JP2012101474A - Resin mold - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin mold having a modifiable surface and excellent in adhesion to a base material and releasability from a transfer material resin and can be used repeatedly.SOLUTION: In the resin mold for nano-imprint which has a fine irregular structure in a first surface of a film base material having the first surface and a second surface opposite to the first surface, the ratio of a fluorine concentration (Es) in the surface part of the fine irregular structure of the resin mold to an average fluorine concentration (Eb) in a resin constituting the resin mold meets the following formula (1): 1<Es/Eb≤30,000 (1), and silicon is contained in the resin constituting the resin mold.

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 for nanoimprinting that contains silicon element.

  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, from the master having a fine concavo-convex structure on the surface produced by the above-mentioned 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-mentioned problems of the prior art, and the problem to be solved by the present invention is that it can be surface-modified, has excellent adhesion to a substrate, and a transfer material resin. It is to provide a resin mold which is excellent in releasability and can withstand repeated use.

In order to solve the above problems, the present inventors have made the resin surface free by making the fluorine element concentration in the vicinity of the surface fine uneven structure in the resin mold higher than the average fluorine element concentration of the resin constituting the resin mold. By reducing the energy and introducing a siloxane bond into the resin mold, it suppresses the penetration of the resin used for transfer, excels in releasability from the transfer material resin, and repeats nanometer-sized uneven shapes. While obtaining a resin mold with excellent releasability that can be easily and repeatedly transferred from the mold to the resin, while finding a high free energy in the vicinity of the base material, it has been found that the adhesion with the base material is improved, 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. The mold is industrially useful from an environmental point of view.

That is, the present invention is as follows.
[1] 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 located on the opposite side of the first surface, the resin mold comprising: 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 constituent resin is represented by the following formula (1):
1 <Es / Eb ≦ 30000 (1)
And the resin mold constituting the resin mold contains a silicon element.

  [2] The resin mold according to claim 1, wherein the concentration of the silicon element in the resin constituting the resin mold is 0.005 atm.% Or more and 80 atm.% Or less.

  [3] The resin mold according to [1] or [2], wherein the silicon element is derived from a silane coupling agent and / or silsesquioxane.

  [4] The resin mold according to any one of [1] to [3], comprising a cured product of a photopolymerizable mixture formed by optical nanoimprint.

  [5] The resin mold according to [4], wherein the photopolymerizable mixture includes (meth) acrylate, fluorine-containing (meth) acrylate, and a photopolymerization initiator.

  [6] 0.1 to 50 parts by weight of the fluorine-containing (meth) acrylate and 0.01 to 10 parts by weight of the photopolymerization initiator are contained with respect to 100 parts by weight of the (meth) acrylate. The resin mold according to [5].

  [7] The above [6], wherein at least one of the silane coupling agent or silsesquioxane is contained in an amount of 0.01 to 80 parts by weight with respect to 100 parts by weight of the (meth) acrylate. Resin mold.

  [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 can be surface-modified, 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, the term “(meth) acrylate” means acrylate and / or methacrylate.
The present invention is a resin mold for nanoimprinting having a fine concavo-convex structure on the first surface of a film base material having a first surface and a second surface located on the opposite side of the first surface, the resin mold 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 following formula (1):
1 <Es / Eb ≦ 30000 (1)
And the silicon resin is contained in the resin constituting the resin mold.
By making the fluorine element concentration on the surface of the fine concavo-convex structure of the resin mold higher than the average fluorine element concentration of the resin constituting the resin mold, the free energy on the resin surface is reduced, and siloxane bonds are formed in the resin constituting the resin mold. By introducing, the penetration of the resin used for transfer is suppressed, it is excellent in releasability from the transfer material resin, and nanometer-sized uneven shapes can be easily and repeatedly transferred from the resin mold to the resin. While obtaining the resin mold which is excellent in releasability and durability, on the other hand, by maintaining high free energy in the vicinity of the base material, it is possible to improve the adhesion to the base material.

  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 determined by the XPS method described later. This is because the penetration length of X-rays in XPS is as shallow as several nm, and the value measured by XPS is the same as Es.

