oil repellency. For example, “Factent” manufactured by Neos Co., Ltd. (for example, M series: Futgent 251, Futgent 215M, Futgent 250, FTX-245M, FTX-290M; S series: FTX-207S, FTX-211S, FTX-220S FTX-230S; F Series: FTX-209F, FTX-213F, Footage 222F, FTX-233F, Footage 245F; G Series: Footent 208G, FTX-218G, FTX-230G, FTS-240G; Oligomer Series: Footer Gent 730FM, tergent 730LM; tergent P series; tergent 710FL; FTX-710HL, etc.), DIC's "Megafuck" (for example, F-114, F-410, F-4) 3, F-494, F-443, F-444, F-445, F-470, F-471, F-474, F-475, F-477, F-479, F-480SF, F-482, F-483, F-489, F-172D, F-178K, F-178RM, MCF-350SF, etc., “Optool (registered trademark)” (for example, DSX, DAC, AES, for example, OPTOOL DAC HP, manufactured by Daikin) ), “Eftone (registered trademark)” (for example, AT-100), “Zeffle (registered trademark)” (for example, GH-701), “Unidyne (registered trademark)”, “Daifree (registered trademark)”, “ “Optoace (registered trademark)”, “Novec EGC-1720” manufactured by Sumitomo 3M Limited, “Fluorosurf” manufactured by Fluoro Technology Co., Ltd., and the like.

The fluorine-containing (meth) acrylate preferably has a molecular weight _Mw of 50 to 50,000. From the viewpoint of compatibility, the molecular weight _Mw is preferably 50 to 5000, and the molecular weight _Mw is 100 to 5000. More preferred. When using a high molecular weight having low compatibility, a diluting solvent may be used. As a dilution solvent, the solvent whose boiling point of a single solvent is 40 to 180 degreeC is preferable, 60 to 180 degreeC is more preferable, and 60 to 140 degreeC is further more preferable. Two or more kinds of diluents may be used. The solvent content may be at least an amount that can be dispersed in the curable resin composition, preferably more than 0 parts by weight to 50 parts by weight with respect to 100 parts by weight of the curable composition, and limit the amount of residual solvent after drying. Considering removal, more than 0 parts by weight to 10 parts by weight is more preferable.

(D) Photopolymerization initiator The photopolymerization initiator causes a radical reaction or an ionic reaction by light, and a photopolymerization initiator that causes a radical reaction is preferable. Examples of the photopolymerization initiator include the following photopolymerization initiators:
Acetophenone-based photopolymerization initiators: acetophenone, p-tert-butyltrichloroacetophenone, chloroacetophenone, 2,2-diethoxyacetophenone, hydroxyacetophenone, 2,2-dimethoxy-2′-phenylacetophenone, 2-aminoacetophenone, dialkyl Aminoacetophenone, etc .;
Benzoin-based photopolymerization initiators: benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-2-methyl Propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyldimethyl ketal and the like;
Benzophenone-based photopolymerization initiators: benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxypropylbenzophenone, acrylic benzophenone, 4,4'-bis (dimethylamino) ) Benzophenone, perfluorobenzophenone, etc .;
Thioxanthone-based photopolymerization initiators: thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, diethylthioxanthone, dimethylthioxanthone, etc .;
Anthraquinone-based photopolymerization initiators: 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone;
Ketal photoinitiators: acetophenone dimethyl ketal, benzyl dimethyl ketal;
Other photopolymerization initiators: α-acyloxime ester, benzyl- (o-ethoxycarbonyl) -α-monooxime, acylphosphine oxide, glyoxyester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, tetramethylthiuram Sulfide, azobisisobutyronitrile, benzoyl peroxide, dialkyl peroxide, tert-butyl peroxypivalate, etc .;
Photopolymerization initiator having a fluorine atom: perfluoro tert-butyl peroxide, perfluorobenzoyl peroxide or the like.
These publicly known photopolymerization initiators can be used alone or in combination of two or more.

  The photopolymerizable compound may contain a photosensitizer. Specific examples of the photosensitizer include n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, s-benzisothiuronium-p-toluenesulfinate, triethylamine, diethylaminoethyl methacrylate. , Triethylenetetramine, 4,4′-bis (dialkylamino) benzophenone, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, tri Known and commonly used photosensitizers such as amines such as ethanolamine can be used, and one or more of these can be used in combination.

Examples of commercially available initiators include “IRGACURE” manufactured by Ciba (for example, IRGACURE 651, 184, 500, 2959, 127, 754, 907, 369, 379, 379EG, 819, 1800, 784, OXE01, OXE02 ) And “DAROCUR” (for example, DAROCUR 1173, MBF, TPO, 4265).
A photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more types. When using 2 or more types together, it is good to select from the viewpoint of the dispersibility of fluorine-containing (meth) acrylate, the fine concavo-convex structure surface portion of the photopolymerizable mixture, and the internal curability. For example, the combined use of an α-hydroxyketone photopolymerization initiator and an α-aminoketone photopolymerization initiator can be mentioned. In addition, as a combination in the case of using two types together, for example, “Irgacure” manufactured by Ciba, “Irgacure” and “Darocure” are combined as Darocure 1173 and Irgacure 819, Irgacure 379 and Irgacure 127, Irgacure 8e1 Irgacure 184 and Irgacure 369, Irgacure 184 and Irgacure 379EG, Irgacure 184 and Irgacure 907, Irgacure 127 and Irgacure 379EG, Irgacure 819 and Irgacure 184, and Dracurure 184
The photopolymerizable compound contains 0.05 to 30 parts by weight of a fluorinated hyperbranched polymer and 0.01 to 10 parts by weight of a photopolymerization initiator with respect to 100 parts by weight of (meth) acrylate. Is a mixture.

