JP2020038324A - Antifouling film and polymerizable composition - Google Patents

Abstract

To provide an antifouling film the antifouling property of which is maintained high even when manufactured continuously for a long period.SOLUTION: Provided is an antifouling film comprising a substrate and a polymer layer having a rugged structure on the surface, with a plurality of protrusions provided at a pitch of the wavelength of visible light or less. The polymer layer is a cured substance of a polymerizable composition, the polymerizable composition containing, in terms of active ingredients, 2.5-12.5 wt.% of fluorine-based oligomer having a (meth)acryloyl group and 1-10 wt.% of a block copolymer comprising a fluorine segment and a non-fluorine segment, the fluorine-based oligomer including a perfluoropolyether-based oligomer and/or a perfluoroalkyl-based oligomer.SELECTED DRAWING: Figure 1

Description

The present invention relates to an antifouling film and a polymerizable composition.

Various optical films having antireflection properties have been studied (for example, see Patent Documents 1 to 3). In particular, it is known that an optical film having a nanometer-sized uneven structure (nanostructure) has excellent antireflection properties. According to such a concavo-convex structure, since the refractive index continuously changes from the air layer to the substrate, the reflected light can be dramatically reduced.

JP-A-9-145903 JP 2007-178724 A JP 2018-59047 A

However, such an optical film has excellent anti-reflection properties, but because of the uneven structure of its surface, when dirt such as fingerprints (sebum) adheres, the adhered dirt tends to spread, In some cases, it was difficult to wipe off dirt that had entered between the copies. Moreover, since the reflectance of the adhered stain is significantly different from the reflectance of the optical film, the stain was easily visually recognized. Therefore, a functional film (antifouling film) having a nanometer-sized uneven structure on its surface and having excellent wiping properties against dirt (for example, fingerprint wiping properties), that is, excellent antifouling properties has been demanded.

On the other hand, the present inventors have studied and found that if a fluorine-based compound is blended as a component in the polymer layer constituting the concave-convex structure of the optical film, the antifouling property is enhanced.

However, the present inventors have further studied, when using a mold when forming the concave-convex structure of the polymer layer, with an increase in the number of times the mold is transferred, the mold releasability of the mold is likely to decrease. As a result, it was found that the antifouling property of the obtained antifouling film was likely to decrease.

As described above, conventionally, there has been a problem of realizing an antifouling film having high antifouling properties even when manufactured continuously for a long period of time. However, means for solving the above problem has not been found. For example, Patent Literatures 1 to 3 do not describe a decrease in the antifouling property of an antifouling film associated with continuous production for a long period of time, and do not solve the above problem.

The present invention has been made in view of the above-mentioned situation, and it is possible to constitute an antifouling film having a high antifouling property even when manufactured continuously for a long time, and a polymer layer of the antifouling film. And a polymerizable composition.

One embodiment of the present invention provides a prevention method including a base material, and a polymer layer provided on a surface of the base material and having a concave-convex structure on the surface, in which a plurality of protrusions are provided at a pitch equal to or less than a wavelength of visible light. In a fouling film, the polymer layer is a cured product of a polymerizable composition, and the polymerizable composition has a fluorine-based oligomer having a (meth) acryloyl group of 2.5 to 12.5% by weight, 1 to 10% by weight of a block copolymer comprising a fluorine segment and a non-fluorine segment, and the fluorine-based oligomer includes at least one of a perfluoropolyether-based oligomer and a perfluoroalkyl-based oligomer And an antifouling film.

Another aspect of the present invention is that, in terms of an active ingredient, 2.5 to 12.5% by weight of a fluorine-based oligomer having a (meth) acryloyl group, and 1 to 10% by weight of a block copolymer composed of a fluorine segment and a non-fluorine segment. %, And the fluorine-based oligomer may be a polymerizable composition containing at least one of a perfluoropolyether-based oligomer and a perfluoroalkyl-based oligomer.

According to the present invention, an antifouling film having high antifouling properties even when manufactured continuously for a long time, and a polymerizable composition capable of constituting a polymer layer of the antifouling film are provided. can do.

