JP5671841B2 - Manufacturing method of mold for nanoimprint - Google Patents

Description

  The present invention relates to a mold used for nanoimprint technology and a method for manufacturing the same.

In recent years, attention has been focused on nanoimprint technology as a microfabrication technology. The nanoimprint technology is a pattern formation technology that uses a mold member (mold) having a fine concavo-convex structure formed on the surface of a substrate, and transfers the concavo-convex structure to a workpiece to transfer the fine structure at the same magnification (Patent Literature). 1).
As the above-mentioned nanoimprint technology, a photoimprint method and a thermal imprint method are known. In the optical imprint method, for example, a photocurable resin layer is formed as a workpiece on the substrate surface, and a mold having a desired concavo-convex structure is pressed against the resin layer. In this state, the resin layer is irradiated with light from the mold side to cure the resin layer, and then the mold is separated from the resin layer. As a result, a concavo-convex structure (concave / convex pattern) in which the concavo-convex portion of the mold is inverted can be formed on the resin layer that is a workpiece (Patent Document 2). Therefore, the mold used for the optical imprinting method is required to have hardness and chemical resistance and to have optical transparency. In the thermal imprint method, instead of the light irradiation, the resin layer is cured by heating, and then the mold is separated from the resin layer. Therefore, the mold used in the thermal imprint method is required to have hardness and chemical resistance and heat resistance.

  Such a mold for nanoimprinting can be manufactured, for example, by subjecting quartz glass or a silicon substrate to precision fine processing by dry etching or the like using a metal mask. However, the mold manufactured by such a manufacturing method is very expensive. For this reason, it has been proposed to reduce the manufacturing cost of the nanoimprint mold by using the mold thus prepared as a master mold to manufacture a replica mold (Patent Document 3).

US Pat. No. 5,772,905 Special Table 2002-539604 JP 2008-207475 A

However, in the replica mold manufacturing method described in Patent Document 3, the master mold and the replica mold material are in close contact with each other in order to ensure the releasability between the master mold and the replica mold material. In this state, photooxidation (curing) due to ultraviolet irradiation of the replica mold material is suppressed. For this reason, after releasing the master mold from the replica mold material, it is necessary to irradiate the replica mold material with ultraviolet rays to carry out photooxidation (curing), and there is a problem that the process is complicated. Further, in addition to such photo-oxidation (curing) by ultraviolet irradiation, it is preferable to perform a post-bake treatment in order to promote further curing of the polysilane by thermal oxidation. For this reason, a mechanism for performing both ultraviolet irradiation and post-baking treatment on the replica mold material is required in the manufacturing process, which causes a problem of increasing the manufacturing cost.
In addition, since the replica mold produced in this way is easy to attach a patterning material to which a fine pattern should be transferred by nanoimprinting, it is necessary to apply a release agent such as a silane coupling agent to the surface to prevent this. There is. However, there is a problem that the release agent is not uniformly applied and stable release properties cannot be obtained.
The present invention has been made in view of the above situation, and has a mold for nanoimprint having high durability and excellent releasability, and a manufacturing method for easily manufacturing such a mold. The purpose is to provide.

In order to achieve such an object , the present invention comprises a base material, a resin layer covering one surface of the base material, and a recess positioned in the resin layer, and has a light-transmitting nanoimprint. In the mold manufacturing method, an application step of applying a coating liquid containing at least an organopolysiloxane and a photocatalyst to one surface of a substrate to provide a wettability changing resin material layer, and the wettability changing resin A material layer and a master mold are pressure-bonded, and in that state, a drying process for forming a resin layer by subjecting the wettability changing resin material layer to a drying process; and a mold releasing process for separating the resin layer and the master mold from each other It was set as the structure which has.

The present invention also provides a master for a nanoimprint mold comprising a substrate, a resin layer covering one surface of the substrate, and a recess positioned in the resin layer, and having light transmittance. Applying a coating solution containing at least an organopolysiloxane and a photocatalyst to the mold to provide a wettability changing resin material layer, and pressing the wettability changing resin material layer and the substrate, The wettability-changing resin material layer is subjected to a drying process to form a resin layer, and a mold releasing step for separating the resin layer from the master mold.
As another aspect of the present invention, the material of the master mold is silicon, and the material of the base material is glass.
As another aspect of the present invention, the master mold is preliminarily subjected to a release treatment.
As another aspect of the present invention, after the mold release step, the resin layer is irradiated with light so that the water contact angle on the surface of the resin layer at the irradiated site is 10 ° or less, and then the mold release is performed on the resin layer. It was set as the structure which has the process of forming a mold release agent layer by apply | coating an agent coating liquid and drying.