  Furthermore, if the fluorine element concentration (Es) on the surface of the resin mold is higher than the average fluorine element concentration (Eb) in the resin constituting the resin mold, the resin surface is separated from the transfer material resin due to low free energy. By obtaining a resin mold that excels in moldability and has excellent releasability and durability that allows repeated resin / resin transfer of nanometer-sized concavo-convex shapes, while maintaining high free energy near the substrate, Adhesiveness with the material 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, a resin mold having a fine concavo-convex 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 is as follows: 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.

  The silicon element present in the resin constituting the resin mold is a silane coupling agent and / or silsesquioxane from the viewpoint of improving mold release when transferring from the resin mold to the resin and improving durability against repeated transfer. It is preferable to derive from. Only one of the silane coupling agent or silsesquioxane may be used, or may be used in combination. A plurality of silane coupling agents and / or a plurality of silsesquioxanes may be used. Furthermore, in order to improve durability against repeated transfer, it is more preferable that the silane coupling agent and the silsesquioxane have a photopolymerizable group.

  A silicon element concentration in the resin constituting the resin mold of 0.005 atm.% Or more and 80 atm.% Or less is preferable because siloxane bonds can be effectively introduced into the resin mold and release can be improved. A silicon element concentration of 0.5 atm.% Or more and 30 atm.% Or less is more preferable because of good curability. If it is 0.5 atm.% Or more and 20 atm.% Or less, the durability against repetitive transfer is more preferable.

  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. In addition, a resin molded body obtained by optical nanoimprinting from a resin mold can be regarded as a resin mold, and a resin molded body obtained by optical nanoimprinting from the resin mold can be used as a resin mold. Hereinafter, the case of synthesizing by photopolymerization and the case of synthesizing by thermal polymerization will be sequentially described.

<Synthesis by photopolymerization>
It is preferable to use (meth) acrylate, fluorine-containing (meth) acrylate, and a photopolymerization initiator in the photopolymerizable mixture, and it is more preferable to add at least one of a silane coupling agent or silsesquioxane. By mixing together (meth) acrylate and fluorine-containing (meth) acrylate, the fluorine element concentration (Es) of the resin mold surface portion becomes higher than the average fluorine element concentration (Eb) in the resin constituting the resin mold. Can be adjusted as follows. Also, by adding at least one of a silane coupling agent or silsesquioxane, siloxane bonds can be effectively introduced into the resin, and the penetration of the resin during the transfer from the resin mold to the resin is suppressed. It is possible to improve the mold release and improve the surface modification property.

Hereinafter, each component will be described.
(A) (Meth) acrylate As (meth) acrylate, any polymerizable monomer other than (B) fluorine-containing (meth) acrylate, (C) silane coupling agent, and (D) silsesquioxane, which will be described later, is limited. However, a monomer having an acryloyl group or a methacryloyl group, a monomer having a vinyl group, or a monomer having an allyl group is 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: Examples of the monomer having an acryloyl group or a methacryloyl group include (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 Hydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, pentaerythritol ethoxy Tetra (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 ECH 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, steari Acid-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) -Tetramethylene 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) Acrylate, 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, Gilt (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 (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methyl (meth) acrylate, methoxytripropylene glycol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene 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) acryl , 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, tribromophenyl (meth) acrylate, EO modified tribromophenyl (meth) acrylate, tridodecyl (meth) acrylate, and the like.

  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) Fluorine-containing (meth) acrylate The fluorine-containing (meth) acrylate is not limited as long as it is a fluorine-containing (meth) acrylate other than (C) silane coupling agent and (D) silsesquioxane described later. , A polyfluoroalkylene chain and / or a perfluoro (polyoxyalkylene) chain, and a polymerizable group, a linear perfluoroalkylene group, or an etheric oxygen atom inserted between carbon atoms and carbon atoms, and A perfluorooxyalkylene group having a trifluoromethyl group in the side chain is more preferred. 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 _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.

  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 fluorine-containing (meth) acrylates 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 (C _{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 = CFCOOCH 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 OCOCH = 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 ) = CH ₂ etc. Fluoro (meth) acrylate (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, manufactured by Daikin) HP), “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 FluoroTechnology Co., Ltd., and the like.