It is a cross section showing an antifouling film of an embodiment. FIG. 2 is a schematic perspective view showing a polymer layer in FIG. 1. FIG. 2 is a schematic diagram showing an image of a fluorine-based compound present on the surface of a polymer layer in FIG. 1. It is a cross section for explaining the example of the manufacturing method of the antifouling film of an embodiment. It is a cross section for explaining the example of the manufacturing method of the antifouling film of an embodiment. It is a cross section for explaining the example of the manufacturing method of the antifouling film of an embodiment. It is a cross section for explaining the example of the manufacturing method of the antifouling film of an embodiment. It is a cross section for explaining the example of the manufacturing method of the antifouling film of an embodiment.

Hereinafter, the present invention will be described in more detail with reference to the drawings by way of embodiments. However, the present invention is not limited to only the embodiments. Further, the configurations of the embodiments may be appropriately combined or changed without departing from the scope of the present invention.

In the present specification, “X to Y” means “X or more and Y or less”.

[Embodiment]
The antifouling film of the embodiment will be described below. FIG. 1 is a schematic cross-sectional view showing the antifouling film of the embodiment. FIG. 2 is a schematic perspective view showing the polymer layer in FIG.

The antifouling film 1 has a substrate 2 and a polymer layer 3 disposed on the surface of the substrate 2.

<Substrate>
Examples of the material of the base material 2 include resins such as triacetyl cellulose (TAC), polyethylene terephthalate (PET), and methyl methacrylate (MMA). The base material 2 may appropriately contain additives such as a plasticizer in addition to the above materials.

The surface of the substrate 2 (the surface on the side of the polymer layer 3) may be subjected to an easy-adhesion treatment (for example, a primer treatment). For example, a triacetyl cellulose film subjected to the easy-adhesion treatment may be used. it can. Further, the surface of the base material 2 (the surface on the side of the polymer layer 3) may be subjected to a saponification treatment. For example, a saponified triacetyl cellulose film may be used.

When the antifouling film 1 is to be attached to a display device having a polarizing plate (for example, a liquid crystal display device), the substrate 2 may constitute a part of the polarizing plate.

The thickness of the substrate 2 is preferably 50 to 100 μm from the viewpoint of ensuring transparency and workability.

<Polymer layer>
The polymer layer 3 has an uneven structure in which a plurality of protrusions (projections) 4 are provided at a pitch P (distance between vertexes of adjacent protrusions 4) equal to or less than the wavelength of visible light (780 nm), that is, a moth-eye structure (moth). On the surface. Therefore, the antifouling film 1 can exhibit excellent antireflection properties (low reflectivity) due to the moth-eye structure.

The thickness T of the polymer layer 3 is such that fluorine atoms in a fluorine-based compound blended in the polymerizable composition described later are localized at a high concentration on the surface of the polymer layer 3 (the surface opposite to the substrate 2). From a viewpoint, it is preferable that it is small. Specifically, the thickness T of the polymer layer 3 is preferably 5 to 20 μm, more preferably 8 to 12 μm.

The shape of the plurality of protrusions 4 is, for example, a shape formed by a columnar lower portion and a hemispherical upper portion (bell-shaped), a conical shape (cone-shaped, conical), or the like, which becomes thinner toward the tip. Shape (tapered shape). In FIG. 1, the bottom of the gap between the adjacent protrusions 4 has an inclined shape, but may have a horizontal shape without being inclined.

The average pitch of the plurality of protrusions 4 is preferably 100 to 400 nm, more preferably 100 to 200 nm, from the viewpoint of sufficiently preventing the occurrence of optical phenomena such as moiré and rainbow unevenness. Specifically, the average pitch of the plurality of protrusions 4 is, specifically, the average of the pitches of all adjacent protrusions (P in FIG. 1) in a 1 μm square region of a plan photograph taken by a scanning electron microscope. Indicates a value.

The average height of the plurality of protrusions 4 is preferably 50 to 600 nm, and more preferably 100 to 300 nm, from the viewpoint of achieving compatibility with a preferable average aspect ratio of the plurality of protrusions 4 described below. Specifically, the average height of the plurality of protrusions 4 is, specifically, the average of the heights (H in FIG. 1) of ten consecutive protrusions in a cross-sectional photograph taken by a scanning electron microscope. Indicates a value. However, when selecting the ten convex portions, the convex portions having missing or deformed portions (such as portions deformed when preparing the measurement sample) are excluded.