  The mold for nanoimprinting of the present invention has a water contact angle on the surface of the resin layer of 80 ° or more and an HV hardness of 400 or more, and thus has high durability and excellent releasability. In addition, the resin layer contains a photocatalyst, and the water contact angle on the surface becomes 10 ° or less by light irradiation. Therefore, if it is necessary to further improve the water repellency of the mold, light irradiation is performed once to make it uniform. By forming a uniform release agent layer by applying a release agent coating solution thereafter, a mold having excellent release properties can be obtained.

  In the production method of the present invention, the formation of the resin layer is completed by subjecting the wettability changing resin material layer to a single drying process, so the process becomes simpler than the conventional method for producing a mold for nanoimprinting, Manufacturing cost can be reduced. In addition, since a wettability-changing resin material layer is provided by applying a coating solution containing at least an organopolysiloxane and a photocatalyst, the resin layer formed by applying a drying treatment to the surface is in contact with water. The angle is 80 ° or more, and the HV hardness is 400 or more. This makes it possible to produce a nanoimprint mold having high durability and excellent release properties.

It is sectional drawing which shows one Embodiment of the mold for nanoimprint of this invention. It is sectional drawing which shows other embodiment of the mold for nanoimprint of this invention. It is process drawing for demonstrating one Embodiment of the manufacturing method of the mold for nanoimprint of this invention. It is process drawing for demonstrating other embodiment of the manufacturing method of the mold for nanoimprint of this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[Nanoimprint mold]
(1) FIG. 1 is a cross-sectional view showing an embodiment of a nanoimprint mold of the present invention. In FIG. 1, a nanoimprint mold 1 includes a base material 2, a resin layer 3 covering one surface 2 a of the base material 2, and a surface 3 a opposite to the interface 3 b between the base material 2 of the resin layer 3. And a light transmitting property.
The base material 2 constituting the nanoimprint mold 1 is a base material capable of transmitting irradiation light for curing a workpiece at the time of light imprinting, and is resistant to heat curing processing at the time of thermal imprinting. It is the base material which comprises. As a material of such a base material 2, for example, quartz glass, silicate glass, calcium fluoride, magnesium fluoride, acrylic glass, or an arbitrary laminated material thereof can be used. Moreover, the thickness of the base material 2 can be set in consideration of the strength of the base material 2, the suitability for handling, the material of the workpiece, and the like, and can be appropriately set within a range of about 300 μm to 10 mm, for example.

The resin layer 3 constituting the nanoimprint mold 1 has a water contact angle on the surface of 80 ° or more, preferably 90 ° or more, and an HV hardness of 400 or more, preferably 600 or more. It can transmit the irradiation light for curing the workpiece. If the water contact angle on the surface of the resin layer 3 is less than 80 °, the mold 1 may have insufficient releasability and may impede nanoimprinting. Further, if the HV hardness of the resin layer 3 is less than 400, the durability of the mold 1 may be insufficient, which is not preferable.
Furthermore, the resin layer 3 contains a photocatalyst, and the water contact angle on the surface can be reduced to 10 ° or less by light irradiation. Thereby, when it is necessary to further improve the water repellency of the mold 1, light irradiation is performed so that the water contact angle on the surface of the resin layer 3 is 10 ° or less (uniform hydrophilicity). A coating solution can be applied to form a release agent layer with a uniform thickness to impart water repellency. When the water contact angle on the surface of the resin layer 3 irradiated with light exceeds 10 °, the thickness of the release agent layer to be formed is not uniform due to the variation in hydrophilicity of the release agent coating solution used. Water repellency may not be obtained.

In the present invention, the water contact angle is measured using a contact angle measuring instrument (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) 30 seconds after dropping a water droplet from a microsyringe. Moreover, HV hardness is measured using a micro Vickers hardness meter (Shimadzu Corporation HMV-FA series).
Such a resin layer 3 may be a resin material containing at least an organopolysiloxane and a photocatalyst, and the thickness thereof can be set in consideration of the depth, shape, etc. of the recess 4, for example, It can set suitably in the range of 0.01-10 micrometers. In addition, formation of this resin layer 3 is demonstrated in the manufacturing method of this invention mentioned later.
The concave portion 4 located on the surface 3a opposite to the interface 3b with the base material 2 of the resin layer 3 is a concave portion corresponding to a shape in which the irregularities of the pattern shape formed by nanoimprint are inverted, and can be appropriately set.

