JP2014066976A - Fine concavo-convex molded body, fine concavo-convex pattern forming mold, and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high-quality fine concavo-convex molded body by preventing poor filling of a transfer material into a mold, loss of convex portions from a transferred product due to demolding resistance, and collapsing of a pattern of the convex portions of a transferred fine concavo-convex structure.SOLUTION: A fine concavo-convex molded body (10) includes a base material (11) and a fine concavo-convex structure (12) having a plurality of convex portions (14) and a plurality of concave portions (15) provided on a surface of the base material (11). The fine concavo-convex molded body (10) further includes regions with densely packed convex portions, in which any convex portion (14) and convex portions (14) most adjacent thereto are closely arranged and which are randomly located when viewed from above.

Description

  The present invention relates to a fine concavo-convex molded body and a fine concavo-convex molded mold used for, for example, an antireflection film, and methods for producing the same.

  In recent years, the refractive index for light incident on a substrate has been changed continuously by providing a concavo-convex structure at the interface in the antireflection technology for improving the display quality of flat panel displays such as liquid crystal displays and plasma displays. Thus, it is known that the discontinuous interface of the refractive index can be eliminated to prevent light reflection.

  Such a fine concavo-convex structure exhibiting an antireflection effect is known as a moth-eye structure.

  The moth-eye structure is generally manufactured by using a mold having an inverted fine concavo-convex structure and transferring the mold onto a transfer material made of resin or the like. However, in the case of a fine concavo-convex structure having a particularly high antireflection effect among the moth-eye structures, for example, a fine concavo-convex structure having a high convexity height ratio (aspect ratio) to the convex minor axis length, improper filling of the transfer material into the mold In addition, there is a problem in that the protruding portion of the transferred product is lost due to an increase in peeling resistance when the transfer material is peeled from the mold.

  In addition, the transferred fine concavo-convex structure also has a problem that pattern collapse occurs due to static electricity at the time of peeling. For example, Patent Document 1 discloses a technique capable of improving transferability by forming a convex portion having a fine concavo-convex structure with a specific tapered main body portion and a tip portion having a curved surface structure.

Japanese Patent No. 4849183

  However, since the technology disclosed in Patent Document 1 includes a convex portion having a fine concavo-convex structure including a specific tapered main body portion and a tip portion having a curved surface structure, it depends on the design of the taper and the convex portion curvature. There was a difficulty in pattern production.

  The present invention is intended to solve the above-described problems, and prevents improper filling of the transfer material into the mold, loss of the convex portion of the transferred product due to peeling resistance, and pattern collapse of the convex portion of the transferred fine concavo-convex structure. It is another object of the present invention to provide a fine concavo-convex molded body of high quality, and to provide a fine concavo-convex molding mold for producing the same, and a method for producing the same.

  The present inventors have found that the above problems can be solved by making the fine concavo-convex molded body and the fine concavo-convex structure of the fine concavo-convex molding mold for producing the same have a specific pattern shape and arrangement. It came to be completed. That is, the present invention is as follows.

  The fine concavo-convex molded article of the present invention is a fine concavo-convex molded article having a base material and a fine concavo-convex structure including a plurality of convex portions and a plurality of concave portions provided on the surface of the base material. A convex portion dense spot where a convex portion and the convex portion nearest to the convex portion are continuous is formed, and the convex portion dense spot is randomly arranged in a top view.

  According to this configuration, when the fine concavo-convex structure has a specific pattern shape and arrangement, when the fine concavo-convex molded body is manufactured, the filling property of the transfer material into the fine concavo-convex structure of the fine concavo-convex molding mold is improved, and The transferred fine concavo-convex structure can obtain a pattern strength that does not lose the peeling resistance when the transfer material is peeled from the fine concavo-convex mold. Furthermore, the convex part of the fine concavo-convex structure of the fine concavo-convex molded body takes a form in which the adjacent convex parts partially meet each other or are partially fused, so that the physical pattern does not fall down Has a stable structure. As a result, a high-quality fine uneven molded body can be obtained.

In the fine concavo-convex molded article of the present invention, convex dense areas where the convex portions of the fine concavo-convex structure and the convex portions closest to the convex portions are connected at an average interval (p _n ) of 200 nm or less. It is preferable that the average interval (P _N ) between the adjacent convex portion dense spots is _pn or more and 400 nm or less.

  Moreover, in the fine uneven | corrugated molded object of this invention, it is preferable that the convex part height ratio with respect to a convex-part short-axis length is 2 or more on average in the cross sectional view of arbitrary said convex parts.

  In the fine concavo-convex molded article of the present invention, the fine concavo-convex structure is a cured product of a resin composition, and the resin composition contains three or more acrylic groups and / or methacrylic groups in one molecule in 100 parts by mass. Composition containing 20 to 60 parts by mass of one or more kinds of monomer components, 5 to 40 parts by mass of monomer components having an N-vinyl group, and 0 to 75 parts by mass of other monomer components It is preferable that it is a thing.

  In the fine uneven molded body of the present invention, the resin composition is preferably a photocurable composition. Moreover, it is preferable that the viscosity at 50 degreeC of the said photocurable composition is 100 mPa * s or less.

  The antireflection film of the present invention is characterized by comprising the fine concavo-convex molded body of the present invention.

  The fine concavo-convex mold of the present invention is a fine concavo-convex mold having a base material and a fine concavo-convex structure including a plurality of convex portions and a plurality of concave portions provided on the surface of the base material. The convex portion and the convex portion closest to the convex portion are connected to form a convex portion dense portion, and the convex portion dense portion is randomly arranged in a top view. .

  According to this configuration, when the fine concavo-convex structure has a specific pattern shape and arrangement, when the fine concavo-convex molded body is manufactured, the filling property of the transfer material into the fine concavo-convex structure of the fine concavo-convex molding mold is improved, and The transferred fine concavo-convex structure can obtain a pattern strength that does not lose the peeling resistance when the transfer material is peeled from the fine concavo-convex mold. Furthermore, the convex part of the fine concavo-convex structure of the fine concavo-convex molded body takes a form in which the adjacent convex parts partially meet each other or are partially fused, so that the physical pattern does not fall down, Has a stable structure. As a result, a high-quality fine uneven molded body can be obtained.

In the fine concavo-convex molding mold of the present invention, a dense portion of convex portions in which an arbitrary interval between the arbitrary convex portion of the fine concavo-convex structure and the convex portion nearest to the convex portion is continuous with an average interval (p _n ) of 200 nm or less. It is preferable that the average interval (P _N ) between the adjacent convex portion dense spots is _pn or more and 400 nm or less.

  In the fine concavo-convex molding mold of the present invention, it is preferable that the ratio of the convex portion height to the convex minor axis length is 2 or more on average in the sectional view of the arbitrary convex portion.

  In the method for producing a fine concavo-convex molded article of the present invention, a solution containing a self-assembled block copolymer is applied on a substrate, a coating layer is produced, and the coating layer is randomly formed by self-assembly. A step of producing an arranged sea-island-like phase separation structure; a step of selectively etching the sea or island portion of the phase-separation structure to produce an uneven sea-island-like resist pattern layer; and the uneven sea-island-like resist pattern. And a step of forming a first pattern having a random shape on the base material and a second pattern having a fine concavo-convex shape along the first pattern by etching using the mask as a mask. And

  According to this configuration, it has a fine concavo-convex structure including a plurality of convex portions and a plurality of concave portions provided on the surface of the base material, and the arbitrary convex portions and the convex portions closest to the convex portions. It is possible to easily obtain a fine concavo-convex structure molded body in which convex portions densely spaced from each other are formed and the convex dense portions are randomly arranged in a top view.

  Further, in the method for producing a fine concavo-convex molded article of the present invention, a convex dense portion where the convex part of the fine concavo-convex molded article and the convex part closest to the convex part are connected is formed. It is preferable that the dense portions of the convex portions are randomly arranged in a top view.

Moreover, in the manufacturing method of the fine uneven | corrugated molded object of this invention, between the arbitrary convex part of the said uneven | corrugated shape and the said convex part nearest to the said convex part was continued with an average space | interval ( _pn ) of 200 nm or less. It is preferable that the average interval (P _N ) between the adjacent dense convex portions that are convex portions dense portions is _pn or more and 400 nm or less.

  Moreover, in the manufacturing method of the fine uneven | corrugated molded object of this invention, it is preferable that the convex part height ratio with respect to a convex-part short-axis length is 2 or more on average in the cross sectional view of the arbitrary convex parts of the said uneven | corrugated shape.

  The method for producing a fine concavo-convex molding mold of the present invention comprises applying a solution containing a self-assembled block copolymer on a substrate to produce a coating layer, and randomly forming the coating layer by self-assembly in the coating layer. A step of producing an arranged sea-island-like phase separation structure; a step of selectively etching the sea or island portion of the phase-separation structure to produce an uneven sea-island-like resist pattern layer; and the uneven sea-island-like resist pattern. And a step of forming a first pattern having a random shape on the base material and a second pattern having a fine concavo-convex shape along the first pattern by etching using the mask as a mask. And

  According to this configuration, it has a fine concavo-convex structure including a plurality of convex portions and a plurality of concave portions provided on the surface of the base material, and the arbitrary convex portions and the convex portions closest to the convex portions. It is possible to easily obtain a fine concavo-convex structure molding mold in which convex portions densely spaced from each other are formed and the convex dense portions are randomly arranged in a top view.