The average aspect ratio of the plurality of protrusions 4 is preferably 0.8 to 1.5, and more preferably 1.0 to 1.3. When the average aspect ratio of the plurality of protrusions 4 is smaller than 0.8, the occurrence of optical phenomena such as moiré and rainbow unevenness cannot be sufficiently prevented, and excellent antireflection properties may not be obtained. . If the average aspect ratio of the plurality of protrusions 4 is larger than 1.5, the workability of the uneven structure is reduced, sticking occurs, or the transfer condition when forming the uneven structure is deteriorated (described later). The mold 5 may be clogged or wrapped around). The average aspect ratio of the plurality of protrusions 4 indicates the ratio (height / pitch) between the average height and the average pitch of the plurality of protrusions 4 described above.

The plurality of projections 4 may be arranged randomly or periodically (regularly). When the plurality of convex portions 4 are periodically arranged, unnecessary diffracted light due to the periodicity may be generated. Therefore, the plurality of convex portions 4 are randomly arranged as shown in FIG. Is preferred.

The polymer layer 3 is a cured product of the polymerizable composition. Examples of the polymer layer 3 include a cured product of an active energy ray-curable polymerizable composition, a cured product of a thermosetting polymerizable composition, and the like. In the present specification, “active energy ray” means ultraviolet light, visible light, infrared light, plasma, or the like. The polymer layer 3 is preferably a cured product of an active energy ray-curable polymerizable composition, and more preferably a cured product of an ultraviolet-curable polymerizable composition.

The polymerizable composition constituting the polymer layer 3 contains, as a fluorine-based compound, a fluorine-based oligomer (R) having a (meth) acryloyl group and a block copolymer (S) including a fluorine segment and a non-fluorine segment. are doing. In the present specification, “(meth) acryloyl group” means an acryloyl group or a methacryloyl group.

(Fluorine oligomer (R))
The fluorine-based oligomer (R) has a (meth) acryloyl group, and has, for example, a structure in which a (meth) acryloyl group is arranged at a terminal of a fluorine-containing hydrocarbon chain. In the fluorinated oligomer (R), the (meth) acryloyl group functions as a polymerizable functional group that reacts with other components by external energy such as light and heat.

By mixing the fluorine-based oligomer (R) in the polymerizable composition, fluorine atoms derived from the fluorine-containing hydrocarbon chain are unevenly distributed on the surface of the polymer layer 3 (the surface opposite to the base material 2), Since the surface free energy of the polymer layer 3 decreases, the antifouling property of the antifouling film 1 increases. On the other hand, according to the fluorine-based oligomer having no (meth) acryloyl group, the antifouling property of the antifouling film 1 is not maintained for a long time because it does not crosslink in the polymerizable composition.

The polymerizable composition contains the fluorine-based oligomer (R) in an amount of 2.5 to 12.5% by weight, preferably 5 to 10% by weight in terms of an active ingredient. When the content of the fluorinated oligomer (R) in the polymerizable composition is lower than 2.5% by weight in terms of the effective component, it is unevenly distributed on the surface of the polymer layer 3 (the surface on the side opposite to the substrate 2). The amount of fluorine atoms decreases, and the antifouling property of the antifouling film 1 decreases. When the content of the fluorinated oligomer (R) in the polymerizable composition is higher than 12.5% by weight in terms of the active ingredient, the compatibility with other components in the polymerizable composition decreases, and as a result, In addition, the transparency of the antifouling film 1 (polymer layer 3) decreases (whitens). When the polymerizable composition contains a plurality of types of fluorine-based oligomers (R), if the total content of the plurality of types of fluorine-based oligomers (R) is 2.5 to 12.5% by weight in terms of an active ingredient. Good. In the present specification, the “active component” of the polymerizable composition is a component that becomes a constituent component of the polymer layer after curing, and excludes a component (for example, a solvent) that does not contribute to the curing reaction (polymerization reaction). means.

The fluorine-based oligomer (R) includes at least one of a perfluoropolyether-based oligomer (R1) and a perfluoroalkyl-based oligomer (R2). In the present specification, “perfluoropolyether-based oligomer” means a fluorine-based oligomer having a perfluoropolyether group. In the present specification, “perfluoroalkyl-based oligomer” means a fluorine-based oligomer having a perfluoroalkyl group. In particular, when the perfluoropolyether-based oligomer (R1) is blended as the fluorine-based oligomer (R), the surface of the polymer layer 3 (the surface on the opposite side to the base material 2) is caused due to its mobility. ) Tends to increase, and as a result, abrasion resistance tends to increase.

