JP6492904B2 - Compact - Google Patents

Description

  The present invention provides a molded body, an imprint mold using the molded body, and an antireflection film that can be manufactured using the molded body.

  A nanoimprint technique is known as a technique for obtaining a fine pattern. The nanoimprint technique is a technique for transferring a fine structure to a base material by pressing a mold (mold) having an uneven fine pattern surface against the base material.

  As a mold used in such a nanoimprint technique, a quartz mold can be generally used, but this is very expensive. Therefore, a technique is known in which such a quartz mold is used as an original plate (also referred to as “master mold” or “mother mold”) to produce a resin replica mold, and this replica mold is used in the nanoimprint technique. .

  Molds used in such nanoimprint technology are required to have high releasability in order to reliably maintain the transferred microstructure when released from the curable resin. However, this replica mold has a problem of low releasability. In order to solve such a problem, for example, Patent Document 1 proposes a mold in which a layer containing a release agent and bonded to the surface of the resin mold is formed on the surface of the resin mold.

International Publication No. 2012/018045

  However, conventional resin replica molds are film-like and are difficult to handle because they are soft. In particular, when the inorganic material is subjected to the nanoimprint process, the conventional resin replica mold is too soft to maintain the uneven shape on the surface, and even with a few transfer times, for example, a single transfer, The releasability was poor and it was difficult to perform continuous transfer.

  Therefore, an object of the present invention is to provide a resin replica mold having a large texture hardness and excellent releasability in a nanoimprint process using not only an organic material but also an inorganic material.

  As a result of intensive studies on the above-mentioned problems, the present inventors have found that the elastic modulus of a molded article having a thermoplastic fluorine-containing resin having a fine concavo-convex structure is set to 2.0 GPa to 20 GPa, so that an appropriate texture hardness can be obtained. Thus, it has been found that a molded article that can be used as a replica mold that can be used in a continuous nanoimprint process can be obtained.

  That is, the present invention provides, in the first aspect, a molded article having a thermoplastic fluororesin having a concavo-convex structure on the surface and having an elastic modulus of 2.0 GPa to 20 GPa.

In the second aspect, the present invention provides the following:
A support formed from a resin material;
A binder layer located on the support;
It is located on the binder layer and comprises a fluorine-containing layer having a concavo-convex structure on the surface,
Provided is a laminate in which a fluorine-containing layer is formed from a thermoplastic fluororesin.

  In the third aspect of the present invention, the surface has a plurality of substantially cylindrical convex portions, the reflectance is 0.1% or less, the transmittance at a wavelength of 500 nm is 90% or more, and the height of the convex portions is high. Provided is an antireflection film formed of an inorganic material, wherein a ratio (B / A) of a diameter A at 10 nm to a diameter B at 10 nm from the top of a convex portion is 0.30 or more and 2.00 or less.

  According to the present invention, by setting the elastic modulus of a molded article comprising a thermoplastic fluorine-containing resin having a fine concavo-convex structure to 2.0 GPa to 20 GPa, it has an appropriate texture hardness and is suitable for a continuous nanoimprint process. It becomes possible to make a replica mold that can be used.

FIG. 1 is an SEM image of the imprint mold obtained in Example 3. FIG. 2 is a diagram for explaining a manufacturing process according to the fourth embodiment. FIG. 3 shows the results of a release durability test in Test Example 1.

  Hereinafter, the molded product of the present invention will be described.

  The molded body of the present invention has a thermoplastic fluororesin having a concavo-convex structure on the surface, and has an elastic modulus of 2.0 GPa to 20 GPa.

  Examples of the thermoplastic fluororesin include, for example, ethylene-tetrafluoroethylene copolymer (ETFE), polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and perfluoroalkoxy copolymer. (PFA), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene-hexafluoropropylene copolymer Polymer (FTFP), vinylidene fluoride-hexafluoropropylene copolymer (VdF-HFP), vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer (VdF-TFE-) FP), other fluorine-based resin, in addition to fluorine rubber or the like, blends resins, it may be a polymer alloy.

  Examples of the thermoplastic fluororesin include polytetrafluoroethylene (PTFE), perfluoroalkoxy copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and ethylene-tetrafluoroethylene copolymer (ETFE). ), Ethylene-tetrafluoroethylene-hexafluoropropylene copolymer (FTFP), polyvinylidene fluoride (PVDF) or polychlorotrifluoroethylene (PCTFE), polytetrafluoroethylene, perfluoroalkoxy copolymer or tetrafluoro An ethylene-hexafluoropropylene copolymer is more preferable.

  In one embodiment, the thermoplastic fluororesin has a melting point of 100 ° C or higher, for example, 150 ° C or higher, 170 ° C or higher, 200 ° C or higher, 220 ° C or higher, 250 ° C or higher, 270 ° C or higher, 300 ° C or higher, or 320 ° C or higher. Having a melting point of

  In one embodiment, the fluorine content in the thermoplastic fluororesin is 20% by mass or more, preferably 30% by mass or more, such as 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80%. It may be greater than or equal to mass%.

  In a preferred embodiment, the thermoplastic fluororesin has a melting point of 100 ° C. or higher and contains 20% by mass or more of fluorine. Preferably, the melting point and fluorine content of the fluororesin may be 100 ° C. or higher and 30% by mass or higher, 150 ° C. or higher and 20% by mass or higher, or 150 ° C. or higher and 30% by mass or higher, respectively.

  In a preferred embodiment, the thermoplastic fluororesin is crosslinked. The crosslinked structure is formed, for example, when a thermoplastic fluororesin that has been heated and melted is irradiated with ionizing radiation to cause a crosslinking reaction and is cured as it is.

  The molded body of the present invention has a flexural modulus of 1.0 GPa to 20 GPa, preferably 2.0 GPa to 15 GPa, and more preferably 2.0 GPa to 10 GPa. By having such a flexural modulus, when the molded body is used as an imprint mold, an imprint mold having an appropriate texture hardness can be obtained, and the mold release durability can be improved.