  Further, in the method for producing a fine concavo-convex molding mold according to the present invention, a convex dense portion where the convex part of the fine concavo-convex molded body and the convex part nearest to the convex part are continuous is formed. It is preferable that the dense portions of the convex portions are randomly arranged in a top view.

Moreover, in the manufacturing method of the fine uneven | corrugated shaping | molding mold of this invention, between the arbitrary convex part of the said uneven | corrugated shape and the said convex part nearest to the said convex part was continued with an average space | interval ( _pn ) of 200 nm or less. It is preferable that the average interval (P _N ) between the adjacent dense convex portions that are convex portions dense portions is _pn or more and 400 nm or less.

  Moreover, in the manufacturing method of the fine uneven | corrugated shaping | molding mold of this invention, it is preferable that the convex part height ratio with respect to a convex-part short-axis length is 2 or more on average in the cross sectional view of the arbitrary convex parts of the said uneven | corrugated shape.

  The method for producing a fine concavo-convex molded article of the present invention is obtained by transferring the fine concavo-convex structure to a transfer material using the fine concavo-convex molded mold obtained by the method for producing a fine concavo-convex molded mold of the present invention. It is characterized by that.

  According to the present invention, when the fine concavo-convex structure has a specific pattern shape and arrangement, when the fine concavo-convex molded body is manufactured, the filling property of the transfer material to the fine concavo-convex structure of the fine concavo-convex molding mold is improved, and The transferred fine concavo-convex structure can obtain a pattern strength that does not lose the peeling resistance when the transfer material is peeled from the fine concavo-convex mold. Furthermore, the convex part of the fine concavo-convex structure of the fine concavo-convex molded body takes a form in which the adjacent convex parts partially meet each other or are partially fused, so that the physical pattern does not fall down, Has a stable structure. As a result, a high-quality fine uneven molded body can be obtained.

It is a cross-sectional schematic diagram which shows the fine uneven | corrugated molded object which concerns on this Embodiment. It is a plane schematic diagram for demonstrating the calculation method of the pitch between the most adjacent convex parts and the pitch between convex part dense locations in the fine grooving | roughness molded object which concerns on this Embodiment. It is the plane schematic diagram and cross-sectional schematic diagram which show the fine grooving | roughness structure of the fine grooving | roughness formation body which concerns on this Embodiment. It is an electron micrograph which shows the top view of the molded object A which concerns on the Example of this invention. It is a photograph which shows the result of the form observation using the scanning probe microscope of the convex part dense location of the molded object A which concerns on the Example of this invention. It is an electron micrograph which shows the cross sectional view of the molded object A which concerns on the Example of this invention.

  Hereinafter, embodiments of the present invention will be specifically described.

  The fine concavo-convex molded body according to the embodiment of the present invention will be specifically described with reference to FIG. FIG. 1 is a schematic cross-sectional view showing a fine uneven molded body according to the present embodiment. As shown in FIG. 1, the fine concavo-convex molded body 10 includes a base material 11 and a fine concavo-convex structure 12 provided on the surface thereof.

  The fine concavo-convex molded body 10 according to the present embodiment is obtained by forming a fine concavo-convex structure 12 on a base material 11, and in addition to exhibiting a light reflection preventing function or the like itself, Both a molding mold for forming the structure 12 and transferring the fine concavo-convex structure 12 to another substrate, and a transfer product in which the fine concavo-convex structure 12 is transferred from the molding mold to the substrate 11 are included. Therefore, unless specifically mentioned in the following description, the fine concavo-convex molded body 10 includes both a mold and a transfer product.

  The fine concavo-convex structure 12 includes a plurality of convex portions 14 and concave portions 15. A convex dense portion where the arbitrary convex portion 14 and the convex portion 14 adjacent to the convex portion 14 are continuous is formed, and the convex portion dense portions are randomly arranged in a top view.

  In the fine concavo-convex structure 12, the height (H) from the reference surface 13 to the apex of the convex portion 14 in a predetermined region is preferably 200 nm or more, more preferably 250 nm or more.

  Here, the predetermined region is an arbitrary 500 nm square region having a pattern, and is hereinafter referred to as a measurement region. Moreover, in the said measurement area | region, let the lowest point of the recessed part 15 be a zero point (it shows by O in FIG. 1), and let the height from a zero point be a convex part height. A plane including the zero point is defined as a reference plane 13. Note that the zero point is the data on the height of the fine concavo-convex structure obtained from the scanning probe microscope extracted by text conversion, and the position where the height is minimized is defined as the zero point.

  In addition, the convex part 14 in this Embodiment shows what has a height of 100 nm or more from the reference plane 13. Further, W in FIG. 1 indicates the short axis length at the bottom of the convex portion 14.

  The fine concavo-convex molded body 10 according to the present embodiment further has a ratio of the height (H) of the convex portion 14 to the minor axis length W of the bottom portion of the convex portion 14 (hereinafter referred to as aspect) in a cross-sectional view of the arbitrary convex portion 14. Ratio) is preferably 3 or more on average, and more preferably 4 or more on average. When the aspect ratio is within the above range, the shape of the protrusions 14 is elongated, the packing density of the protrusions 14 is increased, and the antireflection effect is higher.

In the fine concavo-convex structure 12 of the fine concavo-convex shaped body 10 shown in FIG. 1, and any protrusion 14, the distance between the convex portion 14 that is the closest thereto (hereinafter, referred to as a pitch p _n between the most adjacent convex portions) is used The distance is smaller than the wavelength of the light to be transmitted. By the nearest protrusion pitch p _n to 200nm or less, the better protrusions filling properties, preferably in that the reflectance characteristics are improved, it is 150nm or less, a high antireflection effect, and the haze It is more preferable in that it can be reduced. In addition, it is more preferable that the pitch _Pn between the most adjacent convex portions is 50 nm or more so that the releasability from the molding mold is improved, and the release property at the time of repeated transfer is improved when it is 80 nm or more.

The method of calculating the pitch p _n between nearest projections, as shown in FIGS. 2A and formula (1), any convex having at any of the convex portions densely locations, from the reference plane 13 than 100nm height A distance obtained by connecting a straight line between the top of the top and another top of the convex that belongs to the same convexity dense portion as the arbitrary convex top and is adjacent to the top is measured. Similarly, 50 points of the distance between the most adjacent protrusions with respect to an arbitrary protrusion is measured, and the average is calculated as _pn .

Formula (1)

  In the fine concavo-convex structure of the fine concavo-convex molded body 10 according to the present embodiment, a convex portion dense portion where an arbitrary convex portion 14 and the convex portion 14 are adjacent to each other is formed.

  Here, "an arbitrary convex portion 14 and a convex portion dense spot where the convex portion 14 and the nearest adjacent convex portion 14 are connected" means that the convex portions 14 are not arranged independently, A portion between the portion 14 and the nearest adjacent convex portion 14 is fused at a place other than the top of the convex portion, and indicates a portion connected in a mountain range.

  Furthermore, in the fine concavo-convex structure 12 of the fine concavo-convex molded body 10 according to the present embodiment, the convex portions densely arranged are randomly arranged in a top view. “Random” means a state in which either the “sea” or “island” pattern of the sea-island pattern is arranged as a random striped pattern when viewed from above. The random shape in the fine concavo-convex molded body 10 in the present embodiment refers to a mountain-shaped convex portion dense spot formed by connecting an arbitrary convex portion 14 of the fine concavo-convex structure 12 and the convex portion 14 adjacent to the convex portion 14. The convex portion dense spots and the nearest neighboring convex portion dense spots are arranged as random striped patterns. With such an arrangement, it is possible to disperse the peeling resistance and reduce damage to the concavo-convex pattern at the time of transfer peeling from the mold, regardless of the peeling direction.

  The case shown in FIG. 3 will be described in detail with reference to an example. FIG. 3A is a schematic plan view showing the fine uneven structure of the fine uneven structure according to the present embodiment. FIG. 3B is a schematic cross-sectional view showing the fine concavo-convex structure of the fine concavo-convex formation body according to the present embodiment at a position corresponding to the line segment b in FIG. A. FIG. 3C is a schematic cross-sectional view showing the fine concavo-convex structure of the fine concavo-convex formation body according to the present embodiment at a position corresponding to line segment a in FIG. 3A.

In the portion corresponding to the line segment b shown in FIG. 3A, as shown in FIG. 3B, the two convex portions 14 are not independent from each other, and the portion between the convex portion 14 and the nearest adjacent convex portion 14 is other than the convex top portion. It is fused at the point of, and constitutes a dense part of convex parts connected in a mountain range. Moreover, in the location corresponding to the line segment a, as shown in FIG. 3C, between the convex portion 14 belonging to a certain convex portion dense location and the convex portion 14 belonging to another adjacent convex portion dense location. Then, the two convex portions 14 are independent of each other. The interval between the convex portion 14 in this case, the distance between adjacent convex portions densely locations corresponding to (hereinafter, referred. Protrusions dense portion pitch P _N).

In this embodiment, protrusions dense portion pitch P _N, in order to function as an anti-reflection, it is preferable that the distance smaller than the wavelength of the light used. Further, by satisfying P _N ≧ _pn , the releasability from the mold is improved. Protrusions dense portion pitch _{P N} is, it is 400nm or less, it is possible to reduce the diffraction of light, and more preferably is 350nm or less. By addition is 300nm or less, it is possible to reduce the deviation between the value of the pitch p _n between nearest protrusion, reduction and reflectance characteristics of the haze is improved.