Fluorine-containing (meth) acrylate preferably has a molecular weight M _w of a 50 to 50,000, preferably has a molecular weight M _w of a 50 to 5000 in view of compatibility, a molecular weight M _w of it is 100 to 5,000 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.

(C) Silane coupling agent As the silane coupling agent, except for (D) silsesquioxane, which will be described later, as long as it is a compound having a group causing a coupling reaction and a hydrolyzable group, it is not particularly defined. Known silane coupling agents can be widely employed. The molecular weight of the silane coupling agent is preferably 100 to 1500 from the viewpoint of compatibility. Effectively introducing a siloxane bond into the resin mold and suppressing the penetration of the resin when transferring from the resin mold to the resin, the mold release From the viewpoint of improving, 100 to 600 is more preferable.

  Examples of the group causing the coupling reaction of the silane coupling agent include vinyl group, epoxy group, acryloyl group, methacryloyl group, acryloxy group, methacryloxy group, amino group, ureido group, chloropropyl group, mercapto group, sulfide group, isocyanate. Group, allyl group, oxetanyl group and the like are preferable, from the viewpoint of compatibility, allyl group, vinyl phase, acryloyl group, methacryloyl group, acryloxy group, methacryloxy group are more preferable, and from the viewpoint of physical stability of the resin mold, acryloxy group or More preferred is a methacryloxy group.

The silane coupling agent used in the present invention may be a fluorine-containing silane coupling agent. As the fluorine-containing silane coupling agent, for example, a general formula (F ₃ C— (CF ₂ ) _n — (CH ₂ ) _m —Si (O—R) ₃ {where n is an integer of 1 to 11, m is an integer of 1 to 4, and R is an alkyl group having 1 to 3 carbon atoms.}, a polyfluoroalkylene chain and / or a perfluoro (polyoxyalkylene) chain. A linear perfluoroalkylene group or a perfluorooxyalkylene group having an etheric oxygen atom inserted between carbon atoms and a trifluoromethyl group in the side chain is further preferred. A linear polyfluoroalkylene chain having a fluoromethyl 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, and the polyfluoroalkylene group may have a functional group.The perfluoro (polyoxyalkylene) chain is At least one selected from the 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. Preferably composed of perfluoro (oxyalkylene) units, composed of (CF ₂ CF ₂ O) units, (CF ₂ CF (CF ₃ ) O) units, or (CF ₂ CF ₂ CF ₂ O) units. it is more preferred. perfluoro (polyoxyalkylene) chain, the physical properties of the fluoropolymer (heat resistance, acid resistance, etc.) because it is excellent, it consists (CF ₂ CF ₂ O) units That the number of particularly preferred. Perfluoro (oxyalkylene) units, since releasability and hardness of the fluoropolymer is high, preferably an integer of 2 to 200, more preferably an integer of from 2 to 50.

  The silane coupling agent used in the present invention may have a photopolymerizable group, but more preferably has a photopolymerizable group. By having a photopolymerizable group, good cured film characteristics can be obtained during photocuring. 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.

  Examples of the silane coupling agent in the present invention include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxy Propylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N- -(Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-tri Of ethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane Hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanate Propyltrie Kishishiran, and the like.

Further, as the silane coupling agent in the present invention, triethoxy-1H, 1H, 2H, 2H-tridecafluoro-octylsilane, heptadecafluorodecyl-trimethoxysilane, CF ₃ (CF ₂ ) ₄ CH ₂ CH ₂ Si (OC _{2 H 5) 3, CF 3} (CF 2) 4 CH 2 CH 2 SiCH 3 (OC 2 H 5) 2, CF 3 (CF 2) 7 CH 2 CH 2 Si (OC 2 H 5) 3, CF 3 CF ₂ CH ₂ CH ₂ Si (OC ₃ H ₇ ) ₃ , CF ₃ (CF ₂ ) ₂ CH ₂ CH ₂ Si (OC ₃ H ₇ ) ₃ , CF ₃ (CF ₂ ) ₄ CH ₂ CH ₂ SiCH ₃ (OC ₃ Perfluoro such as H ₇ ) ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ SiCH ₃ (OC ₃ H ₇ ) ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCH ₃ (OC ₃ H ₇ ) ₂ Examples include alkylalkylenealkoxysilane compounds.
Only one type of silane coupling agent in the present invention may be used, or two or more types may be used. Moreover, you may use together with silsesquioxane.