  The uneven structure on the surface of the molded body of the present invention has the same structure as the uneven structure of the fluorine-containing layer of the laminate described below.

  The molded article of the present invention can be used as an imprint mold, preferably as a nanoimprint mold.

  In the present specification, the mold refers to a mold for transferring a nanometer-order fine pattern on the surface of the mold onto a resin, a film, or the like. The transfer can be performed using light (for example, ultraviolet rays) or heat.

In one aspect, the present invention provides:
A support formed from a resin material;
A binder layer located on the support;
Provided is a laminate comprising a fluorine-containing layer located on a binder layer and having a concavo-convex structure on the surface.

  The resin material forming the support is not particularly limited, and various thermoplastic resins or thermosetting resins can be used. Specifically, as such resin, polyolefin such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), cyclic polyolefin, modified polyolefin, polyvinyl chloride, polyvinylidene chloride, Polystyrene, polyamide, polyimide, polyamideimide, polycarbonate, poly- (4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, acrylic-styrene copolymer (AS resin), butadiene-styrene copolymer, Polyesters such as ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycyclohexane terephthalate (PCT), polyether, polyether Luketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, others Various thermoplastic elastomers such as fluorine resin, styrene, polyolefin, polyvinyl chloride, polyurethane, fluoro rubber, chlorinated polyethylene, epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester, silicone Examples thereof include resins, polyurethane, and the like, and copolymers, blends, and polymer alloys mainly composed of these. From the viewpoint of transparency and flexibility of the support, the resin material is preferably polyethylene terephthalate (PET), cycloolefin resin (COP), acrylic resin (PMMA), ethylene-tetrafluoroethylene copolymer (ETFE). More preferred is polyethylene terephthalate or cycloolefin resin, and more preferred is polyethylene terephthalate.

  The support preferably has a flexural modulus of 1.0 GPa to 20 GPa, more preferably 2.0 GPa to 15 GPa, and still more preferably 2.0 GPa to 10 GPa. When the support has the bending elastic modulus as described above, the same bending elastic modulus can be given to the laminate of the present invention, and a laminate having an appropriate texture hardness can be obtained. When the flexural modulus of the support is 1.0 GPa or more, preferably 2.0 GPa or more, the laminate of the present invention can be easily handled. In addition, by setting the flexural modulus of the support to 20 GPa or less, preferably 10 GPa or less, the laminate does not become too hard, and continuous imprinting is facilitated when used as an imprint mold.

  Although the thickness of the said support body is not specifically limited, For example, 10 micrometers-10 mm, Preferably they are 25 micrometers-1 mm, More preferably, they are 50 micrometers-0.5 mm, More preferably, they are 75 micrometers-0.2 mm. Increasing the thickness increases the flexural modulus of the support.

  The support may be a single phase or may be a laminate of two or more layers.

  The binder layer (hereinafter also referred to as “adhesion layer”) functions to adhere the support and the fluorine-containing layer.

  The material for forming the binder layer is not particularly limited as long as it has high adhesion to the support and the fluorine-containing layer, and a photocurable resin or a thermosetting resin can be used. Resin, urethane resin, polyester resin, acrylic resin, melamine resin, epoxy resin, polyamide resin, vinyl chloride resin, vinyl chloride vinyl acetate copolymer resin and the like. These materials may be used alone or in combination of two or more. Preferably, a photocurable polymer such as a (meth) acrylate resin (for example, a beam set 1402 (Arakawa Chemical Industries, Ltd.)) can be used for the binder layer.

  Although the thickness of a binder layer is not specifically limited, Preferably it is 0.01-50 micrometers, More preferably, it is 0.1-10 micrometers.

  The material for forming the fluorine-containing layer having an uneven structure on the surface is a fluororesin. As the fluororesin, a thermoplastic fluororesin is preferable. Examples of the thermoplastic fluororesin include those listed as the thermoplastic fluororesin of the molded article.

  Although the thickness of the said fluorine-containing layer is not specifically limited, The thickness in a convex part becomes like this. Preferably it is 10-200 micrometers, More preferably, it is 30-125 micrometers, More preferably, it is 30-60 micrometers.

  The concavo-convex portion of the fluorine-containing layer preferably has a structure in which a plurality of substantially cylindrical shapes are arranged, that is, a so-called inverted moth-eye structure, that is, a structure in which a plurality of substantially cylindrical concave portions are arranged.

  The shape of the recess is preferably substantially cylindrical, but is not limited thereto, and may be other shapes, for example, a truncated cone shape with a narrow bottom, a triangular prism, a quadrangular prism such as a quadrangular prism, and the side surface thereof. May have irregularities.

  The diameter of the cross section of the substantially cylindrical recess, which is coplanar with the surface of the fluorine-containing layer, is preferably less than or equal to the wavelength of visible light, for example about 10 to 500 nm, more preferably about 50 to 400 nm, Preferably it can be about 100-300 nm.

  The diameter of the bottom of the substantially cylindrical recess is preferably not more than the diameter of the cross section on the same plane as the surface of the fluorine-containing layer, preferably not more than 95%, more preferably not more than 90%, still more preferably 80%. Hereinafter, it may be 85% or less even more preferably. Moreover, the diameter of the bottom part of a recessed part becomes like this. Preferably it is 40% or more of the diameter of the cross section which is on the same plane as the surface of the said fluorine-containing layer, More preferably, it is 60% or more, More preferably, it is 70% or more.

  The depth of the recess may be preferably about 30 to 500 nm, more preferably about 50 to 400 nm, and still more preferably about 100 to 300 nm.

  The distance between adjacent recesses (hereinafter also referred to as “pitch”) is preferably not more than the wavelength of visible light, for example, preferably about 30 to 500 nm, more preferably about 50 to 400 nm, and further preferably about 100 to 300 nm. obtain.