The method of calculating the protrusion dense portion pitch P _N, as shown in FIGS. 2B and the following formula (2), any convex having at any of the convex portions densely locations, from the reference plane 13 than 100nm height Starting from the top of the part, the distance between the arbitrary top of the convex part and the other adjacent top of the convex part via the dense part of the concave part is measured in a straight line when viewed from above. Similarly, 50 points are measured and the average is calculated as _PN .

Formula (2)

  When the fine concavo-convex structure 12 according to the present embodiment has the above-described structure, the filling density of the convex portions 14 of the fine concavo-convex structure 12 is increased, and a physically stable fine structure without substantial pattern collapse. The uneven molded body 10 can be obtained. As a result, the fine concavo-convex molded article 10 having a high antireflection effect suitable for an optical element can be provided. Further, the fine concavo-convex structure 12 may have a shape obtained by roughening the surface of a random pattern. Thereby, the hierarchical fine concavo-convex structure 12 is formed, the refractive index gradient from the light incident side can be adjusted, and more effective antireflection characteristics are exhibited.

  Next, the material of the fine uneven molded body 10 according to the present embodiment will be described. As described above, the fine concavo-convex molded body 10 according to the present embodiment is composed of the base material 11 and the fine concavo-convex structure 12 formed on the surface of the base material 11. The concavo-convex structure 12 may be either a single layer structure having the same composition, or a multilayer structure in which the base material 11 and the fine concavo-convex structure 12 have different compositions.

  Here, the single-layer configuration means that there is no substantial interface between the base material 11 and the fine concavo-convex structure 12, and the refractive index difference is zero or as close to zero as possible. For example, the fine concavo-convex structure 12 and the base material 11 have the same composition, or the fine concavo-convex structure 12 is directly molded on the base material 11.

  Hereinafter, the material of the fine concavo-convex structure 12 that can be applied to both the single-layer structure and the multilayer structure will be described.

  As a material of the fine concavo-convex structure 12, an inorganic material such as glass, ceramic, or metal, or an organic material such as resin can be arbitrarily selected depending on the application. From the viewpoint of easy processability, it is preferably made of resin, and the type thereof is not particularly limited as long as the effects of the present invention are satisfied. Examples thereof include ionizing radiation curable resins such as thermosetting resins, thermoplastic resins, photocurable resins, and electron beam curable resins. Among these, it is preferable to use a photocurable resin that can be roll-to-roll molded and has good processing throughput.

  When using a photocuring composition as a composition which comprises the fine concavo-convex structure 12, it is preferable that the viscosity at 50 degreeC of the photocuring composition before hardening is 100 mPa * s or less. When the photocurable composition is applied to the surface of the substrate 11 by the roll-to-roll method by setting the viscosity to 100 mPa · s or less, the thickness uniformity of the photocurable composition layer can be increased, The filling rate of the photocurable composition into the uneven structure portion of the stamper can be increased, and as a result, the transfer fidelity to the optical element can be increased. The viscosity is even lower, more preferably not more than 50 mPa · s, and even more preferably 20 mPa · s, because the resin can be filled quickly to the details of the mold pattern because of its lower viscosity. Further, in order to obtain the desired thickness of the photocurable composition layer, even if the viscosity is appropriately adjusted within the above viscosity range by further adding a thickener or thickener to the photocurable composition. Good.

  Hereinafter, an example of a photocuring composition is given. As the types of monomers and oligomers (hereinafter also referred to as monomer components), radical polymerization monomer components are more preferable from the viewpoints of reaction rate and continuous productivity. Further, from the viewpoint of increasing the reactivity at the deep part of the concavo-convex structure pattern of the molding mold, a cationic polymerization monomer component having a long reaction lifetime may be mixed with the radical polymerization monomer. As the cationic polymerization monomer for photocuring, a monomer having an epoxy group, a vinyloxy group, an oxetanyl group, an oxazolyl group or the like as a polymerizable functional group is preferable.

  Examples of the radical monomer component include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, isoamyl acrylate, n-lauryl acrylate, and isomyristyl acrylate. , Stearyl acrylate, n-butoxyethyl acrylate, butoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol acrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, caprolactone acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate The Noxyethyl acrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, diethylaminoethyl acrylate, Dimethylaminoethyl acrylate quaternized product, acrylic acid, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl 2-hydroxyethyl Phthalic acid, neopentyl glycol acrylic acid benzoate, 2-acryloyloxyethyl 2-hydroxypropyl phthalate, glycidyl acrylate, 2 Acryloyloxyethyl acid phosphate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, PEG # 200 diacrylate, PEG # 400 diacrylate, PEG # 600 diacrylate, 1,4-butanediol diacrylate, neo Pentyl glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol Diacrylate, 1,10-decanediol diacrylate, glycerin diacrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, bisphenol A-EO adduct di Acrylate, trifluoroethyl acrylate, tetrafluoropentyl acrylate, octafluoropentyl acrylate, perfluorooctyl ethyl acrylate, nonylphenol-EO adduct acrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane acrylic acid benzoate, hydroxypivalic acid Neopentyl glycol diacrylate, tetrafurfuryl alcohol oligoacrylate, ethyl carbitol oligoacrylate, 1,4-butanediol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, pentamethyl Piperidyl acrylate, tetramethylpiperidyl acrylate , Paracumylphenol-EO modified acrylate, N-acryloyloxyethyl hexahydrophthalimide, isocyanuric acid-EO modified diacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl Methacrylate, isodecyl methacrylate, isoamyl methacrylate, n-lauryl methacrylate, isomyristyl methacrylate, stearyl methacrylate, n-butoxyethyl methacrylate, butoxydiethylene glycol methacrylate, methoxytriethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, tripropylene glycol dimethacrylate, tetraethylene Glico Rudimethacrylate, caprolactone methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxypropyl methacrylate, diethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate quaternized product, methacrylic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid , 2-methacryloyloxy Ethyl phthalic acid, 2-methacryloyloxyethyl 2-hydroxyethyl phthalic acid, neopentyl glycol methacrylic acid benzoate, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, glycidyl methacrylate, 2-methacryloyloxyethyl acid phosphate, Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, PEG # 200 dimethacrylate, PEG # 400 dimethacrylate, PEG # 600 dimethacrylate, 1,4-butanediol dimethacrylate, neopentylglycol dimethacrylate, 3- Methyl-1,5-pentanediol dimethacrylate, 2-butyl-2-ethyl-1,3-propanediol dimethacrylate 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, glycerin dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, bisphenol A-EO addition Dimethacrylate, trifluoroethyl methacrylate, tetrafluoropentyl methacrylate, octafluoropentyl methacrylate, perfluorooctyl ethyl methacrylate, nonylphenol-EO adduct methacrylate, dimethylol tricyclodecane dimethacrylate, trimethylolpropane methacrylic acid benzoate, hydroxy Pivalic acid neopentyl glycol dimethacrylate, tetrafurfuryl alcohol oligomethacrylate, Tylcarbitol oligomethacrylate, 1,4-butanediol oligomethacrylate, 1,6-hexanediol oligomethacrylate, trimethylolpropane oligomethacrylate, pentaerythritol oligomethacrylate, pentamethylpiperidylmethacrylate, tetramethylpiperidylmethacrylate, paracumylphenol-EO Modified methacrylate, N-methacryloyloxyethyl hexahydrophthalimide, isocyanuric acid-EO modified dimethacrylate, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyloxetane-3-yl) methoxy] Methyl} benzene, 3-ethyl-3-{[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane, 3-ethyl-3- (2-ethyl) Hexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (cyclohexyloxy) methyloxetane, oxetanylsilsesquioxane, oxetanyl silicate, phenol novolak oxetane, and 1,3- Bis [(3-ethyloxetane-3-yl) methoxy] benzene is mentioned.

  The composition ratio in the composition constituting the fine concavo-convex structure 12 is one or more monomer components having three or more acrylic groups and / or methacryl groups in one molecule in a total of 100 parts by mass of monomer components. Are preferably 20 to 60 parts by mass, the monomer component having an N-vinyl group is 5 to 40 parts by mass, and the other monomer components are preferably 0 to 75 parts by mass. By setting the content of one or more monomer components having three or more acrylic groups and / or methacrylic groups in one molecule to 20 parts by mass or more, the composition portion constituting the fine relief structure 12 is high. Since the strength and the crosslink density are increased, bleeding out of unreacted monomers and low-polymerization degree oligomers from the composition part constituting the fine concavo-convex structure 12 and generation of by-products can be minimized. . Moreover, the viscosity of the composition which comprises the fine concavo-convex structure 12 by making content of 1 or more types of monomer components which have 3 or more acryl group and / or methacryl group in 1 molecule into 60 mass parts or less. The rise can be suppressed, and a decrease in the filling rate of the composition into the uneven pattern of the molding mold can be prevented. The content of one or more monomer components containing three or more acrylic groups and / or methacryl groups in one molecule is 100 parts by mass in total of the monomer components in the composition constituting the fine relief structure 12. Among them, the content is more preferably 25 parts by mass to 50 parts by mass, and further preferably 30 parts by mass to 40 parts by mass.