(2) FIG. 2 is a cross-sectional view showing another embodiment of the nanoimprint mold of the present invention. In FIG. 2, a nanoimprint mold 1 ′ includes a base material 2, a resin layer 3 covering one surface 2 a of the base material 2, and a surface opposite to the interface 3 b between the resin layer 3 and the base material 2. A concave portion 4 located at 3'a and a release agent layer 5 that covers the surface 3'a of the resin layer 3 including the concave portion 4 are provided and have light transmittance.
This mold 1 ′ has a surface 3 ′ a whose surface water contact angle is 10 ° or less by irradiating the resin layer 3 with light. The release agent layer 5 is obtained by applying a hydrophilic release agent coating liquid to the surface 3 ′ a of the resin layer 3 and performing a drying process. Such a release agent layer 5 has a small variation in thickness. Therefore, the uniform release property by the release agent layer 5 is expressed, and stable nanoimprinting is possible.
The light applied to make the surface of the resin layer 3 a surface 3′a having a water contact angle of 10 ° or less includes at least light within the excitation wavelength region of the photocatalyst contained in the resin layer 3, For example, VUV (vacuum ultraviolet light), ultraviolet light, visible light, infrared light, or the like can be used.
Examples of the release agent used for the release agent layer 5 include a silane coupling agent having a fluoroalkyl group or a methyl group as a water repellent functional group, and more specific liquids include Daikin Industries, Ltd. Manufactured Optool DSX, hexamethyldisilazane (HMDS) and the like can be mentioned, and one or a combination of two or more of these can be used.

As described above, the mold 1 ′ includes the resin layer 3 having the surface 3 ′ a having a water contact angle of 10 ° or less, and the mold release agent layer 5 on the surface 3 ′ a of the resin layer 3. Except that, it is the same as the mold 1 described above. Therefore, the base material 2 and the resin layer 3 constituting the mold 1 ′ can be the same as those of the mold 1 described above.
The nanoimprint mold described above is an example, and the present invention is not limited to these embodiments.
In addition, as described above, the nanoimprint mold of the present invention is light transmissive, and may have a light transmittance suitable for light imprinting. For example, the light transmittance is 70% or more, preferably It may be 90% or more. The light transmittance can be measured using a spectrophotometer (U-3900 manufactured by Hitachi High-Tech Co., Ltd.).

[Method of manufacturing mold for nanoimprint]
Next, the manufacturing method of the nanoimprint mold of the present invention will be described.
(1) FIG. 3 is a process diagram for explaining an embodiment of a method for producing a nanoimprint mold of the present invention, and illustrates the nanoimprint mold 1 described above as an example.
(Coating process)
In the present invention, in the coating step, a wettability-changing resin material layer 3 ′ is provided by applying a coating solution containing at least organopolysiloxane and a photocatalyst to one surface 2a of the substrate 2 (FIG. 3). (A)).
As the base material 2, the base material described in the above-described nanoimprint mold 1 can be used.
The coating liquid used for forming the wettability changing resin material layer 3 'contains organopolysiloxane, and this organopolysiloxane is changed in wettability by the photocatalyst and hardly deteriorated or decomposed by the action of the photocatalyst. It shall have a main chain. Therefore, the coating liquid used in the present invention is a wettability changing resin material containing at least an organopolysiloxane and a photocatalyst.