  The aspect ratio of the recess (depth of the recess / diameter of the cross section of the recess coplanar with the surface of the fluorine-containing layer) is preferably about 0.8 to 5.0, more preferably 1.2 to 4.0. More preferably, it is 1.5-3.0. By setting the aspect ratio of the recess to 1.0, the reflectance is further lowered.

  The diameter of the cross section of the concave portion, the diameter and depth of the bottom portion, and the pitch can be measured by observation with a scanning electron microscope (SEM).

  Furthermore, in a preferred embodiment, the fluorine-containing layer can also bring a graft chain to the uneven surface with various fluorine monomers. By providing such a graft chain, the release property and the release durability are further enhanced.

  In the above aspect, the graft chain in the fluorine-containing layer is preferably at least 0.1 μm in depth and up to 200 μm in depth, more preferably at least 1 μm in depth and up to 40 μm in depth from the fluorine-containing layer. Is at least 3 μm deep and up to a depth of 20 μm, for example 10 to 20 μm deep. The greater the thickness at which the graft chain is present, the better the mold release durability. Moreover, the strength of the fluorine-containing layer is improved as the thickness where the graft chain is present is smaller.

  The “graft chain” means a side chain bonded in a branched manner to the main chain of the polymer constituting the fluorine-containing layer, and is not limited by the production method. That is, the graft chain includes, for example, a chain introduced into the main chain of the polymer constituting the resin substrate by other methods in addition to the graft chain formed by the above graft polymerization.

  In a preferred embodiment, the “graft chain” is a branched chain that is branched with respect to the polymer main chain of the fluorine-containing layer, and can be obtained by covalently bonding the graft monomer to the polymer main chain by irradiation with ionizing radiation. .

  Preferably, the depth at which the graft chain is present is from the surface of the fluorine-containing layer to a depth of 0.001 to 95% with respect to the thickness of the fluorine-containing layer, for example, a depth of 0.01 to 95% or 0 Can be up to 1-95% deep. The depth at which the graft chain is present may more preferably be 5 to 80% deep, more preferably 10 to 60% deep, and even more preferably 20 to 60% deep. .

  The depth at which the graft chain is present in the fluorine-containing layer can be measured, for example, by observing the cross section of the film with a scanning electron microscope. More specifically, it can be measured by performing EDX (Energy dispersive X-ray) analysis, EPMA (Electron Probe Microanalyser) analysis, or positron lifetime measurement using a scanning electron microscope (SEM).

  In a preferred embodiment, in the fluorine-containing layer having the graft chain, the graft ratio may be 0.1 to 1,500%.

“Graft ratio” means the ratio of graft chains introduced to the fluorine-containing layer. Specifically, the graft ratio (Dg) can be calculated by the following formula by measuring the weight change of the fluorine-containing layer before and after the graft polymerization reaction.
Graft ratio: Dg [%] = (W ₁ −W ₀ ) / W ₀ × 100
[Wherein W ₀ is the weight of the fluorine-containing layer before graft polymerization, and W ₁ is the weight of the fluorine-containing layer after graft polymerization. ]
In addition, since the graft ratio Dg is calculated by allocating by the total weight of the base material, when the graft layer is extremely thin with respect to the film thickness, it becomes a small value and may show a value of 0.1% or less. However, the region of the graft chain in the depth direction can be verified by elemental analysis using SEM-EDX or EPMA. For example, when a graft chain containing a perfluoropolyether group of 5 μm is introduced into a resin having a specific gravity of 2 and a weight of 30 g in a sheet having a thickness of 5 mm, it is 0.1% of the thickness of the fluorine-containing layer, The graft ratio is approximately less than 0.1%.

  The graft ratio can also be calculated by thermogravimetric analysis (TG). Specifically, a fluorine-containing layer having a graft chain is measured by changing the temperature of the fluorine-containing layer according to a certain program (heating or cooling), and measuring the change in the weight of the fluorine-containing layer. Can be calculated. The thermogravimetric measurement can be performed, for example, using a TGA measuring instrument manufactured by Rigaku or Shimadzu Corporation.

  The graft rate may preferably be 0.1-250%, more preferably 0.2% -150%, even more preferably 5-120%, such as 10-100% or 20-80%.

  The ionizing radiation is not particularly limited as long as it can generate radicals when irradiated to the fluorine-containing layer. For example, an electron beam, X-ray, γ-ray, neutron beam, ion, or the like can be used. An electron beam is preferable because the penetration depth (range) of ionizing radiation is easy and radicals are easily generated in the resin.

  The absorbed dose of the ionizing radiation to be irradiated is 1-1000 kGy, preferably 10-500 kGy, more preferably 50-300 kGy. By setting the absorbed dose to 1000 kGy or less, deterioration of the fluorine-containing layer on the surface layer can be minimized. Further, by setting the absorbed dose to 1 kGy or more, a sufficient amount of radicals for surface graft polymerization can be generated. The energy absorption amount of the fluorine-containing layer can be measured with a scintillation detector or a semiconductor detector, but more preferably, for example, measured with a cellulose triacetate (CTA) dosimeter or a radiochromic film dosimeter can do.

  In the case of using an electron beam, the electron energy of the electron beam irradiated onto the sample is preferably 5 keV to 100 keV, more preferably 10 keV to 80 keV, still more preferably 30 keV to 70 keV, and even more, using the electron accelerator. Preferably, it is 40 keV to 70 keV. By setting the electron energy on the sample surface to 100 keV or less, the electron beam is substantially absorbed only near the surface of the fluorine-containing layer, and the electron beam penetrating into the inside of the substrate is reduced. Deterioration of the fluorine-containing layer can be suppressed. Furthermore, since the absorption of electron beams inside the resin not involved in surface graft polymerization is small, and the number of electron beams passing through the fluorine-containing layer is small, the energy absorption efficiency can be improved. On the other hand, by setting the energy of electrons on the sample surface to 5 keV or more, radicals sufficient for surface graft polymerization can be generated on the surface of the fluorine-containing layer.