(D) Silsesquioxane The silsesquioxane is not particularly limited as long as it is a polysiloxane represented by the composition formula (RSiO _3/2 ) _n , such as a cage type, a ladder type, and a random type. Polysiloxane having any structure may be used, and polysiloxane having a cage-type or ladder-type structure is more preferable, and the physical stability of the resin mold is improved and the mold release is improved. More preferably it is. In the composition formula (RSiO _3/2 ) _n , R may be a substituted or unsubstituted siloxy group or any other substituent. n is preferably 8 to 12, and more preferably 8 to 10 because the polymerizability in obtaining a resin mold is improved. N is more preferably 8 from the viewpoint of suppressing penetration of the resin during transfer from the resin mold to the resin and improving mold release. The n Rs may be the same or different.

  Moreover, the silsesquioxane in this invention may contain the photopolymerizable group, and since the superposition | polymerization containing a photopolymerizable group advances favorably, it is more preferable. By having a photopolymerizable group, good cured film characteristics can be obtained during photocuring. Examples of the photopolymerizable group include acryloyl group, methacryloyl group, acryloxy group, methacryloxy group, vinyl group, epoxy group, allyl group, and oxetanyl group. Because better cured film properties can be obtained, acryloyl group, methacryloyl group, acryloxy group, methacryloxy group, and vinyl group are more preferable. Resin permeation during transfer from resin mold to resin can be suppressed, and mold release is improved. Therefore, an acryloxy group or a methacryloxy group is more preferable.

Further, the silsesquioxane in the present invention may be fluorosilsesquioxane. The fluorosilsesquioxane here means that R in the composition formula is independently composed of at least one of fluoroalkyl, fluoroaryl or fluoroarylalkyl, and these substituents are at least in n Rs. Means one or more. In order to improve mold release, 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 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 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.

Only one type of silsesquioxane in the present invention may be used, or two or more types may be used. Moreover, you may use together with a silane coupling agent.
Examples of the silsesquioxane in the present invention include polyhydrogenated silsesquioxane, polymethylsilsesquioxane, polyethylsilsesquioxane, polypropylsilsesquioxane, polyisopropylsilsesquioxane, polybutylsilsesquioxane. Sun, poly-sec-butylsilsesquioxane, poly-tert-butylsilsesquioxane, polyphenylsilsesquioxane, polynaphthylsilsesquioxane, polystyrylsilsesquioxane, polyadamantylsilsesquioxane, etc. Is mentioned. Further, at least one of n Rs may be substituted with the substituents exemplified below for these silsesquioxanes. Examples of the substituent include trifluoromethyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3. -Pentafluoropropyl, 2,2,2-trifluoro-1-trifluoromethylethyl, 2,2,3,4,4,4-hexafluorobutyl, 2,2,3,3,4,4,5 , 5-octafluoropentyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3 , 4,4,5,5-octafluoropentyl, 3,3,3-trifluoropropyl, nonafluoro-1,1,2,2-tetrahydrohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl , Hepadecafluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1H, 1H, 2H, 2H-dodecyl, perf Oro-1H, 1H, 2H, 2H-tetradecyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, acryloyl group, methacryloyl group, acryloxy group, methacryloxy group, vinyl group, An epoxy group, an allyl group, an oxetanyl group, etc. are mentioned.

  Commercially available silsesquioxane can also be used. For example, various cage-type silsesquioxane derivatives described in the trade name POSS of Hybrid Plastics, silsesquioxane derivatives of trade name POSS described in the Aldrich Silsesquioxane-related reagent catalog, and the like.

(E) 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 mixture 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).
The photopolymerizable mixture contains 0.1 to 50 parts by weight of fluorine-containing (meth) acrylate and 0.01 to 10 parts by weight of photopolymerization initiator with respect to 100 parts by weight of (meth) acrylate. The mixture contains at least one of a silane coupling agent and silsesquioxane and has a silicon element concentration of 0.005 atm.% To 80 atm.%.