As the photocatalyst, when the irradiated light is absorbed, the chemical structure of the surrounding organic substance is changed. For example, titanium oxide (TiO ₂ ), zinc oxide (ZnO), known as a photo semiconductor, Examples include metal oxides such as tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide (Bi ₂ O ₃ ), and iron oxide (Fe ₂ O ₃ ). These can be used alone or in combination of two or more.
Among such photocatalysts, titanium oxide can be preferably used in the present invention because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available. Titanium oxide includes anatase type and rutile type, and both can be used in the present invention, but anatase type titanium oxide is preferable. This anatase-type titanium oxide has an excitation wavelength of 380 nm or less, and preferably has a smaller particle size because the photocatalytic reaction occurs efficiently. For example, the average particle size is 50 nm or less, more preferably 20 nm or less. Those are preferred. Examples of such anatase-type titanium oxide include hydrochloric acid peptizer-type anatase-type titania sol (STS-02 (average particle size: 7 nm) manufactured by Ishihara Sangyo Co., Ltd.), nitrate-peptide-type anatase-type titania sol (Nissan Chemical). TA-15 (average particle size: 12 nm)) manufactured by Co., Ltd.
The content of the photocatalyst in the solid content of the coating solution can be set in the range of 5 to 60% by weight, preferably 20 to 60% by weight. When the content of the photocatalyst is less than 5% by weight, the wettability change becomes insufficient or the time required for the wettability change becomes longer. When the photocatalyst content exceeds 60% by weight, the wettability changed resin material layer 3 ′ is dried. The mechanical strength of the resin layer 3 formed by the treatment becomes insufficient, which is not preferable.

In addition, as described above, the organopolysiloxane used in the coating liquid has a main chain that changes in wettability by the photocatalyst and is difficult to be degraded or decomposed by the action of the photocatalyst. For example, (1) Sol-gel reaction Examples include organopolysiloxanes that exhibit high strength by hydrolyzing and polycondensing chloro or alkoxysilanes, etc., and (2) organopolysiloxanes crosslinked with reactive silicones that are excellent in water and oil repellency. .
In the case of (1) above, the general formula Y _n SiX _(4-n)
(Where Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group, an acetyl group or a halogen. N is an integer from 0 to 3. is there.)
It is preferable that it is the organopolysiloxane which is a 1 type, or 2 or more types of hydrolysis condensate or cohydrolysis condensate of the silicon compound shown by these. In addition, it is preferable that carbon number of the group shown by Y exists in the range of 1-20, and it is preferable that the alkoxyl group shown by X is a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

  Specifically, methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane; ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, Ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-t-butoxysilane; n-propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxy Silane, n-propyltri-t-butoxysilane; n-hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hex Lutriisopropoxysilane, n-hexyltri-t-butoxysilane; n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltriisopropoxysilane, n- Decyltri-t-butoxysilane; n-octadecyltrichlorosilane, n-octadecyltribromosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltrit-butoxysilane; Phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane; tetrachlorosilane Tetrabromosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane; dimethyldichlorosilane, dimethyldibromosilane, dimethyldimethoxysilane, dimethyldiethoxysilane; diphenyldichlorosilane, diphenyldibromosilane, Diphenyldimethoxysilane, diphenyldiethoxysilane; phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane; trichlorohydrosilane, tribromohydrosilane, trimethoxyhydrosilane, triethoxyhydrosilane, triisopropoxy Hydrosilane, tri-t-butoxyhydrosilane; vinyltrichlorosilane, vinyltribromosilane, vinyltri Methoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltrit-butoxysilane; trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyl Triisopropoxysilane, trifluoropropyltri-t-butoxysilane; γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy Propyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane; γ-methacryloxypropylmethyldimeth Silane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ-methacryloxypropyl Tri-t-butoxysilane; γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ- Aminopropyltri-t-butoxysilane; γ-mercaptopropylmethyldimethoxylane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysila , Γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltri-t-butoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxylane, β- (3,4-epoxycyclohexyl) ethyltriethoxylane And partial hydrolysates thereof; and mixtures thereof can be used.