  When an electron beam from an electron accelerator is used, if the space between the electron gun and the sample is a vacuum environment, the electron energy corresponds to the acceleration voltage, and the acceleration voltage is preferably 5 to 100 kV, more preferably 10 to 80 kV. More preferably, it may be 30 to 70 kV, and even more preferably 40 to 70 kV.

  For example, when the acceleration voltage of the electron beam is 60 kV, the arrival depth of the electron beam can be about 20 μm.

  On the other hand, in the case of an electron accelerator where there is an irradiation window for extraction into the atmosphere between the electron gun and the sample, the electron energy is attenuated when passing through the irradiation window even in irradiation in vacuum. Therefore, the acceleration voltage needs to be higher according to the decay of electron energy. Of course, when passing through a nitrogen stream, it is also necessary to increase the energy in consideration of the energy that attenuates according to the density and distance in the stream to the sample.

When using an electron beam, irradiation dose of the electron irradiating the ^{sample, 10μC / cm 2 ~10mC / cm} 2, ^{preferably, 50μC / cm 2 ~1mC / cm} 2, more preferably 100μC ^/ cm 2 ~300μC ^/ cm ² , for example 200 μC / cm ² . By setting the irradiation dose in such a range, radicals can be generated efficiently.

The irradiation with ionizing radiation to the fluorine-containing layer is preferably performed in an atmosphere substantially free of oxygen from the viewpoint of suppressing the pair annihilation of the generated radical, for example, an oxygen concentration of 1000 ppm or less, more preferably 500 ppm, Even more preferably, it is performed under an atmosphere of 100 ppm or less. For example, the irradiation with ionizing radiation is performed in a vacuum or in an inert gas atmosphere, for example, in a nitrogen or argon atmosphere. The vacuum need not be a complete vacuum, but may be substantially a vacuum, for example, a low vacuum of about 10 ³ Pa or a high vacuum of about 10 ⁻² Pa. In another embodiment, the irradiation with ionizing radiation may be performed in the atmosphere in order to obtain peroxide radicals, and oxygen may be supplied after radical generation. In addition, in order to prevent the deactivation of radicals generated in the fluorine-containing layer, the fluorine-containing layer after irradiation is preferably stored at a low temperature not higher than the glass transition temperature of the polymer constituting the fluorine-containing layer. Alternatively, storage in an inert atmosphere is more preferable.

  The penetration depth of ionizing radiation is preferably 0.1 to 95% of the thickness of the fluorine-containing layer, more preferably 5 to 80%, still more preferably 10 to 60%, and even more preferably 20 to 60%. For example, the penetration depth of the ionizing radiation is from the surface of the fluorine-containing layer to a depth of 0.1 to 200 μm, preferably a depth of 1 to 40 μm, more preferably a depth of 2 to 30 μm, and even more preferably a depth. It may be up to 3-20 μm, for example, 5-20 μm deep or 10-20 μm deep.

  The penetration depth of ionizing radiation means the depth at which the fluorine-containing layer absorbs the energy of ionizing radiation. The penetration depth of ionizing radiation is substantially the same as the region where surface graft polymerization occurs, but the surface of the sample slightly swells due to the surface graft reaction, so there are graft chains in the fluorine-containing layer after the graft reaction. The depth of the ionization can be deeper than the penetration depth of the ionizing radiation. The depth at which the graft chain exists is the cross section of the molded product after surface graft polymerization, such as EDX (Energy dispersive X-ray) analysis by Scanning Electron Microscope (SEM), EPMA (Electron Probe Microanalyser) analysis, etc. Can be measured. The depth at which the graft chain exists can also be measured with a microscopic FT-IR, a Raman microscope, or the like.

  Formation of the concavo-convex structure on the surface of the fluorine-containing layer is performed, for example, by pressing a master mold having a predetermined pattern on which the outermost surface of the air has been subjected to mold release treatment, against the fluorine-containing film. Such molding can be performed by any of the batch production method and the continuous production method described below.

(1) Batch production method The master mold made of silicon, nickel metal or quartz whose outermost air surface has been subjected to release treatment is applied to a fluorine-containing film at a predetermined temperature and pressure using a nanoimprint apparatus, for example, 250 ° C., By pressing at a pressure of 5 MPa for a predetermined time, for example, 3 minutes, a pattern shape in which the pattern of the master mold is accurately inverted can be formed.

(2) Continuous production method While extruding a fluorine-containing film continuously from a film roll, using an imprint apparatus, a master mold made of silicon, nickel metal, or quartz whose outermost surface has been subjected to mold release treatment is predetermined. Under the temperature and pressure conditions of, for example, in a temperature range of 50 ° C. to 200 ° C., at a pressure of 20 MPa to 60 MPa, particularly at 100 ° C. and a pressure of 40 MPa, the pattern of the master mold is accurately reversed. Pattern shapes can be formed.

  Alternatively, the surface of the fluorine-containing layer can be formed by applying a resin or a monomer of the resin that forms the fluorine-containing layer on the master mold, and the resulting film is irradiated with light, electron beam By curing by irradiating or heating and peeling off the obtained cured film from the master mold, a pattern shape in which the pattern of the master mold is accurately inverted can be formed.

  In one aspect, for example, formation of the concavo-convex structure on the surface of the fluorine-containing layer can be formed as follows. First, a monomer dispersion is applied to the surface of the master mold, and the monomer dispersion is cast onto the surface of the master mold by spin coating or the like. As a result, the monomer dispersion enters the groove portion of the concavo-convex structure in the master mold, and can form a pattern forming layer having a uniform surface on the surface of the master mold. Next, the monomer dispersion is heated in an oxygen-free atmosphere to heat and melt the monomer, and the entire pattern forming layer is irradiated uniformly with ionizing radiation. When the pattern forming layer is irradiated with ionizing radiation, the monomer undergoes a crosslinking reaction, and the linear monomer is networked and cured as it is to form a concavo-convex structure.