  If the fluorinated hyperbranched polymer is 0.01 parts by weight or more with respect to 100 parts by weight of (meth) acrylate, it is excellent in releasability, and if it is 30 parts by weight or less, it has excellent adhesion to the substrate. In particular, when it is 0.1 to 25 parts by weight, it is excellent in mold release when it is repeatedly transferred from the resin mold to the resin due to the low resin permeability of the fluorinated hyperbranched polymer. More preferably, it is 1 to 15 parts by weight. In addition, the photopolymerization initiator is excellent in polymerizability if it is 0.01 parts by weight or more with respect to 100 parts by weight of (meth) acrylate, and if it is 10 parts by weight or less, it starts unreacted after curing. Bleed-out can be reduced to the resin surface of the agent and decomposition product, and if it is 0.5 to 5 parts by weight, the resin permeability after curing is excellent.

  In addition, fluorine-containing (meth) acrylate is added to the photopolymerizable compound, and 0.05 to 30 parts by weight of fluorine-containing hyperbranched polymer is added to 100 parts by weight of (meth) acrylate. A photopolymerizable compound containing 0.1 to 50 parts by weight of (meth) acrylate and 0.05 to 30 parts by weight of a photopolymerization initiator may be used.

  If the fluorinated hyperbranched polymer is 0.01 parts by weight or more with respect to 100 parts by weight of (meth) acrylate, it is excellent in releasability, and if it is 30 parts by weight or less, it has excellent adhesion to the substrate. If it is 0.1 to 25 parts by weight, it is excellent in mold release when it is repeatedly transferred from the resin mold to the resin due to the low resin permeability of the fluorinated hyperbranched polymer. More preferably, it is 1 to 15 parts by weight. In addition, if the fluorine-containing (meth) acrylate is 0.1 parts by weight or more, it is excellent in releasability, and if it is 50 parts by weight or less, it is excellent in adhesion to the substrate, and 0.5 to 20 parts by weight. If present, the compatibility and surface segregation of the fluorine-containing (meth) acrylate are excellent. More preferably, it is 1 to 20 parts by weight. The photopolymerization initiator is excellent in polymerizability if it is 0.01 parts by weight or more with respect to 100 parts by weight of (meth) acrylate, and if it is 10 parts by weight or less, an unreacted initiator after curing and Bleed-out to the resin surface of the decomposition product can be reduced, and if it is 0.5 to 5 parts by weight, the resin permeability after curing is excellent.

(E) Resin mold Hereinafter, the resin mold is expressed as F. Where the pattern shape or the inverted shape of the pattern shape is described, it is expressed as unevenness or uneven pattern, and among them, the resin mold according to the present invention having the uneven pattern shape is expressed as F (+), and F (+). The resin mold having a concavo-convex pattern transferred from is denoted as F (−).

  In the present invention, a resin mold can be formed by using a cured product of a photopolymerizable compound (hereinafter referred to as curable resin composition). The resin mold is a first pattern obtained by optical nanoimprint transfer using a curable resin composition as a transfer agent from a master mold having a fine pattern on the surface and a fine concavo-convex structure on the surface, and the opposite side to the first surface It is the resin molding which comprised the fine concavo-convex structure on the 1st surface of the film base material which has a 2nd surface located in this. Further, in the present invention, the resin mold can be easily and repeatedly transferred using not only the curable resin composition according to the present invention but also the known photosensitive resin composition using a resin molded body. It is defined as a mold. Here, “repetitive transfer” includes at least one of the following two meanings ((1) and (2)). (1) It means that a plurality of transferred concavo-convex pattern transfer products can be produced from an F (+) resin mold having a concavo-convex pattern shape. (2) In particular, when a curable resin composition is used as a transfer agent, an inverted F (−) resin mold is obtained from the resin mold F (+), and then the reverse transfer is performed using the F (−) resin mold as a mold. It means that the pattern inversion / transfer can be repeated repeatedly to obtain the F (+) resin mold.

(Contact angle)
If the water contact angle to the resin mold is 110 ° or more, filling when transferring from the resin mold to the resin is easy, and if it is 130 ° or more, separation when transferring from the resin mold to the resin is preferable. It is more preferable because the mold becomes easy, and if it is 140 ° or more, it is still preferable because good reproducibility can be obtained when it is repeatedly transferred from the resin mold to the resin.
In addition, the contact angle with respect to water was measured for each water drop by placing the water drop on three measurement surfaces on the base material according to JIS R3257 “Testing method for wettability of substrate glass surface” by the static drop method. The droplet was 2 μL / droplet, and the measurement was performed at 20 ° C. As the contact angle, an average value (n = 3) of three measured values is used.