In particular, a polysiloxane containing a fluoroalkyl group can be preferably used, and specific examples thereof include one or two or more hydrolytic condensates and cohydrolytic condensates of the following fluoroalkylsilanes: In general, those known as fluorine-based silane coupling agents can be used.
_{CF 3 (CF 2) 3 CH} 2 CH 2 Si (OCH 3) 3;
_{CF 3 (CF 2) 5 CH} 2 CH 2 Si (OCH 3) 3;
_{CF 3 (CF 2) 7 CH} 2 CH 2 Si (OCH 3) 3;
_{CF 3 (CF 2) 9 CH} 2 CH 2 Si (OCH 3) 3;
(CF ₃ ) CF (CF ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ;
(CF ₃ ) CF (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ;
(CF ₃ ) CF (CF ₂ ) ₈ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ;
_{CF 3 (C 6 H 4)} C 2 H 4 Si (OCH 3) 3;
_{CF 3 (CF 2) 3 (} C 6 H 4) C 2 H 4 Si (OCH 3) 3;
_{CF 3 (CF 2) 5 (} C 6 H 4) C 2 H 4 Si (OCH 3) 3;
_{CF 3 (CF 2) 7 (} C 6 H 4) C 2 H 4 Si (OCH 3) 3;
_{CF 3 (CF 2) 3 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 5 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 7 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 9 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
(CF ₃ ) CF (CF ₂ ) ₄ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ;
(CF ₃ ) CF (CF ₂ ) ₆ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ;
(CF ₃ ) CF (CF ₂ ) ₈ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ;
_{CF 3 (C 6 H 4)} C 2 H 4 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 3 (} C 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 5 (} C 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 7 (} C 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 3 CH} 2 CH 2 Si (OCH 2 CH 3) 3;
_{CF 3 (CF 2) 5 CH} 2 CH 2 Si (OCH 2 CH 3) 3;
_{CF 3 (CF 2) 7 CH} 2 CH 2 Si (OCH 2 CH 3) 3;
_{CF 3 (CF 2) 9 CH} 2 CH 2 Si (OCH 2 CH 3) 3; and
_{CF 3 (CF 2) 7 SO} 2 N (C 2 H 5) C 2 H 4 CH 2 Si (OCH 3) 3.

ただし、ｎは２以上の整数であり、Ｒ¹、Ｒ²はそれぞれ炭素数１〜１０の置換もしくは非置換のアルキル、アルケニル、アニールあるいはシアノアルキル基であり、モル比で全体の４０％以下がビニル、フェニル、ハロゲン化フェニルである。また、Ｒ¹、Ｒ²がメチル基のものが表面エネルギーが最も小さくなるので好ましく、モル比でメチル基が６０％以上であることが好ましい。また、鎖末端もしくは側鎖には、分子鎖中に少なくとも１個以上の水酸基等の反応性基を有することが好ましい。 In addition, examples of the reactive silicone (2) include compounds having a skeleton represented by the following general formula.

However, n is an integer of 2 or more, and R ¹ and R ² are each a substituted or unsubstituted alkyl, alkenyl, anneal, or cyanoalkyl group having 1 to 10 carbon atoms, and the molar ratio is 40% or less. Vinyl, phenyl and phenyl halide. In addition, it is preferable that R ¹ and R ² are methyl groups because the surface energy is the smallest, and it is preferable that the methyl groups are 60% or more by molar ratio. Further, the chain end or side chain preferably has at least one reactive group such as a hydroxyl group in the molecular chain.

Moreover, you may mix the stable organosilicone compound which does not produce a crosslinking reaction like dimethylpolysiloxane with said organopolysiloxane.
Further, the coating liquid can further contain a surfactant. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Megafac F-141, 144 manufactured by Ink Chemical Industry Co., Ltd., Fientent F-200, F-251 manufactured by Neos Co., Ltd. Yunidyne DS-401, 402 manufactured by Daikin Industries, Ltd., manufactured by 3M Co., Ltd. Fluorine-based or silicone-based nonionic surfactants such as Fluorard FC-170 and 176 can be mentioned, and cationic surfactants, anionic surfactants and amphoteric surfactants can also be used.
In addition to the above surfactants, the coating solution includes polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate, Polyvinyl chloride, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, oligomers, polymers, etc. It can be included.

Such a coating liquid can be prepared by dispersing the above-described components in a solvent together with other additives as necessary. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable.
Application onto the substrate 2 can be performed by a known application method such as spin coating, spray coating, dip coating, roll coating, or bead coating.
The thickness of the wettability-changing resin material layer 3 ′ to be formed can be set in consideration of the depth, shape, etc. of the recess 4 formed in a later step, and is set, for example, in the range of about 0.01 to 10 μm. be able to.

(Drying process)
Next, in the drying step, the wettability changing resin material layer 3 ′ and the master mold 11 are pressure-bonded, and a drying process is performed in this state to form the resin layer 3 (FIG. 3B).
The master mold 11 has a convex portion 12 having a desired shape, and the material may be made of an inorganic material such as silicon, glass, quartz, or metal, or may be made of a resin material. Good.
The drying process for the wettability changing resin material layer 3 ′ can be appropriately set within a temperature range of 20 to 200 ° C., for example.
The resin layer 3 formed by performing such a drying treatment has a water contact angle on the surface of 80 ° or more, preferably 90 ° or more, and an HV hardness of 400 or more, preferably 600 or more. It becomes possible to transmit irradiation light for curing the workpiece during printing.