  Examples of the monomer component containing three or more acrylic groups and / or methacrylic groups in one molecule include trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, penta Erythritol triacrylate, propoxylated glyceryl triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tris (2-hydroxyethyl) isocyanurate tri Acrylate, trisacryloyloxyethyl phosphate, trifunctional or higher polyester acrylate Oligomer, trifunctional or higher urethane acrylate oligomer, trifunctional or higher epoxy acrylate oligomer, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane trimethacrylate, propoxylated trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, propoxy Glyceryl trimethacrylate, pentaerythritol tetramethacrylate, ethoxylated pentaerythritol tetramethacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, tris (2-hydroxyethyl) isocyanurate Trimethacrylate, Trismetaacryl Yl oxy ethyl phosphate, tri- or higher-functional polyester methacrylate oligomer, trifunctional or higher urethane methacrylate oligomer, and include 3 or more functional epoxy methacrylate oligomer. Here, the ethoxylated and propoxylated monomer component refers to a monomer component containing 1 to 20 equivalents of one or more ethoxy groups and / or propoxy groups per monomer molecule.

  Among the monomer components containing three or more acrylic groups and / or methacrylic groups in one molecule, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane Trimethacrylate, ethoxylated trimethylolpropane trimethacrylate, and propoxylated trimethylolpropane trimethacrylate are preferred because of a good balance of physical properties. Among these, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate are more preferable because they are excellent in the release property of the cured molded product from the cured stamper. One type or two or more types of monomer components containing three or more acrylic groups and / or methacrylic groups in one molecule may be used.

  The monomer component having an N-vinyl group is more preferably contained in an amount of 15 parts by mass to 38 parts by mass in a total of 100 parts by mass of the monomer components in the composition constituting the fine relief structure 12, and 25 parts by mass. It is more preferable to contain -35 mass parts. By containing 5 parts by mass or more of the monomer component having an N-vinyl group, the adhesion of the molded body to the base material can be improved, and the mold release property of the molded body after curing can be improved. In addition, by containing 40 parts by mass or less, bleed-out can be suppressed to the minimum from the molded body of the unreacted monomer and the low-polymerization degree oligomer, and excessive moisture absorption of the molded body can be suppressed. It is possible to improve the moisture resistance.

  As the monomer component having an N-vinyl group, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, and N-vinylcaprolatum are particularly preferably used. One or more kinds of monomer components having an N-vinyl group may be used.

  The composition constituting the fine concavo-convex structure 12 may contain a silicon compound containing an acryl group and / or a methacryl group. It is preferable that 0.1 mass part-10 mass parts of silicon compounds containing an acryl group and / or a methacryl group are contained with respect to a total of 100 mass parts of monomer components of the composition constituting the fine concavo-convex structure 12. It is more preferable to contain 2-5 mass parts, and it is still more preferable to contain 0.3-2 mass parts. By containing 0.1 part by mass or more, the releasability from the molded mold after curing can be further improved, and by containing 10 parts by mass or less, the strength of the fine concavo-convex structure 12 can be maintained.

  As a kind of silicon compound containing an acryl group and / or a methacryl group, for example, a silicon acrylate compound can be exemplified. BYK-UV3500, BYK-UV3570 (manufactured by Big Chemie Japan), and ebecryl 350 (manufactured by Daicel-Cytech), in which an acrylic group is bonded to a polydimethylsiloxane skeleton, constitutes a fine relief structure 12 after curing. The bleed-out from is less and more preferable.

  When using a photocurable composition as a composition which comprises the fine concavo-convex structure 12, a photoinitiator can be contained. Examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Benzophenone, 1-hydroxycyclohexyl phenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [ 4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane, phenylglyoxylic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinof Nyl) -butanone, 1,2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, bis (2,4,6 -Trimethylbenzoyl) -phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (η5-2,4- Cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] ethanone and 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime). Particularly in the present invention, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1,2-octanedione, 1- [4- (phenylthio) -2- (O -Benzoyloxime)] ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like can be preferably used.

  The blending ratio of the photopolymerization initiator is preferably 0.1 parts by mass to 5.0 parts by mass with respect to 100 parts by mass of the total monomer components in the photocuring composition. These photopolymerization initiators can be applied alone, but can also be used in combination of two or more.

  When using a photocurable composition as a composition which comprises the fine concavo-convex structure 12, it can also be used for a photocurable composition in combination with a photoinitiator, a photosensitizer, etc. For example, photosensitizers include n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, s-benzisoisouronium-p-toluenesulfinate, triethylamine, diethylaminoethyl methacrylate, Triethylenetetramine, 4,4′-bis (dialkylamino) benzophenone, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanol Photosensitizers such as amines such as amines can be used alone or in combination of two or more.

  When the fine concavo-convex structure 12 has a laminated structure, the base material 11 is used. The material is not particularly limited as long as the substrate 11 can support the fine concavo-convex structure 12. An inorganic material such as glass, ceramic, or metal, or an organic material such as resin can be arbitrarily selected depending on the application. In particular, in order to reduce the reflectance at each interface, the difference in refractive index between the interfaces is preferably small, preferably 0.2 or less, preferably 0.001 or more, 0.1 or less, 0.001 More preferably, it is 0.05 or less, and most preferably 0.001 or more.

  Moreover, when using the base material 11 as a base material for transfer, the adhesiveness with the resin cured material layer which comprises the fine concavo-convex structure 12 is good, a refractive index difference is small with a resin cured material layer, and a haze is small. It is desirable to use the substrate 11. Examples of the material that satisfies these include glass and resin.

  Examples of the resin include polymethyl methacrylate resin (PMMA resin), acrylic resin, polycarbonate resin (PC resin), polystyrene resin (PS resin), methyl methacrylate-styrene resin (MS resin), styrene resin, cyclohexane Olefin resin (COP resin), polyarylate resin, polyetherimide resin, polyether sulfone resin, polysulfone resin, polyether ketone resin, polyethylene terephthalate resin (PET resin), polyethylene naphthalate resin (PEN resin), polytri Examples include methylene terephthalate resin, aromatic polyester resin, triacetyl cellulose resin (TAC resin), polyimide resin, acrylic resin, epoxy resin, urethane resin, and other ultraviolet curable resins and thermosetting resins. In particular, PMMA resin, acrylic resin, PC resin, PS resin, styrene resin, COP resin, PET resin, PEN resin, aromatic polyester resin, and TAC resin are preferable.

  An additive may be added to the transparent resin as necessary within a range where the effects of the present invention are obtained. This additive may be directly contained in the resin or may be layered on the surface of the resin substrate. Examples of the additive include organic and / or inorganic particles, plasticizers, antioxidants, ultraviolet absorbers, antistatic agents, antifogging agents, and easy adhesives.

  Moreover, you may form a barrier resin layer in the surface of the base material 11 which consists of the said transparent resin by coating etc. in the range with which the effect of this invention is acquired. This is because the base material 11 can be protected from deterioration factors such as heat, light, moisture, oxygen, carbon dioxide, nitrogen and hydrogen by forming a barrier resin layer on the base material surface.

  On the other hand, when the substrate 11 is glass, a surface treatment such as a silane coupling agent, primer treatment, or UV treatment can be applied. Moreover, you may use combining these surface treatments. Moreover, you may use the base material in which the surface coating, the contact bonding layer, and the interference reduction layer are formed as the base material 11. FIG.

  The shape of the base material 11 can be appropriately selected according to the purpose of use, for example, a plate, a sheet, a film, a thin film, other arbitrary shapes, and a composite of these.

  The thickness of the transfer substrate can be appropriately selected depending on the purpose of use and the production method as long as the effects of the present invention can be obtained.

  The fine concavo-convex structure 12 formed on the substrate 11 preferably has a thickness from the top of the convex portion to the surface in contact with the substrate 11 of 200 nm or more from the viewpoint of the scratch resistance effect. From the viewpoint of transparency, it is preferable to reduce the optical path length, the thickness is preferably 3 μm or less, and more preferably 2 μm or less. Further, in order to reduce curling due to cure shrinkage of the resin, 1.5 μm or less is more preferable, and in order to reduce surface waviness accompanying cure shrinkage, it is most preferable to be 1 μm or less.

Above this exemplary fine irregularities shaped body 10 according to the embodiment of the described, the height of the convex portion 14 of the fine unevenness 12 (H) is not less 200nm or more, the wavelength of light used is a pitch p _n between nearest protrusion And is calculated by the following formula (A), which is an average height (H) av of the plurality of convex portions 14 and a standard deviation (σ) of the height (H) of the convex portions 14. When the variable ratio of the height (H) of the convex portion 14 is 8% or more, when the incident angle of light becomes wider, it is possible to prevent the difference in reflectance particularly in the visible wavelength region from increasing. While suppressing that a reflective color becomes strong, destruction of a fine uneven | corrugated pattern can be prevented, and it is excellent also in mold release property.
Formula (A)
σ / Hav * 100

  Moreover, the fine concavo-convex molded body 10 according to the present embodiment forms a dense portion where the convex portions 14 and the convex portions 14 that are adjacent to the arbitrary convex portions 14 are connected to each other. Since the concave portion dense portions where the concave portions 15 are connected between the convex portion dense portions and the adjacent convex portion dense portions are arranged in a sea-island shape, the filling density of the convex portions 14 is increased and the antireflection effect is further improved. Furthermore, the fine concavo-convex structure 12 becomes more difficult to break, and the releasability is further improved.

  The fine uneven molded body 10 according to the present embodiment can be used as an antireflection film. The antireflection film is sufficient if it includes at least the fine concavo-convex molded body 10 having the light antireflection property, but may include at least one functional layer. The antireflection film provided with the fine concavo-convex molded body 10 according to the present embodiment can reduce the surface reflection sufficiently only by providing the concavo-convex structure on the surface, and when the incident angle of light becomes wider, especially It is possible to prevent an increase in the difference in reflectance in the visible wavelength region, and to achieve an excellent effect of suppressing an increase in reflected color.