  Alternatively, the concavo-convex structure on the surface of the fluorine-containing layer can also be formed by pressing a heated thermoplastic resin onto the master mold, cooling to cure, and then peeling off from the master mold. .

  The laminate of the present invention can be produced by applying a material for forming a binder layer to a support formed from the resin material described above, and further laminating a fluorine-containing layer thereon. Contrary to the above, a material for forming a binder layer may be applied to the fluorine-containing layer, and then the support may be laminated. When the material for forming the binder layer is a photo-curable material, the film mold and the substrate can be bonded and cured by irradiating with ultraviolet rays or electron beams after lamination.

  The laminate of the present invention preferably has a flexural modulus of 1.0 GPa to 20 GPa, more preferably 2.0 GPa to 15 GPa, and still more preferably 2.0 GPa to 10 GPa. By making the flexural modulus of the laminated mold 1 GPa or more, particularly 2.0 GPa or more, handling becomes easy. Further, when the flexural modulus of the laminated mold is 20 GPa or less, particularly 10 GPa or less, continuous nanoimprinting is facilitated.

  Although the thickness of the laminated body of this invention is not specifically limited, For example, 10 micrometers-10 mm, Preferably they are 25 micrometers-1 mm, More preferably, they are 50 micrometers-0.5 mm, More preferably, they are 75 micrometers-0.2 mm.

  In a preferred embodiment, the laminate of the present invention can have high light transmittance in the ultraviolet region. Specifically, the light transmittance at 365 nm is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. By having such a high light transmittance, it can be suitably used in imprints utilizing ultraviolet curing.

  The laminate of the present invention can be used as an imprint mold, preferably as a nanoimprint mold. Since the imprint mold of the laminate of the present invention has an appropriate bending elastic modulus due to the laminate structure, the imprint structure is less likely to be distorted during imprinting compared to conventional imprint molds, and can be stably imprinted. In addition, the mold release durability is improved. Moreover, since the fluorine-containing layer having a support and a concavo-convex structure is firmly held by the binder layer, peeling of the layer hardly occurs. This effect becomes more remarkable as the imprint area increases.

In one embodiment, when the laminate of the present invention is used as an imprint mold, the planar area of the uneven surface of the mold is preferably 100 cm ² or more, more preferably 200 cm ² or more, and even more preferably 300 cm ² or more, for example 400 cm ^2. Or more than 500 cm ² . As described above, since the imprint mold of the laminate of the present invention has an appropriate bending elastic modulus due to the laminate structure, it is difficult to cause distortion in the concavo-convex structure at the time of imprint, so such a large area of 100 cm ² or more. Even so, imprinting can be performed satisfactorily.

In one embodiment, the laminate of the present invention has excellent release durability when used as an imprint mold. Specifically, ultraviolet nanoimprinting is performed 200 times with an ultraviolet light amount of 1 to 1000 mJ. For example, the contact angle is 110 ° or more at 1 to 10 μL of water, 105 ° or more at 500 times, and 98 ° or more at 900 times. The nano-imprint is performed a predetermined number of times, and then the static contact angle of the mold surface with respect to water is measured with 1 μL of water using a contact angle measuring device. Nanoimprint is a continuous type consisting of a Step & Repeat method in which 0.2 ml of a photo-curing resin (for example, product name PAK-01 manufactured by Toyo Gosei Co., Ltd.) is dropped on the concavo-convex surface of a laminated nanoimprint mold, and a polycarbonate film is placed thereon. At the same time as pressing with an optical nanoimprint apparatus at 1.0 MPa, ultraviolet irradiation (10 mW / cm ² ) is performed for 20 seconds, and the cured photocurable resin is peeled off from the laminated mold.

  When the laminate of the present invention is used as an imprint mold, it has high release properties and release durability, and therefore can be suitably used for imprinting inorganic materials.

  Examples of the inorganic material include sol-gel materials.

A preferable sol-gel material is, for example, hydrogen silsesquioxane (HSW). Hydrogen silsesquioxane has a trifunctional structure (HSi (O _1/2 ) ₃ ), and by heat treatment, hydrogen is released and a tetrafunctional structure (HSi (O _{1) / 2} ) ₄ ), that is, a silica structure.

  Nanoimprinting using a sol-gel material can be performed, for example, as follows using the laminate of the present invention as a laminated nanoimprint mold.

(1) A sol-gel material (for example, HSQ) is applied on the substrate.
(2) The laminated nanoimprint mold of the present invention is pressed against the sol-gel material at room temperature without applying heat or ultraviolet light. The sol-gel material undergoes hydrolysis / dehydration condensation reaction over time and is cured to obtain an inorganic layer.
(3) The laminated nanoimprint mold is peeled from the cured inorganic layer to obtain an inorganic layer having a transfer pattern on the substrate.

  Alternatively, in step (1), the sol-gel material may be applied to the laminated nanoimprint mold instead of the substrate, and in step (2), the substrate may be pressed against the laminated mold coated with the sol-gel material.

  The method for applying the sol-gel material on the substrate in the step (1) is not particularly limited, and spin coating, screen printing, dipping, spray coating and the like can be used. Preferably spin coating is used.

  Although the press in a process (2) can be suitably selected according to the material to be used, it may be 10-100 Pa, for example, Preferably it may be 30-80 Pa, for example 40 Pa.

  Although hardening of the sol-gel material in a process (2) may stand still at room temperature, in order to accelerate | stimulate reaction, you may heat. The heating temperature is not particularly limited as long as it does not adversely affect the laminated nanoimprint mold, and may be, for example, 30 to 200 ° C or 60 to 150 ° C.