(Fine uneven pattern shape)
The surface of the resin mold is a structure obtained by transferring the shape of the master mold, and has a fine uneven structure. A structure suitable for an optical member, a bio member, a micro / nano channel member, a heat member, etc. is preferable, a lattice shape, a pillar or hole structure, a line and space structure, etc. are more preferable, and a plurality of these structures are included. May be. In addition, the uneven shape of the cross section may be a rectangle, a square, a trapezoid, a rhombus, a hexagon, a triangle, a circle, a shape having a curvature, or the like. Further, the pattern arrangement may be either a random arrangement shape or a periodically arranged pattern shape. In particular, in the case of a pattern in which patterns are periodically arranged, the periodic pitch size is preferably 10 nm to 500 μm, more preferably 30 nm to 100 μm, and even more preferably 50 nm to 10 μm. The uneven pattern height is preferably 10 nm to 10 μm, and more preferably 30 nm to 5 μm. Furthermore, the aspect ratio of the convex or concave cross-sectional shape is preferably 0.5 to 10, and more preferably 1 to 5. The aspect ratio here is defined as a value (a / b) obtained by dividing the height (a) of the convex or concave sectional shape by the half width (b) at the height position of b / 2.

  For the convex part cross-sectional area (S convex part) of the material to be transferred (master mold or resin mold) used as a mold, the inverted transfer molded product (general-purpose photosensitive resin or photopolymerizable compound according to the present invention) It is preferable to use a mold or a transfer material that can be transferred with a transfer area accuracy of 80% or more with a cross-sectional area of the recess (S recess) having a cross-sectional area ratio (S recess / S protrusion × 100). In particular, when the resin mold is used as a mold, the transfer accuracy is more preferably 80% or more. Furthermore, in order to maintain high transfer accuracy by repeated reversal transfer such as unevenness / concave / concave / concave / concave / recessed, the transfer accuracy at one time is preferably 85% or more, more preferably 90% or more. preferable.

(Master mold)
The master mold has a fine concavo-convex pattern on the surface, and examples of the material include quartz glass, ultraviolet transmissive glass, sapphire, diamond, polydimethylsiloxane, and other silicone materials, fluororesin, silicon wafer, SiC substrate, mica substrate, and the like. It is done. In order to further improve the releasability during pattern transfer, a release treatment may be performed. As the release treatment agent, a silane coupling release agent is preferable, and a fluorine-containing release agent is more preferable. Examples of commercially available mold release agents include OPTOOL DSX manufactured by Daikin Industries, Durasurf HD1101 and HD2101, Novec manufactured by Sumitomo 3M Limited, and the like.

(F) Manufacturing method of resin mold By performing the following processes 11-14 in order, a resin mold can be produced from a master mold using the curable resin composition according to the present invention as a transfer agent.
Process 11: The process of apply | coating curable resin composition on a board | substrate (process of apply | coating resin).
Step 12: A step of pressing the curable resin composition against the master mold in the above step 11 (step of pressing the resin against the mold).
Step 13: A step of radically polymerizing the curable resin composition in Step 12 to obtain a cured product (a step of photocuring the resin).
Step 14: A step of peeling the cured product from the master mold to obtain a resin mold (F) having an inverted shape of the pattern shape of the master mold (a step of peeling the cured product from the mold).

By performing the following steps 21 to 28 in order, a resin mold (F) having an uneven pattern shape that is the same as the uneven pattern shape of the master mold can be manufactured.
Step 21: A step of applying a curable resin composition on a substrate (a step of applying a resin).
Step 22: A step of pressing the curable resin composition against the master mold in the above step 21 (step of pressing the resin against the mold).
Step 23: a step of radically polymerizing the curable resin composition in Step 22 to obtain a cured product (a step of photocuring the resin).
Step 24: A step of peeling the cured product from the master mold in the step 23 to obtain a resin mold (F (+)) having a reverse shape of the master mold shape (a step of peeling the cured product from the mold).
Process 25: The process of apply | coating curable resin composition on a board | substrate (process of apply | coating resin).
Step 26: A step of pressing the curable resin composition onto the resin mold (F (+)) in the above step 25 (step of pressing the resin against the mold).
Step 27: a step of radically polymerizing the curable resin composition in Step 26 to obtain a cured product (a step of photocuring the resin).
Step 28: A step of removing the cured product from the resin mold (F (+)) in the above step 27 to obtain a resin mold (F (−)) having the same pattern shape as that of the master mold (molding the cured product as a mold) The process of peeling from.

By performing the following steps 31 to 34 in sequence, a resin transfer product having the above inverted shape can be produced from a resin mold using a known and commonly used photosensitive resin composition as a transfer agent.
Process 31: The process of apply | coating a well-known and usual photosensitive resin composition on a board | substrate (process of apply | coating resin).
Step 32: A step of pressing the photosensitive resin composition to the resin mold in the step 31 (step of pressing the resin against the mold).
Step 33: A step of radically polymerizing the photosensitive resin composition in Step 32 to obtain a cured product (a step of photocuring the resin).
Step 34: A step of peeling the cured product from the resin mold in the step 33 to obtain a transfer product having a pattern shape and an inverted shape of the resin mold (F) (step of peeling the cured product from the mold).

By performing the following steps 41 to 47 in order, a resin roll stamper obtained by processing a resin molded body into a roll shape can be manufactured.
Step 41: A step of applying a curable resin composition on a substrate (step of applying a resin).
Step 42: A step of pressing the curable resin composition against the master mold in the above step 41 (step of pressing the resin against the mold).
Step 43: A step of radically polymerizing the curable resin composition in Step 42 to obtain a cured product (a step of photocuring the resin).
Step 44: A step of peeling the cured product from the master mold in the above step 43 to obtain a resin mold (F (+)) having an inverted shape of the master mold shape (step of peeling the cured product from the mold).
Step 45: A step of sandwiching the curable resin composition between the resin mold (F (+)) prepared in the above step 44 and the roll base (a step of pressing the resin against the mold).
Step 46: Step of photocuring the curable resin composition in the step 45 to obtain a cured product (step of photocuring the resin).
Step 47: Step of removing the cured product from the resin mold (F (+)) in the above step 47 to obtain a resin roll stamper (F (−)) having the same pattern shape as the pattern shape of the master mold (cured product) Step of peeling off from the mold).