  Next, the manufacturing method of the fine uneven | corrugated molded object 10 which concerns on this Embodiment is demonstrated. First, the case where the fine uneven | corrugated molded object 10 is the multilayer structure which the base material 11 and the fine uneven structure 12 consist of mutually different compositions is demonstrated. In this case, first, a fine concavo-convex molding mold (hereinafter also referred to as a molding mold) is manufactured, and using this molding mold, the fine concavo-convex structure is transferred to a transfer material on the base material, so that the fine concavo-convex structure as a transfer product is obtained. The molded object 10 can be obtained.

  The molding mold according to the present embodiment will be described. The mold is made by applying a solution containing a self-assembled block copolymer onto a substrate to produce a coating layer, and forming a sea-island-like phase separation structure consisting of molecular aggregates by self-organization in the coating layer. The first step to be manufactured, the second step to etch the coating layer as a resist film, and the uneven sea-island resist pattern layer to be etched, and the uneven sea-island resist pattern as a mask are used for etching. It can be obtained by a third step of producing a sea-island-shaped first pattern and a second pattern of fine irregularities along the first pattern.

  The base material of the molding mold used here is not particularly limited as long as it is at least an etchable material, but if it is a material made of an inorganic material or an inorganic organic composite material, it is effective to use a commercially available release agent. It is preferable at the point which can perform a mold release process. In particular, glass, silicon-based materials, and the like are more preferable in that they are easily chemically bonded to a release agent having a silane coupling system and stable release properties can be obtained. On the surface of the transfer substrate, an oxide layer may be formed or a neutralized film may be laminated.

  The self-assembled block copolymer used in the first step includes an aromatic ring-containing polymer and a (meth) acrylate polymer. Here, self-organization means self-assembly by intramolecular or intermolecular interaction to form a structural form according to a certain rule. However, in the present invention, it is not necessary to have a strict regular form, and non-uniformity may be mixed in the structure form.

  The ratio of the monomer unit including the aromatic ring-containing polymer part and the (meth) acrylate polymer part to the entire block copolymer is 50 mol% or more.

  The aromatic ring-containing polymer that is one of the essential components of the block constituting the block copolymer used in the present embodiment is a homopolymer of a vinyl monomer having a heteroaromatic ring such as an aromatic ring or a pyridine ring as a side chain. For example, polystyrene (hereinafter also referred to as PS), polymethylstyrene, polyethylstyrene, polyt-butylstyrene, polymethoxystyrene, polyN, N-dimethylaminostyrene, polychlorostyrene, polybromostyrene, polytristyrene Fluoromethylstyrene, polytrimethylsilylstyrene, polydivinylbenzene, polycyanostyrene, polyα-methylstyrene, polyvinyl naphthalene, polyvinyl biphenyl, polyvinyl pyrene, polyvinyl phenanthrene, polyisopropenyl naphthalene, and polyvinyl pyridi It can be mentioned.

  Here, the aromatic ring-containing polymer most preferably used in the present embodiment is polystyrene from the viewpoint of excellent phase separation, availability of raw material monomers, and ease of synthesis.

  The (meth) acrylate polymer, which is another essential component of the block constituting the block copolymer used in the present embodiment, is at least one homopolymer or copolymer selected from the group consisting of the following acrylate monomers and methacrylate monomers. It is a polymer. Examples of the group consisting of acrylate monomers and methacrylate monomers that can be used here include methyl methacrylate (hereinafter also referred to as MMA), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and n-butyl methacrylate. , Isobutyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic Mention may be made of t-butyl acid, n-hexyl acrylate and cyclohexyl acrylate.

  Here, the poly (meth) acrylate most preferably used in the present embodiment is a methyl methacrylate homopolymer polymethacrylic acid from the viewpoint of excellent phase separation, availability of raw material monomers, and ease of synthesis. It is methyl (hereinafter also referred to as polymethyl methacrylate or PMMA).

  The block copolymer used in the present embodiment is a diblock, triblock or higher multiblock copolymer in which one end or both ends of the aromatic ring-containing polymer and one end or both ends of the poly (meth) acrylate are bonded. From the viewpoint of ease of synthesis, a diblock copolymer in which one end of an aromatic ring-containing polymer and poly (meth) acrylate is bonded to each other is preferable, and polystyrene (PS) and polymethyl methacrylate ( PMMA).

  In addition to the aromatic ring-containing polymer portion and the poly (meth) acrylate portion, the block copolymer may contain other polymer component blocks in a proportion not exceeding 50 mol% in terms of monomer units. Specific examples of the other polymer component include, for example, polyethylene oxide, polypropylene oxide, and polytetramethylene glycol.

  The block copolymer can be synthesized by living anion polymerization, living radical polymerization, coupling of polymers having reactive end groups, or the like.

  For example, in living anionic polymerization, an aromatic ring-containing polymer is first synthesized by synthesizing an aromatic ring-containing polymer using an anionic species such as butyl lithium as an initiator, and then polymerizing a (meth) acrylate monomer using the terminal as an initiator. Block copolymers of polymers and poly (meth) acrylates can be synthesized. At this time, the number average molecular weight of the resulting polymer can be increased by lowering the amount of initiator added, and the number average molecular weight of the polymer can be set as designed by removing impurities in the system such as water and air. Can be controlled. Further, when polymerizing the poly (meth) acrylate moiety, the side reaction can be suppressed by lowering the temperature of the system to 0 ° C. or lower.

  In living radical polymerization, first, a halogen compound such as bromine is added to the double bond of the (meth) acrylate monomer, the terminal is halogenated, and poly (meth) acrylate is synthesized using a copper complex as a catalyst. A block copolymer of an aromatic ring-containing polymer and a poly (meth) acrylate can be obtained by synthesizing an aromatic ring-containing polymer.

  In addition, an aromatic ring-containing polymer is synthesized by living anionic polymerization, and the terminal is halogenated. Then, a (meth) acrylate monomer is reacted in the presence of a copper catalyst to form a block copolymer of the aromatic ring-containing polymer and poly (meth) acrylate. It can also be synthesized.

  When synthesizing using a coupling between polymers having reactive end groups, for example, an aromatic ring-containing polymer having an amino group at the terminal and a poly (meth) acrylate having maleic anhydride at the terminal are reacted to produce an aromatic. A method of forming a block copolymer of a ring-containing polymer and poly (meth) acrylate may be mentioned.

  The number average molecular weight of the block copolymer used in the present embodiment is 3 million or less, preferably 1 million or less, from the viewpoint of optical properties, and 100,000 or more, preferably 150,000 or more, from the viewpoint of pattern transferability. is there.

  The number average molecular weight of the block copolymer is determined by the following method. First, the number average molecular weight of the aromatic ring-containing polymer portion is measured by the following method (1), and then the number average molecular weight of the poly (meth) acrylate portion is measured by the following method (2).

  When the block copolymer is composed only of an aromatic ring-containing polymer portion and a poly (meth) acrylate portion, the number average molecular weight of the block copolymer is the number average molecular weight of the aromatic ring-containing polymer portion obtained in (1), (2 ) Is calculated as the sum of the number average molecular weights of the poly (meth) acrylate moieties obtained.

  When the block copolymer contains an aromatic ring-containing polymer part, a poly (meth) acrylate part, and other polymer parts, measurement is performed by (3) the number average molecular weight measurement method of the other polymer parts following (2). I do. In this case, the number average molecular weight of the block copolymer is the number average molecular weight of the aromatic ring-containing polymer (a) part obtained in (1) and the number average molecular weight of the poly (meth) acrylate part obtained in (2). Calculated as the sum of the molecular weight and the number average molecular weight of the other polymer moieties obtained in (3).

(1) Method for measuring number average molecular weight of aromatic ring-containing polymer portion in block copolymer When synthesizing a block copolymer by living anion polymerization, generally an aromatic ring-containing monomer is first polymerized, and then a (meth) acryl monomer is polymerized from the terminal. However, when a portion of the aromatic ring-containing monomer is polymerized and the reaction is stopped, only the aromatic ring-containing polymer portion in the block copolymer can be obtained. The aromatic homopolymer thus obtained is measured for elution time distribution using gel permeation chromatography (hereinafter also referred to as GPC). Next, the elution time of several kinds of standard polystyrenes having different number average molecular weights is measured, and the elution time is converted into the number average molecular weight.

(2) Method for measuring number average molecular weight of poly (meth) acrylate moiety in block copolymer A block copolymer is dissolved in a deuterated solvent such as deuterated chloroform, and a ¹ H NMR spectrum is measured. At that time, the molar ratio between the aromatic ring-containing polymer portion and the poly (meth) acrylate portion in the block copolymer is determined by comparing the number of protons derived from the aromatic ring-containing polymer and the number of protons derived from the poly (meth) acrylate. Can do. Therefore, as described above, the number average molecular weight of the poly (meth) acrylate portion can be determined from the number average molecular weight of the aromatic ring-containing polymer portion determined in advance by GPC.