  If the fluorine-containing (meth) acrylate is 0.1 parts by weight or more with respect to 100 parts by weight of the (meth) acrylate, it is excellent in releasability, and if it is 50 parts by weight or less, it has excellent adhesion to the substrate. If it is 5-30 weight part, it is excellent in the surface segregation property of fluorine-containing (meth) acrylate. More preferably, it is 5 to 20 parts by weight. Moreover, 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 order to contain the silicon element in the resin, for example, it is sufficient that at least one of a silane coupling agent or silsesquioxane is contained, and the silane coupling agent or 100 parts by weight of (meth) acrylate. If either one of the silsesquioxanes is 0.01 parts by weight to 80 parts by weight, a hydroxyl group having excellent surface modification properties can be effectively introduced into the resin mold surface, and preferably 0.1 parts by weight to 50 parts by weight. More preferably, the siloxane bond can be effectively introduced into the resin mold in the case of parts by weight and the penetration of the resin during transfer from the resin mold to the resin can be further suppressed. It is still preferable because the mold has better curability. Further, if the silicon element concentration is 0.005 atm.% Or more and 80 atm.% Or less with respect to the entire photopolymerizable mixture, it is preferable because a siloxane bond can be effectively introduced into the resin mold and release can be improved. A silicon element concentration of 0.5 atm.% Or more and 30 atm.% Or less is more preferable because of good curability. Most preferably, it is 0.5 atm.% Or more and 20 atm.% Or less.

(F) 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 mixture (hereinafter referred to as curable resin composition). A resin mold is a resin molding with a fine concavo-convex pattern shape (fine concavo-convex structure) obtained by optical nanoimprint transfer using a curable resin composition as a transfer agent from a master mold having a fine pattern shape on the surface. Is the body. 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.

(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. The pattern arrangement may be either a randomly arranged 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 height of the concavo-convex pattern 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 cross-sectional area (S convex portion) 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 mixture 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.

(G) 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 peeling the cured product from the resin mold (F (+)) in the step 27 to obtain a resin mold (F (−)) having the same pattern shape as the pattern shape of the master mold.

(Process of peeling the cured product from the mold)
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 46 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, the detail of each above-mentioned process is demonstrated.
(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.
By prebaking after applying the resin composition to the substrate, when the solvent is contained, the solvent can be distilled off or the surface migration of the internally added fluorine-containing polymerizable (meth) acrylate can be promoted. By segregating the internally added fluorine-containing polymerizable (meth) acrylate on the surface, when pressing the master mold or resin mold, the fluorine-containing polymerizable (meth) acrylate is efficient inside the microstructure of the master mold or resin mold. In addition to suppressing deterioration of the master mold or resin mold, the value Es / Eb obtained by dividing the surface fluorine element concentration (Es) of the obtained resin mold by the bulk fluorine element concentration (Eb) is greatly improved. And release properties 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 It is preferable to perform a treatment, a surface roughening treatment, a porous treatment, or 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 deterioration 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 heat treatment in this process, not only unreacted groups are reduced, but also siloxane bonds can be effectively introduced into the resin mold, and release is facilitated. 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, the hydrolysis and polycondensation of the silane coupling agent and / or silsesquioxane can be further promoted, and thereby the penetration of the resin when transferring from the resin mold to the resin It can suppress and can improve mold release. 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 synthesized by thermal polymerization, the fluorine-containing (meth) acrylate is a thermopolymerizable mixture containing 0.1 to 10 parts by weight of fluorine-containing (meth) acrylate with respect to 100 parts by weight of (meth) acrylate. Use. Further, in order to contain silicon element in the resin, it is only necessary to contain at least one of a silane coupling agent or silsesquioxane, and the silicon element concentration is 0.005 atm with respect to the entire thermally polymerizable mixture. If it is.% Or more and 80 atm.% Or less, a siloxane bond can be effectively introduced into the resin mold and release can be improved, which is preferable. A silicon element concentration of 0.5 atm.% Or more and 30 atm.% Or less is more preferable because of good curability, and more preferably 0.5 atm.% Or more and 20 atm.% Or less.