By performing the following steps 51 to 54 in order, roll-to-roll type continuous transfer using the photosensitive resin composition as a transfer agent can be performed using the resin roll stamper molded body produced in the order of the above steps 41 to 47. . In particular, when the curable resin composition according to the present invention is used as a transfer agent, a continuously transferred transfer product can be used as a resin continuous molded body.
Process 51: The process of apply | coating the photosensitive resin composition on a board | substrate (process of apply | coating resin).
Step 52: A step of pressing the photosensitive resin composition to the resin roll stamper in the above step 51 (step of pressing the resin against the mold).
Step 53: A step of radically polymerizing the photosensitive resin composition in Step 52 to obtain a cured product (a step of photocuring the resin).
Step 54: A step in which the cured product is peeled from the resin mold (F) in the above step 53, and a transfer product having a pattern shape and an inverted shape of the resin mold (F) can be continuously produced (the cured product is peeled from the mold). Process).

By sequentially performing the following steps 61 to 64, the pattern shape can be continuously transferred from the continuum to the continuum using the resin continuous molded bodies prepared in the order of the above steps 51 to 54.
Process 61: The process of apply | coating the photosensitive resin composition on a board | substrate (process of apply | coating resin).
Step 62: A step of pressing the photosensitive resin composition to the resin continuous molded body (F) in the above step 61 (step of pressing the resin against the mold).
Step 63: A step of obtaining a cured product by photoradical polymerization of the photosensitive resin composition in the step 62 (step of photocuring the resin).
Step 64: The step of peeling off the cured product from the resin mold (F) continuous molded body in the above-mentioned step 63 and continuously producing a transfer product having a reverse shape of the pattern shape of the resin mold (F). Step of peeling from the mold).

Hereinafter, each process described above will be described in detail.
(Process of applying resin composition to substrate)
As a method of applying the resin composition on the substrate, casting method, potting method, spin coating method, roller coating method, bar coating method, cast method, dip coating method, die coating method, Langmuir projet method, spray coating method, Examples include an air knife coating method, a flow coating method, and a curtain coating method. The coating thickness of the curable resin composition is preferably 50 nm to 5 mm, more preferably 80 nm to 200 μm, and still more preferably 100 nm to 100 μm.

  When the substrate is larger than the master mold or the resin mold, the resin composition may be applied to the entire surface of the substrate, or the resin composition is present only in a range where the master mold or the resin mold is embossed. May be applied to part of the substrate.

  After the resin composition is applied to the substrate, it is pre-baked to remove the solvent when it contains a solvent, or to migrate the surface of the internally added fluorinated hyperbranched polymer and / or fluorine-containing polymerizable (meth) acrylate. Can be promoted. When the master mold or the resin mold is pressed by segregating the fluorinated hyperbranched polymer and / or fluorine-containing polymerizable (meth) acrylate added to the surface, the fluorinated hyperbranched polymer and / or Or the fluorine-containing polymerizable (meth) acrylate is efficiently filled inside the microstructure of the master mold or the resin mold, and not only suppresses the deterioration of the master mold or the resin mold, but also the surface fluorine element concentration ( The value Es / Eb obtained by dividing Es) by the bulk fluorine element concentration (Eb) can be greatly improved, and the releasability can be improved. The temperature is preferably 20 ° C to 120 ° C, more preferably 25 ° C to 100 ° C, further preferably 30 ° C to 100 ° C, and most preferably 50 ° C to 100 ° C. The prebake time is preferably 30 seconds to 30 minutes, more preferably 1 minute to 15 minutes, and even more preferably 2 minutes to 10 minutes.

  There is no restriction | limiting in particular regarding the material of a board | substrate, It can use regardless of organic materials, such as inorganic materials, such as glass, a ceramic, a metal, and a plastics. Depending on the application of the molded body, a plate, a surface having a curvature, a sheet, a film, a thin film, a woven fabric, a non-woven fabric, and other arbitrary shapes or composites thereof can be used. It is particularly preferred to include excellent sheets, films, thin films, woven fabrics, non-woven fabrics and the like. Examples of flexible materials include polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, cycloolefin resin (COP), cross-linked polyethylene resin, polyvinyl chloride resin, polyacrylate resin, polyphenylene ether resin, and modified polyphenylene ether resin. Amorphous thermoplastic resins such as polyetherimide resin, polyether sulfone resin, polysulfone resin, polyether ketone resin, polyethylene terephthalate (PET) resin, polyethylene naphthalate resin, polyethylene resin, polypropylene resin, polybutylene terephthalate Crystalline thermoplastic resins such as resins, aromatic polyester resins, polyacetal resins, polyamide resins, and ultraviolet (UV) hard materials such as acrylic, epoxy, and urethane RESIN or thermosetting resins. Moreover, a base material can also be comprised by combining ultraviolet curable resin and thermosetting resin, inorganic board | substrates, such as glass, the said thermoplastic resin, and a triacetate resin, or using independently.