(Release process)
Next, in the mold release step, the resin layer 3 and the master mold 11 are separated (FIG. 3C). In this release step, the water contact angle on the surface of the resin layer 3 is 80 ° or more, so that the release from the master mold 11 is easy, and damage to the resin layer 3 is prevented. Thereby, the mold 1 for nanoimprinting is obtained.

(2) Next, another embodiment of the method for producing a nanoimprint mold of the present invention will be described using the nanoimprint mold 1 as an example with reference to FIG.
(Coating process)
In the present invention, in the coating step, a coating solution containing at least organopolysiloxane and a photocatalyst is applied to the master mold 11 to provide the wettability changing resin material layer 3 '(FIG. 4A). The master mold 11 to be used is the same master mold as in the above-described embodiment, and the coating liquid and the coating method described in the above-described embodiment can be used as the coating liquid and the coating method. The thickness of the wettability changing resin material layer 3 ′ can be set in consideration of the height, shape, etc. of the convex portion 12 of the master mold 11, and is set, for example, in the range of about 0.01 to 10 μm. be able to.
(Drying process)
Next, in the drying step, the wettability changing resin material layer 3 ′ and the base material 2 are pressure-bonded, and a drying process is performed in this state to form the resin layer 3 (FIG. 4B). The base material 2 can use the same base material as the above-mentioned embodiment, and can also perform a drying process similarly to the above-mentioned embodiment. The resin layer 3 formed by performing such a drying treatment has a water contact angle on the surface of 80 ° or more, preferably 90 ° or more, and an HV hardness of 400 or more, preferably 600 or more. It becomes possible to transmit irradiation light for curing the workpiece during printing.
(Release process)
Next, in the mold release step, the resin layer 3 and the master mold 11 are separated (FIG. 4C). In this release step, the water contact angle on the surface of the resin layer 3 is 80 ° or more, so that the release from the master mold 11 is easy, and damage to the resin layer 3 is prevented. Thereby, the mold 1 for nanoimprinting is obtained.

  According to the present invention, since the formation of the resin layer 3 is completed by subjecting the wettability-changing resin material layer 3 ′ to a single drying process, the steps are compared with the conventional method for manufacturing a nanoimprint mold. It becomes simple and the manufacturing cost can be reduced. Further, since the wettability changing resin material layer 3 ′ is provided by applying a coating liquid containing at least an organopolysiloxane and a photocatalyst, the resin layer 3 formed by performing a drying process on the resin layer 3 The water contact angle is 80 ° or more and the HV hardness is 400 or more, which makes it possible to produce a nanoimprint mold having high durability and excellent releasability. Further, when the material of the master mold 11 is silicon and the material of the base material 2 is glass, the wettability changing resin material layer 3 ′ and the adhesion between the formed resin layer 3 and the base material 2 are remarkably improved. On the other hand, since the formed resin layer 3 exhibits excellent releasability with respect to the master mold 11, the manufacturing stability of the mold is further improved.

The above-described method for producing a mold for nanoimprinting is an exemplification, and the present invention is not limited to these embodiments.
For example, the master mold 11 may be subjected to a mold release process in advance. This mold release treatment is, for example, a silane coupling agent having a fluoroalkyl group or a methyl group as a water repellent functional group, and more specifically, Daikin Industries, Ltd. OPTOOL DSX, hexamethyldisilazane (HMDS), etc. Can be performed by a dip coating method, a spin coating method, a gas phase method, or the like. In this way, by subjecting the master mold 11 to the mold release process in advance, the formed resin layer 3 exhibits a further excellent mold release property with respect to the master mold 11, so that the mold manufacturing stability is further improved. .

  In addition, after the mold release step, the resin layer 3 is irradiated with light so that the water contact angle on the surface of the resin layer at the irradiation site is 10 ° or less, and then a release agent coating solution is applied to the resin layer 3. The release agent layer may be formed by drying and curing. Thereby, the above-mentioned nanoimprint mold 1 ′ can be produced. As the release agent coating solution, for example, a release agent such as a silane coupling agent having a fluoroalkyl group or a methyl group as a water-repellent functional group, more specifically, OPTOOL DSX, hexamethyl manufactured by Daikin Industries, Ltd. A hydrophilic release agent coating solution comprising one or a combination of two or more of disilazane (HMDS) can be used.