  The inorganic layer peeled from the laminated mold in the step (3) may then be heated in order to make the sol-gel reaction proceed more completely. A heating temperature will not be specifically limited if it is below the glass transition temperature of a base material and an inorganic material, For example, it may be 100-500 degreeC or 200-300 degreeC.

  The inorganic material layer formed as described above has a pattern in which the concavo-convex structure of the laminated nanoimprint mold is inverted on the surface, that is, a moth-eye structure. Therefore, this inorganic material layer functions as an antireflection film.

  Therefore, the present invention provides an antireflection film having the inorganic material layer.

  The reflectance of the antireflection film is 550 nm, preferably 1.0% or less, more preferably 0.5% or less, still more preferably 0.1% or less, and even more preferably 0.08% or less. obtain.

  Since the moth-eye structure is formed by nanoimprinting rather than etching, the antireflection film can have high transparency. The transmittance of visible light (wavelength 550 nm) of the antireflection film is preferably 90% or more, more preferably 95% or more, still more preferably 98% or more, and even more preferably 99% or more.

  The shape of the convex portion on the antireflection film is preferably substantially cylindrical, but is not limited to this, and other shapes such as a truncated cone shape with a narrow bottom, a triangular prism shape, a quadrangular prism shape such as a quadrangular prism shape, etc. May be. Moreover, the top part of the convex part may be rounded, and the side surface of the convex part may have irregularities.

  The diameter at the lowest part of the convex portion may be preferably not more than the wavelength of visible light, for example, about 10 to 500 nm, more preferably about 50 to 400 nm, and further preferably about 100 to 300 nm.

  The diameter of the top of the convex part is preferably not more than the diameter at the lowest part, preferably not more than 95%, more preferably not more than 90%, still more preferably not more than 80%, and even more preferably not more than 85%. . Moreover, the diameter of the top part of a convex part becomes like this. Preferably it is 40% or more of the diameter of the cross section which is on the same plane as the surface of the said fluorine-containing layer, More preferably, it is 60% or more, More preferably, it is 70% or more.

  The height of the convex portion may be preferably about 30 to 500 nm, more preferably about 50 to 400 nm, and still more preferably about 100 to 300 nm.

  The ratio (B / A) of the diameter A at the height of the convex portion at 10 nm to the diameter B at 10 nm from the top of the convex portion is preferably 0.30 or more, more preferably 0 from the viewpoint of the strength of the convex portion. .50 or more, more preferably 0.70 or more, for example 1.0 or more or 1.5 or more. The B / A ratio is preferably 1.00 or less, more preferably 2.00 or less, further preferably 1.50 or less, more preferably 1.00 or less, for example 0, from the viewpoint of reducing the reflectance. .70 or less or 0.60 or less.

  The distance between adjacent convex portions (hereinafter also referred to as “pitch”) is preferably not more than the wavelength of visible light, for example, preferably about 30 to 500 nm, more preferably about 50 to 400 nm, and still more preferably about 100 to 300 nm. possible.

  The aspect ratio of the convex part (height of the convex part / diameter of the lowest part of the convex part) is preferably about 0.8 to 5.0, more preferably 1.2 to 4.0, still more preferably 1.5. ~ 3.0. By setting the aspect ratio of the recess to 1.0, the reflectance is further lowered.

  In a preferred embodiment, the antireflection film of the present invention has a substantially cylindrical convex portion, a reflectance of 0.1% or less, a transmittance at a wavelength of 500 nm of 90% or more, and a height of the convex portion. The ratio (B / A) between the diameter A at 10 nm and the diameter B at 10 nm from the top of the convex portion may be 0.30 or more and 2.00 or less.

  In one aspect, the concave portion of the antireflection layer may be filled with another material.

  As the other material, a material having a refractive index larger than the refractive index of the material constituting the convex portion is preferable, and either an organic material or an inorganic material can be used. You may disperse | distribute a material with a big refractive index in other materials, for example, a nano diamond.

  By filling the recess with another material as described above, it is possible to prevent the recess from being filled with a substance that adversely affects the transparency of the antireflection film.

  Since the antireflection film of the present invention has low reflectance and high transparency, it can be suitably used for various applications such as automotive glass, display front panel, show window glass, and the like.

Example 1: Batch production of imprint molds A master mold (diameter 230 nm, pitch 460 nm, depth 200 nm pillar shape) made of 12 cmφ silicon was dispersed in polytetrafluoroethylene (PTFE) in water (Daikin Industries, Ltd.). D-210C) was coated by spin coating, heated and melted at 380 ° C., and then irradiated with an electron beam at 600 kGy in a nitrogen atmosphere using a low energy electron beam (irradiation condition: acceleration voltage 250 kV).

  Next, in the same manner on the thin film, coating and electron beam irradiation were repeated until the water dispersion of polytetrafluoroethylene (PTFE) became 30 μm, and the film was peeled off from the master mold made of silicon. A nanoimprint film mold having a fine pattern having a hole shape in which the pattern was accurately inverted was formed.

  Next, using a PET film (E5100 standard type: thickness 100 μm, manufactured by Toyobo Co., Ltd., surface corona treatment), a photocurable resin (Beamset BM-200, Arakawa Chemical Co., Ltd.) having a thickness of 1 μm on the corona-treated surface. The adhesive layer was provided by spin coating. Furthermore, the back surface of the film mold for nanoimprint obtained above is laminated thereon, UV light is applied so as to irradiate 2J with a UV irradiation type belt conveyor, the film mold and the substrate are adhesively cured, and the lamination mold Got.