  It is preferable to perform the process which improves the adhesiveness of a board | substrate and a resin composition. For example, on the surface to be bonded, chemical bonding with the resin composition, easy adhesion coating for physical bonding such as penetration, primer treatment, corona treatment, plasma treatment, UV / ozone treatment, high energy ray irradiation treatment It is preferable to perform surface roughening treatment, porosification treatment, and the like.

(Step of pressing the resin composition against the substrate)
It is preferable that a highly flexible substrate is gently coated on a mold (a master mold, a resin mold, a resin roll stamper, etc.) from the end so as to prevent bubbles from entering and pressed under a certain pressure. The press pressure at the time of pressing is preferably more than 0 MPa to 10 MPa, more preferably 0.01 MPa to 5 MPa, and further preferably 0.01 MPa to 1 MPa.

(Process for photocuring resin)
When the light transmittance of the master mold is low, it is preferable to expose from the substrate side. On the other hand, when the master mold has a high transmittance for light of an ultraviolet wavelength, for example, in the case of a synthetic quartz material, it is preferable to expose from at least one side of the substrate side or the master mold side. It is more preferable to expose from both sides. When a resin mold is used, it is preferable to expose from at least one side of the substrate side or the resin mold (F) side, and more preferable to expose from both the substrate side and the resin mold (F) side. Instead of using a substrate, only the curable resin composition may be applied to the master mold and cured. In that case, in order to prevent polymerization inhibition due to oxygen, the cured product is removed by a method of exposing in a nitrogen atmosphere or an argon atmosphere, coating with a substrate with low adhesion, and peeling off the substrate and the resin mold after curing. Can be manufactured.

As an exposure light source to be used, a metal halide lamp, a high-pressure mercury lamp, a chemical lamp, or a UV-LED is preferable. From the viewpoint of suppressing heat generation during long-time exposure, it is preferable to use a filter (including a band-pass filter) that cuts a wavelength longer than the visible wavelength. As integrated light quantity is preferably 300 mJ / cm ² or more at a wavelength of 365 nm, in order to obtain a high cured reactive rate (E), preferably 800 mJ / cm ² or ^more, more preferably 800mJ / cm ² ~6000mJ / cm 2 In order to prevent resin degradation due to light, 800 mJ / cm ^{2 to} 3000 mJ / cm ² is particularly preferable.

  Regardless of the thickness of the cured product, the total light transmittance at 350 nm to 450 nm is preferably 50% or more, and more preferably 70% or more for efficient photoreaction. When the thickness of the cured product is more than 0 nm to 50 μm, the total light transmittance at 350 nm to 450 nm is preferably 50% or more, and more preferably 70% or more.

(Process of peeling the cured product from the mold)
When the master mold has flexibility, it is preferable to peel at a constant rate from at least one of the mold surface side or the substrate surface side. As the peeling method, wire peeling is preferable. For example, in the case of a material having a high master mold rigidity, particularly an inorganic material, if the master mold is peeled off from the master mold side, the peeled area is partially increased due to surface peeling, and there is a concern that the cured product may be damaged. Therefore, it is preferable to peel from the flexible substrate side. As for the peeling speed, linear peeling at a constant speed from a specific direction at a speed of more than 0 m / min to 5 m / min is preferable in that the risk of damage to the cured product can be reduced.

  Moreover, it is preferable to heat-process between after hardening and before peeling. By performing the heat treatment in this process, not only the unreacted groups are reduced, but also the grouping of the fluorine-containing groups on the surface of the resin mold can be made uniform, and the mold release becomes easy. Moreover, since it takes a stable state in a heating environment, the durability of the mold is improved when the obtained resin mold is used as a mold. The temperature is preferably 50 ° C to 120 ° C, more preferably 50 ° C to 100 ° C, and further preferably 60 ° C to 100 ° C. The heating time is preferably 30 seconds to 30 minutes, more preferably 1 minute to 15 minutes, and further preferably 2 minutes to 10 minutes.

  On the other hand, you may heat-process after peeling. By performing the heat treatment after peeling, if there is a solvent, it can be removed or stable at the heating temperature, so that the penetration of the resin when repeatedly transferring from the resin mold to the resin is suppressed, The mold release can be improved. The temperature is preferably 50 ° C to 120 ° C, more preferably 50 ° C to 100 ° C, and further preferably 60 ° C to 100 ° C. The heating time is preferably 30 seconds to 30 minutes, more preferably 1 minute to 15 minutes, and further preferably 2 minutes to 10 minutes.

<Synthesis by thermal polymerization>
The thermoplastic resin having a fine pattern on the surface includes a step of thermocompression bonding the master mold to the thermoplastic resin to form a fine pattern of the master mold on the thermoplastic resin, and a step of releasing the master mold from the thermoplastic resin. Manufactured by the method. The thermoplastic resin having a fine pattern on the surface can be produced by a method of thermosetting after applying by a cast method in addition to a method of thermocompression bonding.

  In the case of thermocompression bonding, it is preferable that the mold heated to a temperature higher than the softening temperature of the thermoplastic resin is bonded to the transfer layer, or the transfer layer is heated to a temperature higher than the softening temperature of the thermoplastic resin and then pressed to the mold. . The temperature in the thermocompression bonding is more preferably (softening temperature of the thermoplastic resin) to (softening temperature of the thermoplastic resin + 60 ° C.), and particularly preferably (softening temperature of the thermoplastic resin + 5 ° C.) to (of the thermoplastic resin). Softening temperature + 40 ° C.). Within this range, the fine pattern of the mold can be efficiently formed on the transfer layer. The pressure for thermocompression bonding is preferably 0.5 MPa to 200 MPa (absolute pressure), more preferably 0.5 MPa to 10 MPa (absolute pressure), and further preferably 0.5 MP to 5 MPa.