Next, the present invention will be described in more detail by showing more specific examples.
[Example 1]
Quartz glass (65 mm square) with a thickness of 6.35 mm was prepared as a base material for a mold for nanoimprinting.
<Application process>
First, a coating liquid (wetability changing resin material) having the following composition is applied and coated on one surface of the base material by a spin coating method, and then subjected to heat treatment (40 ° C., 2 minutes) to get wet. A property change resin material layer was formed.
(Composition of coating solution (wetability changing resin material))
・ Amorphous silica (Grasca HPC7002 manufactured by JSR Corporation): 50 parts by weight ・ Change in wettability (Grasca HPC402H manufactured by JSR Corporation): 10 parts by weight ・ Photocatalyst (TA-15 manufactured by Nissan Chemical Co., Ltd.) Diameter 12 nm)) 20 parts by weight Solvent component (toluene) 20 parts by weight

<Drying process>
Next, the silicon substrate was processed to produce a master mold in which columnar convex portions having a diameter of 100 nm were arranged in a 30 mm square region at a pitch of 200 nm. This master mold was pressure-bonded to the wettability changing resin material layer and subjected to a drying treatment (150 ° C., 10 minutes) to form a resin layer (thickness 1 μm).
<Mold release process>
Next, the master mold and the resin layer were separated from each other to obtain a nanoimprint mold having a recess (depth: 200 nm, diameter: 100 nm) in a central 30 mm square region of the resin layer.

<Evaluation>
The water contact angle on the surface of the resin layer of the nanoimprint mold produced in this way was 95 °, and the HV hardness was 610. The light transmittance of the nanoimprint mold was 97%. Thereby, it was confirmed that the produced mold for nanoimprinting has high durability and excellent releasability.
The water contact angle was measured using a contact angle measuring instrument (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) 30 seconds after dropping a water droplet from a microsyringe to a non-formed portion of the recess. Moreover, HV hardness was measured using the micro Vickers hardness meter (Shimadzu Corporation HMV-FA series). The light transmittance was measured using a spectrophotometer (U-3900 manufactured by Hitachi High-Tech Co., Ltd.). The same applies to the following examples and comparative examples.
Moreover, about 100 nanoimprint molds produced in this way, as a result of observing the concave portion of the resin layer with an optical microscope, no damage occurred.

[Example 2]
In the same manner as in Example 1, a base material for a nanoimprint mold was prepared, and a master mold was prepared.
<Application process>
First, the surface of the master mold on which the cylindrical convex portions are formed is coated with a coating liquid (wetability changing resin material) having the following composition by spin coating, followed by heat treatment (40 ° C. 2 minutes) to form a wettability changing resin material layer.
(Composition of coating solution (wetability changing resin material))
・ Amorphous silica (Grasca HPC7002 manufactured by JSR Corporation) 60 parts by weight. Changeable wettability component (Grasca HPC402H manufactured by JSR Corporation) 15 parts by weight. Photocatalyst TA-15 (average grain manufactured by Nissan Chemical Co., Ltd.) Diameter 12 nm)) 20 parts by weight Solvent component (toluene) 5 parts by weight <Drying step>
Next, one surface of the base material was pressure-bonded to the wettability changing resin material layer and subjected to a drying treatment (150 ° C., 10 minutes) to form a resin layer (thickness 4 μm).
<Mold release process>
Next, the master mold and the resin layer were separated from each other to obtain a nanoimprint mold having a recess (depth: 200 nm, diameter: 100 nm) in a central 30 mm square region of the resin layer.

<Evaluation>
The water contact angle on the surface of the resin layer of the nanoimprint mold produced in this way was 98 °, and the HV hardness was 700. The light transmittance of the nanoimprint mold was 97%. Thereby, it was confirmed that the produced mold for nanoimprinting has high durability and excellent releasability.
Moreover, about 100 nanoimprint molds produced in this way, as a result of observing the concave portion of the resin layer with an optical microscope, no damage occurred.