(3) Method for measuring number average molecular weight of other polymer portion in block copolymer A block copolymer is dissolved in a deuterated solvent such as deuterated chloroform, and a ¹ H NMR spectrum is measured. At that time, by comparing the number of protons derived from the aromatic ring-containing polymer and the number of protons derived from the other polymer part, the molar ratio of the aromatic ring-containing polymer part and the other polymer part in the block copolymer in the monomer unit is obtained. It is done. Therefore, as described above, the number average molecular weight of the other polymer portion can be obtained from the number average molecular weight of the aromatic ring-containing polymer obtained in advance by GPC.

  The pattern used in this embodiment is preferably a dot pattern or a random pattern, more preferably a random pattern, from the viewpoint of optical characteristics.

In order to form a dot pattern, when the mass of the aromatic ring-containing polymer is W _a and the mass of the (meth) acrylate polymer is W _b , the (meth) acrylate polymer portion is the island phase, and the aromatic ring-containing polymer is the sea phase. Thus, the lower limit of W _a / W _b is 4 or more, preferably 5 or more. On the other hand, the upper limit of W _a / W _b is 20 or less, preferably 10 or less.

In order to form a random pattern, the lower limit of W _a / W _b is 0.25 or more, preferably 0.67 or more, and more preferably 1.5 or more. On the other hand, the upper limit of W _a / W _b is 4 or less, preferably 3 or less.

  The block copolymer can be dissolved in a solvent to form a pattern forming solution. Any solvent can be used as long as it can dissolve the block copolymer. For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, cyclopentanone, cyclohexanone, isophorone. , N, N-dimethylacetamide, dimethylimidazolinone, tetramethylurea, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl Ether acetate (hereinafter also referred to as PGMEA), methyl lactate, ethyl lactate, butyl lactate Methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, and, methyl 3-methoxypropionate. These can be used alone or in admixture of two or more.

  Examples of more preferable solvents include N-methylpyrrolidone, cyclopentanone, cyclohexanone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and PGMEA.

  The mass ratio of the block copolymer to the solution is preferably 0.1 to 30% by mass from the viewpoint of forming a thin film.

  Next, the manufacturing method of the shaping | molding die with which the convex part dense location and recessed part dense location which are the preferable aspects of this invention are arrange | positioned at sea island shape is demonstrated.

[First step]
When forming the phase separation structure, at least a step of applying the above-described pattern forming solution on the substrate to obtain a coating layer and a step of heating the coating layer together with the substrate are sequentially performed.

When the phase separation structure is a lamella, for example, when W _a / W _b is 1, a neutralized film may be applied on the substrate in order to vertically align the lamella.

  As a method for coating on a substrate, the pattern forming solution is applied by a spin coater, bar coater, blade coater, curtain coater, spray coater or ink jet method, a screen printing machine, a gravure printing machine, or offset printing. Examples of the printing method include a printing machine.

  Next, the obtained coating film is heat-dried or vacuum-dried by air drying, oven, hot plate or the like to volatilize the solvent. The film thickness after volatilizing the solvent is preferably 10 nm to 500 nm, more preferably 10 nm to 300 nm, and still more preferably 10 nm to 100 nm, from the viewpoint of pattern transfer performance.

  Examples of the method for measuring the film thickness include a contact method in which a film is scratched and a terminal is brought into contact with the surface to measure the step, and a non-contact method using ellipsometry.

  The method of heating the coating film together with the base material can be broadly classified into a method of directly transferring heat from the lower side of the base material like a hot plate and a method of convection of a high-temperature gas like an oven. Direct heat transfer is preferable because a phase separation structure can be obtained in a shorter time.

  The heating temperature in the heating step is preferably 130 ° C. or higher and 280 ° C. or lower, more preferably 140 ° C. or higher and 270 ° C. or lower, and further preferably 150 ° C. or higher and 260 ° C. or lower.

  The heating time is 10 seconds or more and 100 hours or less, preferably 10 hours or less, more preferably 1 hour or less. In the case of direct heat transfer, it is preferably from 10 seconds to 1 hour, more preferably from 10 seconds to 30 minutes. If the heating temperature is 130 ° C. or higher, a phase separation structure can be formed higher than Tg, and if it is 280 ° C. or lower, polymer decomposition is suppressed. In the case of direct heat transfer, a phase separation structure can be formed if the heating time is 10 seconds or longer, and decomposition of the polymer is suppressed if it is 1 hour or shorter. The higher the heating temperature, the faster the phase separation structure can be obtained. Also, the higher the heating temperature, the longer the distance between the islands and the average center of gravity of the islands in the case of a dot pattern.

  In the present embodiment, in the case of a dot pattern, a sea-island pattern in which the aromatic ring-containing polymer is the sea and the poly (meth) acrylate polymer is the island is obtained.

  The atmosphere of the heating process is not particularly limited, such as air, nitrogen, vacuum, or the like.

  The sea-island pattern produced as described above can be produced on a substrate by using a dry etching method.

  The dry etching apparatus to be used is preferably a plasma generation and bias power supply that can be controlled independently, and is capable of increasing the density of the generated plasma.

  In order to produce a pattern on a substrate, it is necessary to produce the pattern in two stages.

  Since a resist pattern made of only a polymer has low dry etching resistance, the resist pattern disappears before the substrate is etched to a desired depth. Therefore, by providing a hard mask with high dry etching resistance in the middle, a resist pattern is produced on the hard mask (second step), and a hard mask pattern is produced on the substrate (third step), thereby creating a sea island pattern. It can be made into a material.

[Second step]
First, a resist pattern is produced. When the aromatic ring-containing polymer is a sea and the poly (meth) acrylate polymer is an island-island pattern, a sea-island pattern can be produced using the difference in etching rate between the two types of polymers.

  Specifically, if dry etching is performed using a gas that causes the poly (meth) acrylate polymer to be etched faster than the aromatic ring-containing polymer, the poly (meth) acrylate polymer is first etched after a predetermined time. The pattern of only the aromatic ring-containing polymer remains, and a sea-island pattern is formed.

Examples of the etching gas to be used include fluorine-containing gas, oxygen gas, argon gas, or a mixed gas thereof. In particular, it is preferable to use CF ₄ , SF ₆ , CHF ₃ , or a gas obtained by mixing an argon gas with an oxygen gas as the gas that increases the etching rate difference.

Next, a hard mask, which is made of a polymer resist pattern with low etching resistance, is preferably a material that is easily etched depending on the gas, but is harder to etch than the material of the substrate. ₂ and a dielectric mask such as Si ₃ N ₄ .

Examples of the method for forming the dielectric mask include sputtering, vapor deposition, CVD, thermal oxidation, etc. Especially when the base material is Si, the surface of the base material can be simplified by the thermal oxidation method that can be more easily produced. Since it is possible to produce the SiO ₂ film thickness with fine control, it is particularly preferable to prepare a base material including a dielectric mask by adjusting only the film thickness.

The etching gas used for producing the hard mask from the resist pattern includes a fluorine-containing gas, oxygen gas, argon gas, or a mixed gas thereof, similarly to the gas for producing the resist pattern. In particular, it is preferable to use CF ₄ , SF ₆ , CHF ₃ , or a gas obtained by mixing an argon gas with an oxygen gas as the gas that increases the etching rate difference.

  In order to simplify the process, it is more preferable to use the same gas to prepare a resist pattern and a hard mask pattern.

[Third step]
Examples of the etching gas used for producing the hard mask pattern on the substrate include a chlorine-containing gas, oxygen gas, argon gas, or a mixed gas thereof.

  Since the etching isotropy and anisotropy that affect the degree of freedom of the shape that can be produced can be controlled by the gas to be mixed and the ratio thereof, it is preferable to use a mixed gas.

As described above, when the Si base and the hard mask are SiO ₂ , it is particularly preferable to use a gas obtained by mixing argon with chlorine gas.

  When a gas in which argon is mixed with chlorine gas is used, the etching rate difference can be adjusted between about 5 and 20 depending on the gas mixture ratio. The film thickness of the dielectric hard mask can be selected in consideration of the relationship with the shape by adjusting the balance.

  From the viewpoints of optical properties and transferability, the thickness of the hard mask is preferably between 10 nm and 100 nm, and more preferably between 10 nm and 30 nm.

  By the above-described two-stage process (second process and third process), it is possible to produce a sea-island pattern with unevenness of a desired height on the base material. It can be used for the manufacture of the fine concavo-convex molded body 10.

  A method for transferring the fine concavo-convex structure to the photocurable composition using the molding mold produced as described above will be described.

  Examples of the transfer method that can be used in the present embodiment include a thermal nanoimprint method, a photo nanoimprint method, a room temperature nanoimprint method, and a casting method according to the curing conditions of the photocurable composition, and a plurality of combinations may be used. The optical nanoimprint method is more preferable from the viewpoint of rapid transfer and continuous production by roll-to-roll.

  When the cured resin layer cured with the photocurable composition is peeled from the mold, the surface of the mold is subjected to a release treatment in advance in order to improve the releasability between the cured resin layer and the mold. Is preferred. As the release treatment agent, a silane coupling release agent is preferable, and a fluorine-containing release agent is more preferable. Examples of commercially available release agents include OPTOOL DSX, OPTOOL HD-1100Z and HD-2100Z manufactured by Daikin Industries, Ltd., Novec manufactured by Sumitomo 3M, and the like.

  First, a soft photocurable composition is applied on the base material 11 (application process). Next, this photocurable composition is pressed against the fine concavo-convex structure of the molding mold (pressing step). The photocurable composition is exposed and cured in the pressed state (exposure process). The obtained cured resin layer is peeled from the molding mold together with the base material 11 to obtain a fine uneven molded body 10 as a transfer product (peeling step).