Known examples of the perfluoropolyether-based oligomer (R1) include “Fomblin (registered trademark) MT70”, “Fluorolink (registered trademark) AD1700”, and “Fluorolink MD700” manufactured by Solvay, manufactured by Shin-Etsu Chemical Co., Ltd. "KY-1203E", "KY-1211", "KY-1207", "OPTOOL DAC-HP" manufactured by Daikin Industries, Ltd., and the like.

Known examples of perfluoroalkyl-based oligomers (R2) include “Megafax (registered trademark) RS-90”, “Megafax RS-75”, “Megafax RS-76-NS”, and DICEL® "EBECRYL (registered trademark) 8110" manufactured by Ornex, and "Fergent (registered trademark) 601ADH2" manufactured by Neos, and the like.

(Block copolymer (S))
The block copolymer (S) is a copolymer composed of a fluorine segment and a non-fluorine segment. In the present specification, the “fluorine segment” means a cured product (polymerized product) of a monomer containing a fluorine-based monomer as a main component. The fluorine-based monomer is not particularly limited as long as it is a radical-polymerizable monomer containing a fluorine atom. In the present specification, the “non-fluorine segment” means a cured product (polymer) of a monomer containing a non-fluorine monomer as a main component. The non-fluorine-based monomer is not particularly limited as long as it is a radical-polymerizable monomer containing no fluorine atom.

The proportion of the fluorine segment in the block copolymer (S) is preferably from 10 to 90% by weight, more preferably from 35 to 65% by weight. When the proportion of the fluorine segment in the block copolymer (S) is lower than 10% by weight, the performance as a fluorine segment, that is, sufficient antifouling property (for example, water repellency, oil repellency) may not be obtained. When the proportion of the fluorine segment in the block copolymer (S) is higher than 90% by weight, the compatibility with other components in the polymerizable composition decreases, and as a result, the antifouling film 1 (polymer layer The transparency of 3) may decrease (whiten).

The number average molecular weight of the block copolymer (S) is preferably 5,000 to 1,000,000, more preferably 10,000 to 300,000, and still more preferably 10,000 to 100,000. When the number average molecular weight of the block copolymer (S) is less than 5000, the fluorine segment is short, and its performance, that is, sufficient antifouling properties (for example, water repellency, oil repellency) may not be obtained. When the number average molecular weight of the block copolymer (S) is larger than 1,000,000, the compatibility with other components in the polymerizable composition is reduced, and as a result, the transparency of the antifouling film 1 (polymer layer 3) is reduced. May be reduced (whitened).

When the block copolymer (S) is blended in the polymerizable composition, the non-fluorine segment functions as a compatible segment having compatibility with other components in the polymerizable composition, while the fluorine segment ( Fluorine atoms originating from the fluorine segment are unevenly distributed on the surface of the polymer layer 3 (the surface on the side opposite to the base material 2). Therefore, the surface free energy of the polymer layer 3 decreases, and the antifouling property of the antifouling film 1 increases.

The block copolymer (S) is preferably a perfluoroalkyl-based copolymer. In the present specification, "perfluoroalkyl-based copolymer" means a fluorine-based copolymer having a perfluoroalkyl group. When the block copolymer (S) is a perfluoroalkyl copolymer, the fluorine segments tend to be unevenly distributed on the surface of the polymer layer 3 (the surface on the side opposite to the substrate 2) (arranged so that rigid molecular chains stand). Fluorine atoms are likely to be densely distributed on the surface of the polymer layer 3 (the surface opposite to the base material 2), and as a result, the antifouling property of the antifouling film 1 is likely to be enhanced. .

The block copolymer (S) may not have a (meth) acryloyl group that functions as a polymerizable functional group. Since the non-fluorine segment of the block copolymer (S) has compatibility with other components in the polymerizable composition, the polymer layer 3 does not have a (meth) acryloyl group as a polymerizable functional group. Easy to be fixed inside.