Example 2 Batch Production of Imprint Molds A master mold (diameter 230 nm, pitch 460 nm, depth 200 nm pillar shape) made of 12 cmφ silicon and a perfluoroalkoxy copolymer (PFA) aqueous dispersion (Daikin Industries Ltd.) After being heated and melted at 350 ° C., the electron beam was irradiated with 600 kGy in a nitrogen atmosphere using a low energy electron beam (irradiation condition: acceleration voltage 250 kV). Then, by the same operation on the thin film, the aqueous dispersion of perfluoroalkoxy copolymer (PFA) was repeatedly coated and irradiated with an electron beam until the thickness became 30 μm, and the film was peeled off from the master mold made of silicon. A nanoimprint film mold having a fine pattern having a hole shape obtained by accurately inverting the fine pattern was formed.

  Next, the film mold for nanoimprint obtained above was laminated via a PET film and an adhesive layer in the same manner as in Example 1 to obtain a laminated mold.

Example 3 Batch Production of Imprint Mold A master mold (diameter: 230 nm, pitch: 460 nm, depth: 200 nm) made of 12 cmφ silicon was used as a perfluoroalkoxy copolymer (PFA) film, and a nanoimprint apparatus was used. An imprint film mold having a pattern shape obtained by accurately inverting the pattern of the master mold treated with a perfluoropolyether release agent at 300 ° C. was used. Furthermore, in order to increase the hardness of the obtained film mold surface, an electron beam was irradiated at 200 kGy in a nitrogen atmosphere using a low energy electron beam at room temperature (irradiation condition: acceleration voltage 250 kV).

  Next, a laminated mold was obtained in the same manner as in Example 1 except that the film mold for nanoimprint obtained above was replaced with a COP film instead of a PET film.

  The surface of the obtained laminated mold was observed with a scanning electron microscope. As a result of observation, the diameter was 230 nm, the pitch was 460 nm, and the depth was 200 nm. The photograph taken is shown in FIG.

Example 4 Continuous Production of Imprint Mold As shown in FIG. 2, the PFA film 130 used in Test Example 3 was continuously extruded from a film roll 131, and a perfluoropolyether system was used using an imprint apparatus 133. A master mold 132 (diameter: 230 nm, pitch: 460 nm, depth: 200 nm) made of nickel metal treated with a mold release agent was brought into contact with the PFA film at 100 ° C. to transfer the pattern to the PFA film. Then, processing, such as cooling, was performed with a plurality of rolls 134 and cut into a desired size using a cutting machine 135 to continuously form an imprint film mold. Furthermore, in order to increase the hardness of the obtained film mold surface, an electron beam was irradiated at 200 kGy in a nitrogen atmosphere using a low energy electron beam at room temperature (irradiation condition: acceleration voltage 250 kV).

  Next, a laminated mold was obtained in the same manner as in Example 1 except that the film mold for nanoimprint obtained above was replaced with a COP film instead of a PET film.

  As a result of observing the surface of the obtained laminated mold with a scanning electron microscope, it was confirmed that a pattern having a diameter of 230 nm, a pitch of 460 nm, and a depth of 200 nm was well formed.

Test Example 1: Mold Release Durability Test 0.2 ml of a photo-curing resin (trade name PAK-01 manufactured by Toyo Gosei Co., Ltd.) was dropped on the concavo-convex surface of the laminated mold obtained in Examples 1 and 2, and polycarbonate was added thereon. The film was covered and pressed with 1.0 MPa using a continuous optical nanoimprinting apparatus comprising the Step & Repeat method, and at the same time, ultraviolet irradiation (10 mW / cm ² ) was performed for 20 seconds, thereby releasing the laminate mold from the above-mentioned laminated mold. A sex test was performed. This releasability test was continuously performed, and the static contact angle (water) on the surface of the laminated mold was measured every 225 times. The static contact angle was measured with 1 μL of water using a contact angle measuring device. The results are shown in FIG.

Test Example 2: Flexural Elasticity Test The flexural modulus of the laminated mold obtained in Examples 2 and 4 was measured with a pure bending tester. As Comparative Example 1, the flexural modulus of the PTFE film mold produced in Example 1 (not laminated) was measured in the same manner. The results are shown in Table 1.

Comparative Example 2
As Comparative Example 2, using a PET film mold (manufactured by Soken Chemical Co., Ltd., diameter 230 nm, pitch 460 nm, depth 200 nm), a releasability test with a PET film mold using a photocurable resin was performed in the same manner as in the above test example. The results are shown in FIG.

Comparative Example 3
As Comparative Example 3, using a master mold (diameter: 230 nm, pitch: 460 nm, depth: 200 nm) made of quartz treated with a conventional perfluoropolyether release agent, the photocurable resin was released as in the above test example. A moldability test was performed. The results are shown in FIG.

Comparative Example 4
As Comparative Example 4, using a master mold (diameter: 230 nm, pitch: 460 nm, depth: 200 nm) made of nickel treated with a conventional perfluoropolyether release agent, the photocurable resin was released as in the above test example. A moldability test was performed. The results are shown in FIG.

  As is clear from FIG. 3, the laminated molds of Examples 1 and 2 maintain a contact angle exceeding 100 ° even when the number of times of release exceeds 500 times compared with the conventional products shown in Comparative Examples 2 to 4 and the like. We were able to. On the other hand, when the PET film mold of Comparative Example 2 exceeded 450 times, it became 100 ° or less, and the quartz and nickel molds subjected to the release treatment of Comparative Examples 3 and 4 became 100 ° or less after less than 200 times.

Example 4
0.2 ml of a photo-curing resin (trade name PAK-01, manufactured by Toyo Gosei Co., Ltd.) was dropped on the laminated mold obtained in Example 3, and a polycarbonate film was placed thereon, and continuous light consisting of the Step & Repeat method. The nanoimprint apparatus was pressed at 1.0 MPa, and at the same time, ultraviolet irradiation (10 mW / cm ² ) was performed for 20 seconds.