  When releasing the mold, it is preferable to cool the transfer layer to a temperature lower than the softening temperature of the thermoplastic resin. More preferably, it is (softening temperature of thermoplastic resin −10 ° C.) to (softening temperature of thermoplastic resin −50 ° C.). In this range, the shape of the fine pattern formed on the transfer layer can be further retained. However, the softening temperature of the thermoplastic resin means a glass transition temperature when the thermoplastic resin is non-crystalline, and means a melting temperature when the thermoplastic resin is crystalline.

  Thermoplastic resins include polyethylene, polypropylene, polystyrene, acrylonitrile / styrene polymer, acrylonitrile / butadiene / styrene polymer, polyvinyl chloride, polyvinylidene chloride, poly (meth) acrylate, polyarylate, polyethylene terephthalate, polybutylene. Terephthalate, polyamide, polyimide, polyacetal, polycarbonate, polyphenylene ether, polyether ether ketone, polysulfone, polyether sulfone, polyphenylene sulfide, polyvinylidene fluoride, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer, tetrafluoroethylene / Ethylene copolymer, vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer Polymer, tetrafluoroethylene / propylene copolymer, polyfluoro (meth) acrylate polymer, fluorinated polymer having a fluorinated aliphatic ring structure in the main chain, polyvinyl fluoride, polytetrafluoroethylene, polychlorotri Fluoroethylene, chlorotrifluoroethylene / ethylene copolymer, chlorotrifluoroethylene / hydrocarbon alkenyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, vinylidene fluoride / hexafluoropropylene copolymer A polymer etc. are mentioned.

  When synthesizing by thermal polymerization, the fluorinated hyperbranched polymer is a thermopolymerizable mixture containing 1 to 30 parts by weight of the fluorinated hyperbranched polymer with respect to 100 parts by weight of (meth) acrylate. Use. The fluorine-containing (meth) acrylate is used as a thermally polymerizable mixture containing 1 to 30 parts by weight of fluorine-containing (meth) acrylate with respect to 100 parts by weight of (meth) acrylate.

G) Applications The resin mold according to the present invention is used in various applications in nanoimprint applications. Specifically, optical devices such as microlens arrays, wire grid type polarization, moth-eye type non-reflective films, diffraction gratings, and photonic crystal elements It is also used when manufacturing for nanoimprint applications such as patterned media. In addition, it can be used for the manufacture of biodevices such as scaffolds for regenerative medicine and biosensor electrodes. In addition, it can be applied to electrodes of various batteries and capacitors, micro / nano channels, heat dissipation surfaces, heat insulation surfaces, and the like.

Hereinafter, the present invention will be described specifically by way of examples.
The physical properties of the resin mold were measured using the following measurement method.
[Residual film thickness measurement]
The residual film thickness of the fine concavo-convex structure transferred by the nanoimprint method using a resin mold was measured by observation with a scanning electron microscope (hereinafter, SEM). First, a sample was cut out to an appropriate size, then cleaved at room temperature and loaded on a sample stage. Next, the observation surface was coated with about 2 nm of Os to obtain a spectroscopic sample. The equipment used and speculum conditions are shown below:
Equipment: HITACHI s-5500
Acceleration voltage: 10 kV
MODE; Normal

[Fluorine element concentration measurement]
The surface fluorine element concentration of the resin mold was measured by X-ray photoelectron spectroscopy (hereinafter referred to as XPS). The resin mold was cut out as a small piece of about 2 mm square and covered with a 1 mm × 2 mm slot type mask and subjected to XPS measurement under the following conditions.
XPS measurement conditions Equipment used: Thermo Fisher ESCALAB250
Excitation source; mono. AlKα 15kV × 10mA
Analysis size: approx. 1 mm (shape is oval)
Capture area Survey scan; 0 to 1, 100 eV
Narrow scan; F 1s, C 1s, O 1s, N 1s
Pass energy
Survey scan; 100 eV
Narrow scan; 20 eV

Hereinafter, typical resin mold fabrication methods and physical properties will be described.
[Example 1] Resin mold manufacturing method 1
A nickel cylindrical mold having a fine concavo-convex structure with a fine concavo-convex size of 150 nm and a pitch of 130 nm on the surface was subjected to a release treatment using Durasurf 2101Z manufactured by Harves. Weight parts of FA-200 (manufactured by Nissan Chemical Industries, Ltd.), trimethylolpropane triacrylate (M350, manufactured by Toagosei Co., Ltd.), Irgacure 184 (produced by Ciba), and Irgacure 369 (produced by Ciba), which are fluorinated hyperbranched polymers And 5: 100: 5.5: 2.0. Subsequently, the mixed solution was applied to a PET film using a micro gravure. Subsequently, the fine concavo-convex structure surface of the nickel mold was bonded to the PET film through a drying process at 60 ° C. After UV exposure, the mold and the PET film were peeled off and passed through a resin continuous molding.
When the resin mold was measured by XPS, the ratio Es / Eb between the fluorine element concentration Es on the surface and the average fluorine element concentration Eb in the resin was 80. The water contact angle was 150 °.