The polymerizable composition contains 1 to 10% by weight, preferably 3 to 8% by weight of the block copolymer (S) in terms of the active ingredient. When the content of the block copolymer (S) in the polymerizable composition is lower than 1% by weight in terms of an active ingredient, the fluorine atoms localized on the surface of the polymer layer 3 (the surface on the opposite side to the substrate 2) The amount decreases, and the antifouling property of the antifouling film 1 decreases. When the content of the block copolymer (S) in the polymerizable composition is higher than 10% by weight in terms of the effective component, the compatibility with other components in the polymerizable composition decreases, and as a result, the antifouling property is reduced. The transparency of the conductive film 1 (polymer layer 3) decreases (whitens). When the polymerizable composition contains a plurality of types of block copolymers (S), the total content of the plurality of types of block copolymers (S) may be 1 to 10% by weight in terms of an active ingredient.

Known examples of the block copolymer (S) include “MODIPER (registered trademark) F606”, “MODIPAR F206”, and “MODIPAR F3636” manufactured by NOF Corporation.

In this embodiment, since the fluorine-based oligomer (R) and the block copolymer (S) are used in combination as the fluorine-based compound, fluorine atoms are present on the surface of the polymer layer 3 (the surface on the side opposite to the base material 2). And the antifouling property of the antifouling film 1 is significantly increased. The inventors of the present invention consider the mechanism for increasing the antifouling property of the antifouling film 1 as follows.

FIG. 3 is a schematic diagram showing an image of a fluorine compound present on the surface of the polymer layer in FIG. As shown in FIG. 3, since the fluorine-based oligomer (R) 10 is a soft segment, the fluorine-based oligomer (R) 10 is arranged along the surface of the polymer layer 3 (the surface on the side opposite to the base material 2) (the molecular chains lie down). And so on). On the other hand, since the block copolymer (S) 20 is a hard segment, the fluorine segments 21 are arranged closer to the surface of the polymer layer 3 (the surface opposite to the base material 2) than the non-fluorine segments 22 (molecules). Arrange the chains so that they stand). In such a state, when the block copolymer (S) 20 is arranged between the fluorine-based oligomers (R) 10, the fluorine atoms are densely attached to the surface of the polymer layer 3 (the surface opposite to the substrate 2). Therefore, for example, the antifouling property of the antifouling film 1 is remarkably improved as compared with the case where only the fluorine-based oligomer (R) 10 or the block copolymer (S) 20 is used.

The polymerizable composition may further contain a monofunctional amide monomer. In the present specification, the “monofunctional amide monomer” means a monomer having an amide group and having one acryloyl group per molecule. When a monofunctional amide monomer is blended in the polymerizable composition, the compatibility with the fluorine-based compound increases, so that the fluorine atoms in the fluorine-based compound cause the fluorine atoms in the surface of the polymer layer 3 (on the side opposite to the base material 2). Surface) and the antifouling property of the antifouling film 1 is further enhanced. Further, curing shrinkage during curing of the polymerizable composition is suppressed, and the cohesive force with the substrate 2 is increased, so that the adhesion between the polymer layer 3 and the substrate 2 is increased.

The polymerizable composition may contain a monofunctional amide monomer in an amount of preferably 1 to 15% by weight, more preferably 5 to 10% by weight in terms of an active ingredient. When the content of the monofunctional amide monomer in the polymerizable composition is lower than 1% by weight in terms of the effective component, the adhesion between the polymer layer 3 and the substrate 2 may not be sufficiently increased. When the content of the monofunctional amide monomer in the polymerizable composition is higher than 15% by weight in terms of the effective component, the crosslink density of the polymer layer 3 does not increase, and as a result, the abrasion resistance may decrease. . When the polymerizable composition contains a plurality of types of monofunctional amide monomers, the total content of the plurality of types of monofunctional amide monomers is preferably within the above range in terms of an active ingredient.

Examples of the monofunctional amide monomer include N-acryloylmorpholine, N, N-dimethylacrylamide, N, N-diethylacrylamide, N- (2-hydroxyethyl) acrylamide, diacetone acrylamide, Nn-butoxymethylacrylamide, And the like.