(H) Applications The resin mold according to the present invention is used in various applications for nanoimprints. Specifically, it is a light such as a microlens array, a wire grid type polarized light, a moth-eye type non-reflective film, a diffraction grating, and a photonic crystal element. It is used for manufacturing nanoimprint applications such as devices and 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 flat plate mold having a fine concavo-convex structure with a fine concavo-convex size of 150 nm and a pitch of 145 nm on the surface was subjected to a release treatment using Durasurf 2101Z manufactured by Harves. OPTOOL DAC HP (manufactured by Daikin Industries, Ltd.), 3 acryloxypropyltrimethoxysilane (KBM5103, manufactured by Shin-Etsu Silicone Co., Ltd.), trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd., M350) and Irgacure 184 (manufactured by Ciba), Irgacure 369 (Ciba) Co., Ltd.) was mixed at a ratio of 10: 10: 90: 5.5: 2.0 by weight 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 65.

[Example 2] Resin mold manufacturing method 2
A nickel cylindrical mold having a fine concavo-convex structure with a fine concavo-convex size of 150 nm and a pitch of 145 nm on the surface was subjected to a release treatment using Durasurf 2101Z made by Harves. OPTOOL DAC HP (manufactured by Daikin Industries, Ltd.), 3 acryloxypropyltrimethoxysilane (KBM5103, manufactured by Shin-Etsu Silicone Co., Ltd.), trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd., M350) 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, 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 76.

[Example 3] Manufacturing method 3 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 145 nm on the surface was subjected to a release treatment using Durasurf 2101Z made 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.

(Repeatable transfer of resin mold)
Using the resin compositions prepared in Examples 1 to 3 as transfer agents, the resin molds produced in Examples 1 to 3 were subjected to reverse transfer. 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. Fifty 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 4] Nanoimprint using resin mold 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane and 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxy A cationically 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 the resin mold produced in Example 1, Example 2 and Example 3 and the resin mold produced through the 50th transfer from the resin mold, and at the same time, pressure was applied by the rubber nip. Then, UV exposure was performed from the resin mold side with the nip pressure removed. 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 resin mold was prepared by preparing a composition containing no fluororesin composition and no silane coupling agent and silsesquioxane in the composition of Example 1. 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 145 nm on the surface was subjected to a release treatment 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.

[Example 5] Resin mold surface modification The resin mold obtained in Example 1 was subjected to a surface modification treatment using Durasurf 2101Z manufactured by Harves. On the surface of the obtained resin mold, it was confirmed by infrared spectroscopy that components other than the resin constituting the resin mold before the surface modification were bonded to the surface.

[Comparative Example 3]
A composition containing no silane coupling agent and silsesquioxane in the composition of Example 1 was prepared to prepare a resin mold. In the same manner as in Example 6, surface modification treatment was performed using Durasurf 2101Z manufactured by Harves. It was confirmed by infrared spectroscopy that the obtained resin mold surface was not substantially different from the resin mold before modification.

  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 located on the opposite side of the first surface, the resin constituting the resin mold 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 is expressed by the following formula (1):
1 <Es / Eb ≦ 30000 (1)
And the resin mold constituting the resin mold contains a silicon element.   2. The resin mold according to claim 1, wherein the concentration of silicon element in the resin constituting the resin mold is 0.005 atm.% Or more and 80 atm.% Or less.   The resin mold according to claim 1 or 2, wherein the silicon element is derived from a silane coupling agent and / or silsesquioxane.   The resin mold of any one of Claims 1-3 which consists of hardened | cured material of the photopolymerizable mixture formed by optical nanoimprint.   The resin mold according to claim 4, wherein the photopolymerizable mixture includes (meth) acrylate, fluorine-containing (meth) acrylate, and a photopolymerization initiator.   It contains 0.1 to 50 parts by weight of the fluorine-containing (meth) acrylate and 0.01 to 10 parts by weight of the photopolymerization initiator with respect to 100 parts by weight of the (meth) acrylate. 5. The resin mold according to 5.   The resin mold according to claim 6, wherein at least one of the silane coupling agent or silsesquioxane is contained in an amount of 0.01 to 80 parts by weight with respect to 100 parts by weight of the (meth) acrylate.   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.