[Example 2] Resin mold manufacturing method 2
A nickel flat plate mold having a fine concavo-convex structure with a fine concavo-convex size of 150 nm and a pitch of 130 nm on the surface was subjected to a mold release process using Durasurf 2101Z manufactured by Harves. Weight parts of FA-200 (manufactured by Nissan Chemical Industries, Ltd.), trimethylolpropane triacrylate (M350, manufactured by Toagosei Co., Ltd.), Irgacure 184 (produced by Ciba), and Irgacure 369 (produced by Ciba), which are fluorinated hyperbranched polymers Were mixed at a ratio of 5: 100: 5.5: 2.0, and dropped onto the fine concavo-convex structure surface of the mold. Subsequently, the mixture was sandwiched between PET films and stretched simultaneously using a hand roller. After UV exposure from the PET film surface side, the mold and the PET film were peeled off to obtain a resin mold.
When the resin mold was measured by XPS, the ratio Es / Eb between the fluorine element concentration Es on the surface and the average fluorine element concentration Eb in the resin was 75. The water contact angle was 150 °.

[Example 3] Resin mold manufacturing method 2
A nickel flat plate mold having a fine concavo-convex structure with a fine concavo-convex size of 150 nm and a pitch of 130 nm on the surface was subjected to a mold release process using Durasurf 2101Z manufactured by Harves. FA-200 which is a fluorinated hyperbranched polymer (manufactured by Nissan Chemical Industries, Ltd.), OPTOOL DAC HP (manufactured by Daikin Industries, Ltd.), trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd. M350), Irgacure 184 (manufactured by Ciba), And Irgacure 369 (manufactured by Ciba) were mixed at a weight ratio of 1: 10: 100: 5.5: 2.0 and dropped onto the fine concavo-convex structure surface of the mold. Subsequently, the mixture was sandwiched between PET films and stretched simultaneously using a hand roller. After UV exposure from the PET film surface side, the mold and the PET film were peeled off to obtain a resin mold.
When the resin mold was measured by XPS, the ratio Es / Eb between the fluorine element concentration Es on the surface and the average fluorine element concentration Eb in the resin was 85. The water contact angle was 150 °.

[Example 4] Manufacturing method 1 of resin mold
A nickel cylindrical mold having a fine concavo-convex structure with a fine concavo-convex size of 150 nm and a pitch of 130 nm on the surface was subjected to a release treatment using Durasurf 2101Z manufactured by Harves. FA-200 which is a fluorinated hyperbranched polymer (manufactured by Nissan Chemical Industries, Ltd.), OPTOOL DAC HP (manufactured by Daikin Industries, Ltd.), trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd. M350), Irgacure 184 (manufactured by Ciba), And Irgacure 369 (manufactured by Ciba) were mixed at a ratio of 1: 10: 100: 5.5: 2.0 by weight. Subsequently, the mixed solution was applied to a PET film using a micro gravure. Subsequently, the fine concavo-convex structure surface of the nickel mold was bonded to the PET film through a drying process at 60 ° C. After UV exposure, the mold and the PET film were peeled off and passed through a resin continuous molding.
When the resin mold was measured by XPS, the ratio Es / Eb between the fluorine element concentration Es on the surface and the average fluorine element concentration Eb in the resin was 85. The water contact angle was 150 °.

[Example 5] Repeatable transferability of resin mold Using the resin composition prepared in Examples 1 to 4 as a transfer agent, reverse transfer of the resin molds produced in Examples 1 to 4 was performed. The resin mold was fixed on the stainless steel plate, and the transfer agent was dropped on the fine concavo-convex structure surface. Subsequently, the transfer agent was sandwiched between PET films and stretched using a hand roller. After UV exposure from the coated PET film surface side, it was heated at 60 ° C. for 3 minutes, and the PET film coated with the resin mold was peeled off to obtain a transfer product A of the resin mold. In the same procedure, a transfer product A was produced 50 times continuously from the same resin mold. Thirty times showed a constant low peel resistance (average 10 mN / mm). Moreover, the visual observation did not confirm the fracture of the transfer surface. In order to confirm transferability in more detail, cross-sectional SEM (scanning electron microscope) observation of the resin mold and the transfer product A was performed. It was confirmed that the concavo-convex structure on the resin mold side and the concavo-convex structure of the transferred product A coincided with each other and the transferability was good. From this result, it was confirmed that the transfer product A was a resin mold having the same pattern shape as the master mold.

  Next, using the transfer product A as a resin mold, in the same manner as in the transfer method described above, an acrylic ultraviolet curable resin (refractive index 1.52) based on a TAC (triacetyl cellulose resin) film was used. Repeated UV transfer was repeated 10 times to produce a transfer product B. The transfer surface was not visually broken and could be peeled off with a resistance of 5 mN / mm to 10 mN / mm. In order to confirm the shape of the transferred product B from the first time to the 10th time, it was evaluated by surface reflection spectrum measurement. The fine concavo-convex structure on the surface reflects the surface refractive index. Therefore, if there is a change in the fine uneven structure, it is observed as a change in the waveform of the reflection spectrum. As a result, it was confirmed that the reflection spectrum waveforms of the first to tenth transfer products B were consistent and there was no pattern change due to continuous repeated transfer. Further, the cross-sectional SEM observation revealed that the concavo-convex structure of the 10th transfer product B and the concavo-convex structure of the transfer product prepared from the master mold were consistent, and thus the transferability during repeated transfer was maintained. .