[Example 3]
The resin layer of the nanoimprint mold produced in Example 1 was irradiated with light. This light irradiation was performed by irradiating 200 mJ / cm ^{2 of} parallel light (vacuum ultraviolet light having a wavelength of 172 nm). As a result, the water contact angle on the surface of the resin layer was 10 °.
Next, a release agent coating solution (Optool DSX, manufactured by Daikin Industries, Ltd.) is applied on the resin layer by a dip coating method, and dried (60 ° C., 60 minutes) to form a release agent layer. Thus, a mold for nanoimprinting was obtained.
As a result of measuring the water contact angle on the surface of the release agent layer of the nanoimprint mold produced in this way at a lattice point of 10 mm pitch, it is 105 ° or more, which is even better than the nanoimprint mold produced in Example 1. It was confirmed that the mold had releasability.

[Comparative Example 1]
Instead of the coating liquid of Example 1 (wetability changing resin material), a resin material having the following composition not containing a wettability changing component was used, and the drying process was performed at 150 ° C. for 10 minutes. In the same manner as in Example 1, a nanoimprint mold was produced.
(Composition of coating liquid (resin material))
Amorphous silica (Glaska HPC7002 manufactured by JSR Co., Ltd.) 82 parts by weight Solvent component (toluene) 18 parts by weight The water contact angle of the surface of the resin layer of the nanoimprint mold produced in this way is 78 °, HV hardness As compared with the nanoimprint molds produced in Examples 1 and 2, the HV hardness was low and the durability was inferior, and the water contact angle was small and the releasability was inferior.
Moreover, about 100 nanoimprint molds produced in this way, as a result of observing the concave portion of the resin layer with an optical microscope, 67 pieces were damaged. From this result and the measurement result of the water contact angle on the surface of the resin layer described above, it is considered that the releasability between the master mold and the resin layer was poor and the resin layer was damaged in the release process.

[Comparative Example 2]
Among the nanoimprint molds produced in Comparative Example 1, those in which no damage was observed in the recesses of the resin layer were irradiated on the resin layer under the same conditions as in Example 3. As a result, the water contact angle on the surface of the resin layer was 20 °. Although the amount of change in the water contact angle is small compared to Example 3, even when the resin layer does not contain a wettability changing component, the water contact angle is reduced by irradiation with vacuum ultraviolet rays because of the organic compound due to ultraviolet rays. This is probably because organic compounds were removed from the surface due to strong oxidation during decomposition and ozone generation and decomposition.
Next, a release agent coating solution having the same composition as that of Example 3 was applied onto the resin layer by a spin coating method, followed by drying (60 ° C., 60 minutes) to form a release agent layer. A mold for nanoimprinting was obtained.
However, the release agent coating solution is partially repelled on the surface of the resin layer, and a uniform release agent layer cannot be formed.

  It can be used for microfabrication using nanoimprint technology.

DESCRIPTION OF SYMBOLS 1,1 '... Nanoimprint mold 2 ... Base material 3 ... Resin layer 3' ... Wetting property change resin material layer 4 ... Recessed part 5 ... Release agent layer 11 ... Master mold

Claims (5)

In a method for producing a mold for nanoimprinting, comprising a base material, a resin layer covering one surface of the base material, and a recess located in the resin layer, and having light transmittance,
An application step of applying a coating liquid containing at least an organopolysiloxane and a photocatalyst to one surface of the substrate to provide a wettability changing resin material layer;
The wettability change resin material layer and the master mold are pressure-bonded, and in that state, a drying process is performed on the wettability change resin material layer to form a resin layer;
A mold release step for separating the resin layer from the master mold. In a method for producing a mold for nanoimprinting, comprising a base material, a resin layer covering one surface of the base material, and a recess located in the resin layer, and having light transmittance,
An application step of applying a coating liquid containing at least organopolysiloxane and a photocatalyst to the master mold to provide a wettability changing resin material layer;
The wettability changing resin material layer and the base material are pressure-bonded, and in that state, the wettability changing resin material layer is subjected to a drying treatment to form a resin layer;
A mold release step for separating the resin layer from the master mold. The method for producing a mold for nanoimprinting according to claim 1 or 2 , wherein the material of the master mold is silicon and the material of the base material is glass. Method of manufacturing a mold for nanoimprinting according to any one of claims 1 to 3, characterized by applying in advance a release treatment on the master mold. After the mold release step, the resin layer is irradiated with light so that the water contact angle of the surface of the resin layer at the irradiated site is 10 ° or less, and then a release agent coating solution is applied to the resin layer, method for producing a mold for nanoimprinting according to any one of claims 1 to 4 characterized by having a step of forming a release agent layer by drying.

Images