  Thereafter, the pattern surface of the resin mold was observed to confirm that the mold had no transfer defects. Further, when the pattern surface of the transferred resin was observed with a scanning electron microscope and an atomic force microscope, it was confirmed that the pattern was well formed (diameter 230 nm, pitch 460 nm, depth 200 nm). Moreover, 900 shot continuous optical nanoimprint was performed using this resin mold. As a result, it was confirmed that imprinting can be performed satisfactorily without transfer defects.

Example 5
A sol-gel material (Hydrogen Silsesquioxane: HSQ) was used instead of the photo-curing resin used in Example 4, and this was applied onto a glass substrate and imprinted at 40 MPa. It was confirmed by cross-sectional observation with an atomic force microscope (AFM) that the system material was patterned (diameter 230 nm, pitch 460 nm, depth 200 nm). Moreover, continuous imprinting of 5 shots was performed using this resin mold. As a result, it was confirmed that imprinting was possible without any transfer defects.

Test Example 3: Measurement of Release Force during Repeated Nanoimprinting A photocurable resin (trade name: PAK-01, manufactured by Toyo Gosei Co., Ltd.) was placed on the surface of the laminated mold obtained in Examples 1 and 3 and the PET film mold surface of Comparative Example 2. .2ml dripped, covered with polycarbonate film, pressed with 1.0MPa using a continuous optical nanoimprinting device consisting of Step & Repeat method, and at the same time UV irradiation (10mW / cm ² ) for 20 seconds, photocuring The release force between the resin and the laminated mold was evaluated.

  In the laminated molds of Examples 1 and 3, the release forces at the time of 450 times and 900 times of release were about 2.0 N (Example 3: 450 times) and about 8.0 N (Example 1: 450 times), respectively. , And about 4.0 N (Example 3: 900 times) and about 8.0 N (Example 1: 900 times), but the film mold of Comparative Example 2 is about 8.0 N (450 times). However, it was confirmed from the graph that the release force is unstable, so that it is not suitable for use as a mold.

  Since the laminated nanoimprint mold of the present invention has an appropriate texture hardness and excellent releasability, it can be suitably used for nanoimprinting of various materials including inorganic materials.

DESCRIPTION OF SYMBOLS 130 ... Film 131 ... Film roll 132 ... Master mold 133 ... Imprint apparatus 133 ... Roll 133 ... Cutting machine

Claims (12)

A molded body comprising a thermoplastic fluororesin having a concavo-convex structure on the surface, the molded body having a flexural modulus of 2.0 GPa to 20 GPa ,
The depth of the concave portion of the concave-convex structure is 30 to 500 nm,
The concave portion has an aspect ratio of 0.8 to 5.0,
The distance between adjacent recesses is 30 to 500 nm,
The molded body is an imprint mold for a sol-gel material .   The molded body according to claim 1, wherein the sol-gel material is hydrogen silsesquioxane. Thermoplastic resin has a 100 ° C. melting point above, characterized in that it contains at least 20 wt% fluorine, molded product according to claim 1 or 2. Thermoplastic fluororesin is ethylene-tetrafluoroethylene copolymer, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, perfluoroalkoxy copolymer, ethylene-chlorotrifluoroethylene copolymer, polyfluoride. One or a mixture of two or more selected from vinyl, polyvinylidene fluoride, polychlorotrifluoroethylene, vinylidene fluoride-hexafluoropropylene copolymer, and vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer The molded body according to any one of claims 1 to 3, wherein the molded body is formed from. A support formed from a resin material;
A binder layer located on the support;
It is located on the binder layer and comprises a fluorine-containing layer having a concavo-convex structure on the surface,
The fluorine-containing layer is a laminate formed of a thermoplastic fluororesin ,
The depth of the concave portion of the concave-convex structure is 30 to 500 nm,
The concave portion has an aspect ratio of 0.8 to 5.0,
The distance between adjacent recesses is 30 to 500 nm,
The laminate is a laminate that is an imprint mold for a sol-gel material .   The laminate according to claim 5, wherein the sol-gel material is hydrogen silsesquioxane. The laminate according to claim 5 or 6 , wherein the thermoplastic fluororesin has a melting point of 100 ° C or higher and contains 20% by mass or more of fluorine. The laminate according to any one of claims 5 to 7 , which has a flexural modulus of 2.0 GPa to 20 GPa. Thermoplastic fluororesin is ethylene-tetrafluoroethylene copolymer, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, perfluoroalkoxy copolymer, ethylene-chlorotrifluoroethylene copolymer, polyfluoride. One or a mixture of two or more selected from vinyl, polyvinylidene fluoride, polychlorotrifluoroethylene, vinylidene fluoride-hexafluoropropylene copolymer, and vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer The laminate according to any one of claims 5 to 8 , wherein the laminate is any one of the following. Thermoplastic fluororesin is polytetrafluoroethylene, perfluoroalkoxy copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-tetrafluoroethylene-hexafluoropropylene copolymer The laminate according to any one of claims 5 to 9 , wherein the laminate is one or a mixture of two or more selected from polyvinylidene fluoride and polychlorotrifluoroethylene. The resin material forming the support is polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, cyclic polyolefin, modified polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, polyamide Imide, polycarbonate, poly- (4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, acrylic-styrene copolymer, butadiene-styrene copolymer, ethylene-vinyl alcohol copolymer, polyethylene terephthalate, Polybutylene terephthalate, polycyclohexane terephthalate, polyether, polyether ketone, polyether ether ketone, polyether imide, polyacetal, polyphenylene oxide, modified One or more selected from polyphenylene oxide, polyarylate, aromatic polyester, polytetrafluoroethylene, polyvinylidene fluoride, epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester, silicone resin and polyurethane The laminate according to any one of claims 5 to 10 , which is a mixture. The laminate according to any one of claims 5 to 11 , wherein the binder layer is formed of a photocurable resin.