  In the coating step, a soft photocurable composition is coated on the substrate 11 to form a film. As a method for applying the photocurable composition onto the substrate 11, a casting method, a potting method, a spin coating method, a roller coating method, a bar coating method, a casting method, a dip coating method, a die coating method, a Langmuir projet method, Examples thereof include spray coating, air knife coating, flow coating, and curtain coating.

  When the area of the base material 11 is larger than the area of the molding mold, the photocurable composition may be applied to the entire surface of the base material 11, or the photocurable composition may be applied to a part of the base material 11 and embossed. The photo-curing composition may be present only in the range.

  By applying the photo-curing composition to the substrate 11 and then pre-baking, the solvent can be distilled off when the solvent is contained, and void formation derived from the residual solvent after curing can be reduced. Another effect is that the surface migration of the internally added additives (for example, fluorine-containing polymerizable (meth) acrylate and silicone-containing (meth) acrylate) can be promoted, and the surface of the cured resin layer is slippery. Will be better. As a result, the scratch resistance of the surface of the cured resin layer is improved, and the release property from the mold is improved, so that a high-quality cured resin layer with low defects can be obtained. The prebaking temperature is preferably 25 ° C to 120 ° C, more preferably 40 ° C to 100 ° C, further preferably 50 ° C to 100 ° C, and most preferably 60 ° C to 100 ° C. The prebaking time is preferably 30 seconds to 30 minutes, more preferably 1 minute to 15 minutes, and further preferably 3 minutes to 10 minutes.

  It is preferable to perform the process which improves the adhesiveness of the base material 11 and a resin cured material layer. For example, easy adhesion coating for physical bonding such as chemical bonding to the resin cured material layer or penetration, primer treatment, corona treatment, plasma treatment, UV / ozone treatment, high energy It is preferable to perform a beam irradiation treatment, a surface roughening treatment, a porous treatment, or the like.

  In the pressing step, it is preferable that the highly flexible base material 11 is gently coated on the fine concavo-convex structure of the molding mold from the end so that bubbles do not enter and pressed under a constant pressure. The press pressure at the time of pressing is preferably more than 0 MPa to 10 MPa, more preferably 0.01 MPa to 5 MPa, and further preferably 0.01 MPa to 1 MPa.

  In the exposure step, it is preferable to expose from the substrate side when the light transmittance of the molding mold is low. On the other hand, when the mold has a high transmittance with respect to ultraviolet light, for example, when the material of the mold is synthetic quartz, it is preferable to expose from at least one side of the substrate side or the mold side. It is more preferable to expose from both sides on the mold side. Instead of using the substrate 11, only the photocurable composition may be applied to a molding mold and cured. In that case, in order to prevent polymerization inhibition by oxygen, a method of exposing in a nitrogen atmosphere or an argon atmosphere, or coating with a substrate having low adhesiveness, and after curing, the substrate and the cured resin layer are peeled off. A cured product can be produced by a method or the like.

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

  In the peeling step, the cured resin layer obtained by curing the photocurable composition by exposure is peeled from the molding mold. In the peeling step, as described above, when the mold release surface is subjected to the release treatment, the cured resin layer can be easily peeled off from the surface of the mold.

  By the manufacturing method described above, a nano-sized moth-eye-like high aspect pattern can be obtained in a micro-sized random arrangement. By realizing this nano / micro size hierarchical pattern arrangement, it is possible to improve the filling property of the resin and to obtain a pattern strength that does not lose the peeling resistance at the time of peeling. Furthermore, the convex part 14 of the fine concavo-convex structure 12 after peeling takes a form in which the adjacent convex parts 14 are close to each other, or partly fused, without substantial pattern collapse, A microstructured compact 10 having a physically stable structure is obtained. As a result, the obtained microstructured molded body 10 has a high antireflection effect and can be suitably used for an optical element such as an antireflection film.

  As described above, in the fine concavo-convex mold according to the present embodiment, the fine concavo-convex structure has a specific pattern shape and arrangement. The filling property of the transfer material into the fine concavo-convex structure is improved, and the fine concavo-convex structure 12 of the transferred fine concavo-convex molded body 10 is a pattern that does not lose the peeling resistance when the transfer material is peeled from the fine concavo-convex mold. Strength can be obtained. Furthermore, the convex part 14 of the fine concavo-convex structure 12 of the fine concavo-convex molded body 10 collapses substantially by taking a form in which the adjacent convex parts 14 are close to each other or partially fused. Without having a physically stable structure. As a result, a high-quality fine uneven molded body 10 can be obtained.

  In addition, according to the method for manufacturing a fine concavo-convex mold according to the present embodiment, it has a fine concavo-convex structure including a plurality of convex portions and a plurality of concave portions provided on the surface of the substrate, It is possible to easily obtain a mold having a fine concavo-convex structure in which a convex portion dense portion where the convex portion and the nearest adjacent convex portion are continuous is formed and the convex portion dense portion is randomly arranged in a top view. .

  In addition, although the fine uneven | corrugated molded object 10 of this invention can be manufactured according to each process demonstrated above, it is not limited to this. In the same manner as the above-described molding mold, the fine concavo-convex molded body 10 of the present embodiment having a single layer structure can be manufactured.

  That is, the fine concavo-convex molded article 10 according to the present embodiment applies a solution containing a self-assembled block copolymer on the base material 11 to produce a coating film layer, and self-organization is performed in the coating film layer. A step of producing a sea-island-like phase separation structure arranged in a random manner, a step of selectively etching the sea or island portion of the phase-separation structure to produce a concavo-convex sea-island-like resist pattern layer, and a concavo-convex sea-island-like resist Etching with the pattern as a mask to form a first pattern having a random shape on the substrate 11 and a second pattern having a fine concavo-convex shape along the first pattern.

  According to the manufacturing method of the fine uneven molded body 10 according to the present embodiment, it has the fine uneven structure 12 including the plurality of convex portions 14 and the plurality of concave portions 15 provided on the surface of the substrate 11, and has an arbitrary convex shape. The fine concavo-convex structure molded body 10 is formed such that a convex portion dense portion where the portion 14 and the convex portion 14 adjacent to the convex portion 14 are continuous is formed, and the convex portion dense portion is randomly arranged in a top view. Can be easily obtained.

  Hereinafter, although demonstrated in detail based on the Example performed in order to clarify the effect of this invention, this invention is not limited at all by the following Examples.

  As an example, a method for producing the molded body A will be described.

[Synthesis example]
In a 2 L flask, 490 g of tetrahydrofuran dehydrated and degassed as a solvent (hereinafter also referred to as THF) and a hexane solution (about 0.16 mol / L) of n-butyllithium (hereinafter also referred to as n-BuLi) as an initiator. ): 1.19 mL, 20.8 g of styrene dehydrated and degassed as a monomer, and stirred for 30 minutes while cooling to −78 ° C. in a nitrogen atmosphere. Next, 12 g of dehydrated and degassed methyl methacrylate (hereinafter referred to as MMA) as a second monomer was added and stirred for 2 hours. Thereafter, the reaction solution was added to a container containing 3 L of methanol while stirring, and the precipitated polymer was vacuum-dried overnight at room temperature.

  After the polymerization of styrene was completed, 3 ml of the reaction solution was collected before adding MMA. From the analysis of GPC, it was identified as polystyrene having a number average molecular weight of 136,000 (hereinafter referred to as PS).

<Method for measuring number average molecular weight of polymer>
The number average molecular weight of the polymer was measured using the following GPC (gel permeation chromatography) apparatus, column, and standard polystyrene.
Device: HLC-8220 manufactured by Tosoh Corporation
Eluent: Chloroform 40 ° C
Column: manufactured by Tosoh Corporation, trademark TSKgel SuperHZ2000, TSKgel SuperHZM-N series
Flow rate: 1.0 ml / min
Reference material for molecular weight calibration: TSK standard polystyrene (12 samples) manufactured by Tosoh Corporation

<Measurement method of ratio of block part of block copolymer>
From the results of analysis of the measured values obtained using the following nuclear magnetic resonance (NMR) apparatus, the molar ratio of the PS part and the PMMA part of the block copolymer (I) was obtained. The NMR apparatus and solvent used are as follows.
Apparatus: JNM-GSX400 FT-NMR manufactured by JEOL Ltd.
Solvent: Heavy dichloroethylene

  Along with the GPC results described above, the block copolymer, which is the main product, has a PS portion number average molecular weight of 136,000 and a polymethyl methacrylate (hereinafter referred to as PMMA) portion number average molecular weight of 82,000. Was identified. The obtained block copolymer was designated as BC-1.

[Fabrication of fine uneven mold (mold A)]
A 2.0% by mass solution of BC-1 in propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) obtained in the above synthesis example was prepared.

  This solution was spin-coated on a silicon substrate having a thermal oxide film having a thickness of 10 nm, and prebaked at 110 ° C. for 90 seconds. The film thickness at this time was 55 nm.

Next, it was heat-treated for 3 minutes on a hot plate manufactured by AS ONE at 230 ° C. and cooled to room temperature. Next, the random pattern was produced on a substrate using a dry etching apparatus NE-550 manufactured by ULVAC. First, CF ₄ gas was used, the gas flow rate was 20 sccm, the gas pressure was 0.5 Pa, the antenna / bias power was set to 50 W / 50 W, and etching was performed for 40 seconds. Thereafter, using a mixed gas of Cl ₂ gas and Ar gas, the gas flow rate was set to 10 sccm / 10 sccm, the gas pressure was set to 0.5 Pa, the antenna / bias power was set to 50 W / 50 W, and etching was performed for 200 seconds. .