Known examples of N-acryloylmorpholine include “ACMO (registered trademark)” manufactured by KJ Chemicals. Known examples of N, N-dimethylacrylamide include “DMAA (registered trademark)” manufactured by KJ Chemicals. Known examples of N, N-diethylacrylamide include "DEAA (registered trademark)" manufactured by KJ Chemicals. Known examples of N- (2-hydroxyethyl) acrylamide include “HEAA (registered trademark)” manufactured by KJ Chemicals. Known examples of diacetone acrylamide include “DAAM (registered trademark)” manufactured by Nippon Kasei Co., Ltd. Known examples of Nn-butoxymethylacrylamide include “NBMA” manufactured by MRC Unitech.

The polymerizable composition may further contain a polyfunctional acrylate. In the present specification, “polyfunctional acrylate” means an acrylate having two or more acryloyl groups per molecule. When the polyfunctional acrylate is blended in the polymerizable composition, the crosslinking density of the polymer layer 3 is increased, and a suitable elasticity (hardness) is provided, so that the abrasion resistance is enhanced.

The polyfunctional acrylate preferably contains at least one polyfunctional acrylate having an ethylene oxide group. Thereby, a suitable elasticity (hardness) is imparted by the polymer layer 3, so that the abrasion resistance is further improved.

The polymerizable composition may contain a polyfunctional acrylate preferably in an amount of 50 to 96% by weight, more preferably 60 to 90% by weight in terms of an active ingredient. When the content of the polyfunctional acrylate in the polymerizable composition is lower than 50% by weight in terms of the effective component, the polymer layer 3 becomes hard, and as a result, the abrasion resistance may decrease. When the content of the polyfunctional acrylate in the polymerizable composition is higher than 96% by weight in terms of the effective component, the crosslink density of the polymer layer 3 does not increase, and as a result, the abrasion resistance may decrease. When the polymerizable composition contains a plurality of types of polyfunctional acrylates, the total content of the plurality of types of polyfunctional acrylates is preferably within the above range in terms of an active ingredient.

Examples of the polyfunctional acrylate include polyethylene glycol (200) diacrylate, trimethylolpropane triacrylate, and the like.

Known examples of polyethylene glycol (200) diacrylate include "MIRAMER (registered trademark) M282" manufactured by MIWON. Known examples of trimethylolpropane triacrylate include "MIRAMER M300" manufactured by MIWON.

The polymerizable composition may further contain a polymerization initiator. When the polymerization initiator is blended with the polymerizable composition, the curability of the polymerizable composition increases.

Examples of the polymerization initiator include a photopolymerization initiator, a thermal polymerization initiator and the like, and among them, a photopolymerization initiator is preferable. The photopolymerization initiator is a polymerization initiator that is active with respect to active energy rays.

Examples of the photopolymerization initiator include a radical polymerization initiator, an anionic polymerization initiator, and a cationic polymerization initiator. Examples of such a photopolymerization initiator include acetophenones such as p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one; Ketones such as benzophenone, 4,4'-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone and 2-isopropylthioxanthone; benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether and the like Benzoin ethers; benzyl ketals such as benzyldimethyl ketal and hydroxycyclohexylphenyl ketone; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; Scan (2,4,6-trimethylbenzoyl) - acylphosphine oxides such as triphenylphosphine oxide; 1-hydroxy - cyclohexyl - phenyl - phenones such as ketones, and the like.

Known examples of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide include "LUCIRIN (registered trademark) TPO" and "IRGACURE (registered trademark) TPO" manufactured by IGM Resins. Known examples of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide include “IRGACURE 819” manufactured by IGM Resins. Known examples of 1-hydroxy-cyclohexyl-phenyl-ketone include "IRGACURE 184" manufactured by IGM Resins.

The polymerizable composition may further contain a solvent. In this case, the solvent may be contained in each component of the polymerizable composition together with the active ingredient, or may be contained independently of each component.

Examples of the solvent include alcohols (1 to 10 carbon atoms: for example, methanol, ethanol, n- or i-propanol, n-, sec-, or t-butanol, benzyl alcohol, octanol, etc.), ketones (carbon numbers 1 to 10). 3-8: For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, dibutyl ketone, cyclohexanone, etc., ester or ether ester (C4-10: for example, ethyl acetate, butyl acetate, ethyl lactate, etc.), γ- Butyrolactone, ethylene glycol monomethyl acetate, propylene glycol monomethyl acetate, ether (4 to 10 carbon atoms: for example, EG monomethyl ether (methylcellosolob), EG monoethyl ether (ethylcellosolov), diethylene glycol Butyl ether (butyl cellosorb, propylene glycol monomethyl ether, etc.), aromatic hydrocarbon (C6-10: for example, benzene, toluene, xylene, etc.), amide (C3-10: for example, dimethylformamide, dimethylacetamide, N -Methylpyrrolidone, etc.), halogenated hydrocarbons (1 to 2 carbon atoms: for example, methylene dichloride, ethylene dichloride, etc.), petroleum solvents (for example, petroleum ether, petroleum naphtha, etc.), and the like.