Example 6 Nanoimprint Using Resin Mold 3-Ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane and 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxy A cationic polymerizable resin containing cyclohexenecarboxylate was applied to a PET film on which SiO ₂ was deposited using a micro gravure. Subsequently, the PET film was bonded to each of the resin molds produced in Examples 1 to 4, and simultaneously, pressure was applied by a rubber nip, and UV exposure was performed from the resin mold side in a state where the nip pressure disappeared. After UV exposure, the resin mold and the PET film were peeled off. Peeling was performed easily and there were no visual defects. When the transferred fine concavo-convex structure was observed with an SEM, the remaining film thickness was uniform at 5 nm or less.

[Comparative Example 1]
As Comparative Example 1, a composition containing no fluorinated hyperbranched polymer or / and OPTOOL DAC HP which is a fluorine-containing (meth) acrylate in the composition of Example 1 to Example 4 was prepared, and a resin mold was prepared. As a result, interfacial peeling from the cured transfer agent was not possible after UV curing.

[Comparative Example 2]
A nickel flat plate mold having a fine concavo-convex structure with a fine concavo-convex size of 150 nm and a pitch of 130 nm on the surface was subjected to a mold release process using Durasurf 2101Z manufactured by Harves. PAC01 manufactured by Toyo Gosei Kogyo Co., Ltd. was dropped on the fine concavo-convex structure surface of the mold. Subsequently, the UV curable resin was sandwiched between PET films and simultaneously stretched using a hand roller. After UV exposure from the PET film surface side, the mold and the PET film were peeled off to obtain a resin mold.
Cationic polymerizable resin comprising 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane and 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate It was applied to a PET film which was deposited on SiO ₂ using a gravure. Subsequently, the PET film was bonded to the resin mold, and at the same time, pressure was applied by a rubber nip, and UV exposure was performed from the resin mold side in a state where the nip pressure disappeared. When the mold and the PET film were peeled off after UV exposure, they were in high contact and could not be peeled off. On the other hand, when the part which was able to peel partially was observed with AFM, transfer of the fine concavo-convex structure was not seen.

[Comparative Example 3]
A nickel cylindrical mold having a fine concavo-convex structure with a fine concavo-convex size of 150 nm and a pitch of 130 nm on the surface was subjected to a release treatment using Durasurf 2101Z manufactured by Harves. CHEMINOX FAMAC-6 (manufactured by Unimattech), 3 acryloxypropyltrimethoxysilane (KBM5103 manufactured by Shin-Etsu Silicone), trimethylolpropane triacrylate (M350 manufactured by Toagosei Co., Ltd.), and Irgacure 184 (manufactured by Ciba), Irgacure 369 (Ciba) The product was mixed at a ratio of 10: 10: 90: 5.5: 2.0 by weight. Subsequently, the mixed solution was applied to a PET film using a micro gravure. Subsequently, after passing through a drying process at 60 ° C. on the PET film, it was bonded to the fine concavo-convex structure surface of the nickel mold. After UV exposure from the PET surface side, the mold and the PET film were peeled off to obtain a continuous resin molded product.
When the resin mold was measured by XPS, the ratio Es / Eb between the fluorine element concentration Es on the surface and the average fluorine element concentration Eb in the resin was 26.
Subsequently, reverse transfer of the resin mold was performed using the resin composition as a transfer agent. The resin mold was fixed on the stainless steel plate, and the transfer agent was dropped on the fine concavo-convex structure surface. Subsequently, the transfer agent was sandwiched between PET films and stretched using a hand roller. After UV exposure from the coated PET film surface side, it was heated at 60 ° C. for 3 minutes, and when the PET film coated with the resin mold was peeled off, the resin mold and the cured transfer agent were intimately adhered and could not be peeled off.

  The resin mold of the present invention can be suitably used in the field of nanoimprint.

Claims (8)

  A resin mold for nanoimprinting having a fine concavo-convex structure on the first surface of a film substrate having a first surface and a second surface opposite to the first surface, the resin constituting the resin mold Is a cured product of a photopolymerizable compound, and the photopolymerizable compound contains (meth) acrylate, a fluorinated hyperbranched polymer, and a photopolymerization initiator. The ratio of the fluorine element concentration (Es) of the surface portion of the fine concavo-convex structure of the resin mold to the average fluorine element concentration (Eb) in the resin constituting the resin mold is represented by the following formula (1):
1 <Es / Eb ≦ 30000 (1)
The resin mold according to claim 1, wherein   The resin mold according to claim 1 or 2, wherein a contact angle with water is 110 ° or more.   The fluorinated hyperbranched polymer is contained in an amount of 0.05 to 30 parts by weight and a photopolymerization initiator is contained in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylate. The resin mold of any one of 1-3.   The resin mold according to claim 1, wherein the photopolymerizable compound further contains a fluorine-containing (meth) acrylate.   0.05 to 30 parts by weight of at least fluorinated hyperbranched polymer, 0.1 to 50 parts by weight of fluorine-containing (meth) acrylate, and light with respect to 100 parts by weight of (meth) acrylate The resin mold according to claim 5, comprising 0.05 to 30 parts by weight of a polymerization initiator.   The resin mold according to any one of claims 1 to 6, wherein the fluorinated hyperbranched polymer includes at least one of a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group as a photopolymerizable group. .   The resin mold according to any one of claims 1 to 7, wherein the fine concavo-convex structure has a structure with a pitch of 10 nm to 500 µm and a height of 10 nm to 10 µm.