  Then, when surface observation was performed with a field emission scanning electron microscope (FE-SEM) S-4800 (manufactured by Hitachi High-Technologies Corporation), the shape of a random uneven pattern (mold A) was obtained.

[Preparation of photocurable resin (resin A)]
32 parts by mass of trimethylolpropane triacrylate as a monomer component containing three or more acrylic groups and / or methacryl groups in one molecule, and N-vinyl-2 as a monomer component containing an N-vinyl group -32 parts by weight of pyrrolidone (NVP), 33 parts by weight of 1,9-nonanediol diacrylate as the other monomer component, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Ciba 2 parts by mass of Specialty Chemicals, Darocur TPO), 1 part by mass of silicon diacrylate as a silicon compound containing an acrylic group, and a composition that forms a concavo-convex structure by filtering foreign matter using a filter having a pore diameter of 1 μm A product was made. The viscosity at 50 ° C. of the photocurable composition constituting the obtained uneven structure was 5 mPa · s. The said viscosity was measured at 50 degreeC using the E-type viscosity meter (the Toki Sangyo company make, model number: RE550L).

[Example of UV transfer]
After the surface of the mold A produced as described above was washed with excimer UV, OPTOOL HD-1100Z (manufactured by Daikin Industries, Ltd.) was uniformly applied to release the mold surface. After drying overnight, the mold surface was rinsed with OPTOOL HD-ZV (manufactured by Daikin Industries, Ltd.) to remove an excessive amount of the release agent. Using this template, the pattern was transferred to a film by the optical nanoimprint method. The resin A prepared above was applied to a 80 μm thick triacetyl cellulose resin (hereinafter abbreviated as TAC) film (TD80UL-H / Fuji Film Co., Ltd., refractive index 1.48), and the mold was applied with the coated surface down. And TAC film so that no air entered. Ultraviolet rays were irradiated from the TAC film side using a metal halide lamp at 1500 mJ / cm ² to transfer the fine concavo-convex structure of the mold. The TAC film was peeled from the mold to obtain a molded product A having a random fine uneven structure.

[Evaluation results]
Molded body A:
The molded product A had a small peeling resistance from the mold, and no visible defect was confirmed. Next, morphological observation using a scanning electron microscope (SEM) was performed. From the top view shown in FIG. 4, it was confirmed that the dense portions of the convex portions were randomly arranged. As shown in FIG. 5, this random arrangement could be confirmed by surface morphology observation using a scanning probe microscope. In FIG. 5, a region of 0 nm or more and less than 100 nm from the reference plane is displayed in a light gray color. A region of 100 nm or more from the reference surface, that is, a dense portion of convex portions is displayed in a dark gray color. Moreover, the pitch ( _pn ) between the most adjacent convex parts was 50 nm, and the pitch (P _N ) between convex part dense spots was 100 nm. On the other hand, from the sectional view of the convex portion shown in FIG. No pattern collapse was confirmed, and even after repeated transfer (20 times or more), no visible defects were generated on the transfer product or the mold surface, and good transferability was exhibited even at a high aspect ratio.

  Next, the optical characteristics of the molded product A were evaluated. The haze value was 0.20%, the positive + diffuse reflectance was 0.5% at a wavelength of 550 nm, and was 0.75% or less in the wavelength range of 400 nm to 750 nm. Even after 20 times of transfer, the optical characteristics were equivalent to the initial transfer product.

Molded body B:
As a comparative example, a pattern mold B in which convex portions having an aspect ratio of 3 or more are independently arranged was produced. Although the transfer from the mold B was attempted using the resin A in the same manner as in the transfer method using the mold A, the transfer substrate could not be peeled off and the transfer substrate was agglomerated and destroyed.

  In addition, this invention is not limited to the said embodiment, It can change and implement variously. In the above-described embodiment, the size, shape, and the like illustrated in the accompanying drawings are not limited to this, and can be appropriately changed within a range in which the effects of the present invention are exhibited.

  The present invention can be suitably applied to, for example, an antireflection film and its production.

DESCRIPTION OF SYMBOLS 10 Fine uneven molded body 11 Base material 12 Fine uneven structure 13 Reference surface 14 Convex part 15 Concave part

Claims (19)

  A fine concavo-convex molded article having a base material and a fine concavo-convex structure including a plurality of convex portions and a plurality of concave portions provided on the surface of the base material, wherein the convex portions and the convex portions are nearest to the convex portions. A fine concavo-convex molded article, wherein convex portions densely linked to the convex portions are formed, and the convex portions densely arranged are randomly arranged in a top view. Contiguous convex portions are formed by forming convex dense portions where any convex portion of the fine concavo-convex structure and the convex portion closest to the convex portion are connected at an average interval (p _n ) of 200 nm or less. The fine concavo-convex molded article according to claim 1, wherein an average interval (P _N ) between the dense spots is _pn or more and 400 nm or less.   The fine concavo-convex molded article according to claim 1 or 2, wherein a ratio of the convex part height to the convex minor axis length is an average of 2 or more in a sectional view of the arbitrary convex part.   The fine concavo-convex structure is a cured product of a resin composition, and the resin composition has one or more types of monomer components having three or more acrylic groups and / or methacrylic groups in one molecule in 100 parts by mass. 20 to 60 parts by mass, 5 to 40 parts by mass of a monomer component having an N-vinyl group, and 0 to 75 parts by mass of other monomer components. The fine uneven | corrugated molded object in any one of Claims 1-3.   The fine concavo-convex molded article according to claim 4, wherein the resin composition is a photocurable composition.   The fine concavo-convex molded article according to claim 5, wherein the photocurable composition has a viscosity at 50 ° C. of 100 mPa · s or less.   An antireflection film comprising the fine concavo-convex molded body according to any one of claims 1 to 6.   A fine concavo-convex molding mold having a base material and a fine concavo-convex structure including a plurality of convex portions and a plurality of concave portions provided on the surface of the base material, wherein the convex portion and the convex portion are nearest to each other A fine concavo-convex molding mold, wherein convex portions densely linked to the convex portions are formed, and the convexly densely populated portions are randomly arranged in a top view. Contiguous convex portions are formed by forming convex dense portions where any convex portion of the fine concavo-convex structure and the convex portion closest to the convex portion are connected at an average interval (p _n ) of 200 nm or less. 9. The fine concavo-convex mold according to claim 8, wherein an average interval (P _N ) between the dense locations is _pn or more and 400 nm or less.   10. The fine concavo-convex mold according to claim 8, wherein a ratio of a convex portion height to a convex minor axis length is an average of 2 or more in a sectional view of an arbitrary convex portion.   A step of applying a solution containing a self-assembled block copolymer on a substrate to prepare a coating layer, and preparing a sea-island-like phase separation structure randomly arranged in the coating layer by self-assembly And selectively etching the sea or island part of the phase-separated structure to produce an uneven sea-island resist pattern layer, and etching using the uneven sea-island resist pattern as a mask, Forming a first pattern having a random shape and a second pattern having a fine concavo-convex shape along the first pattern.   A convex dense portion where the convex portions adjacent to the convex portion and the convex portion nearest to the convex portion are continuous is formed, and the convex dense portions are randomly arranged in a top view. The method for producing a fine concavo-convex forming body according to claim 11, wherein: An adjacent convex portion dense spot is formed by forming a convex dense spot where an arbitrary convex part of the concave and convex shape and the convex part closest to the convex part are connected at an average interval (p _n ) of 200 nm or less. The method for producing a fine concavo-convex molded article according to claim 11 or 12, wherein an average interval ( _PN ) between the pn is _pn or more and 400 nm or less.   The fine unevenness according to any one of claims 11 to 13, wherein, in a cross-sectional view of an arbitrary protrusion having the uneven shape, the height ratio of the protrusion to the short axis length of the protrusion is an average of 2 or more. Manufacturing method of a molded object.   A step of applying a solution containing a self-assembled block copolymer on a substrate to prepare a coating layer, and preparing a sea-island-like phase separation structure randomly arranged in the coating layer by self-assembly And selectively etching the sea or island part of the phase-separated structure to produce an uneven sea-island resist pattern layer, and etching using the uneven sea-island resist pattern as a mask, Forming a first pattern having a random shape and a second pattern having a fine concavo-convex shape along the first pattern.   A convex dense portion where the convex portions adjacent to the convex portion and the convex portion nearest to the convex portion are continuous is formed, and the convex dense portions are randomly arranged in a top view. The method for producing a fine unevenness forming mold according to claim 15, wherein the mold is formed. An adjacent convex portion dense spot is formed by forming a convex dense spot where an arbitrary convex part of the concave and convex shape and the convex part closest to the convex part are connected at an average interval (p _n ) of 200 nm or less. The method for producing a fine concavo-convex mold according to claim 15 or 16, wherein an average interval (P _N ) between each other is _pn or more and 400 nm or less.   18. The fine unevenness according to claim 15, wherein, in a cross-sectional view of an arbitrary protrusion having the uneven shape, the height ratio of the protrusion to the short axis length of the protrusion is an average of 2 or more. A method for producing a mold.   A fine concavo-convex molded article is obtained by transferring the fine concavo-convex structure to a transfer material using the fine concavo-convex mold obtained by the method for producing a fine concavo-convex mold according to any one of claims 15 to 18. A method for producing a fine concavo-convex molded article.