From the viewpoint of antifouling properties, the contact angle of water to the surface of the polymer layer 3 (the surface opposite to the substrate 2) is preferably 120 ° or more, and the contact angle of hexadecane is preferably 30 ° or more. The contact angle of water is preferably 140 ° or more, and the contact angle of hexadecane is more preferably 70 ° or more, and the contact angle of water is more preferably 150 ° or more and the contact angle of hexadecane is more preferably 90 ° or more.

The application of the antifouling film 1 is not particularly limited as long as it utilizes the excellent antifouling property, and may be, for example, an optical film application such as an antireflection film. Such an antireflection film contributes to improvement in visibility by being attached to the inside or outside of the display device.

The antifouling property of the antifouling film 1 may mean that dirt attached to the surface of the polymer layer 3 (the surface on the side opposite to the substrate 2) can be easily removed. This may mean that dirt hardly adheres to the surface 3 (the surface opposite to the substrate 2). Further, according to the antifouling film 1, an effect of the moth-eye structure can provide higher antifouling properties than a conventional antifouling film having a normal surface such as a flat surface (for example, a fluorine-containing film).

The antifouling film 1 may be manufactured, for example, by the following manufacturing method. 4A, 4B, 4C, 4D, and 4E are schematic cross-sectional views illustrating an example of a method for manufacturing an antifouling film according to the embodiment.

(A) Release Processing of Die As shown in FIG. 4A, a release agent 7 is applied on the surface of the die 5.

Examples of the method of applying the release treatment agent 7 include a method of applying by a spray method, a gravure method, a slot die method, a bar coat method, a potting method, and the like.

(B) Application of Polymerizable Composition As shown in FIG. 4B, the polymerizable composition 6 is applied on the surface of the substrate 2.

Examples of the method of applying the polymerizable composition 6 include a method of applying by a spray method, a gravure method, a slot die method, a bar coat method, and the like. Among them, a method of applying a gravure method or a slot die method is preferable from the viewpoint of making the film thickness uniform and improving productivity.

The polymerizable composition 6 contains the fluorine-based oligomer (R) and the block copolymer (S) at the above-described predetermined ratio as the fluorine-based compound. Here, when the polymerizable composition 6 further contains a solvent, a heat treatment (drying treatment) for removing the solvent may be performed after the application of the polymerizable composition 6. This heat treatment is preferably performed at a temperature equal to or higher than the boiling point of the solvent.

(A) and (B) may be performed at the same timing or at different timings.

(C) Formation of Concavo-convex Structure With the polymerizable composition 6 interposed therebetween, the substrate 2 is pressed against the surface of the mold 5 on which the release agent 7 has been applied. As a result, as shown in FIG. 4C, an uneven structure is formed on the surface of the polymerizable composition 6 (the surface on the side opposite to the substrate 2).

(D) Formation of polymer layer The polymerizable composition 6 is cured. As a result, a polymer layer 3 is formed as shown in FIG. 4D.

Examples of the method for curing the polymerizable composition 6 include a method using irradiation with active energy rays, heating, and the like. The curing of the polymerizable composition 6 is preferably performed by irradiation with active energy rays, and more preferably performed by irradiation with ultraviolet rays. The irradiation of the active energy ray may be performed from the base material 2 side of the polymerizable composition 6 or may be performed from the mold 5 side of the polymerizable composition 6. Further, the number of times of irradiation of the polymerizable composition 6 with the active energy ray may be only once or may be plural times.

The above (C) and the above (D) may be performed at the same timing or at different timings.

(E) Peeling of mold As shown in FIG. 4E, the mold 5 is peeled from the polymer layer 3. As a result, the antifouling film 1 is completed.

In this specification, a series of processes as described in the above (B) to (E) is also referred to as “mold transfer”. In the present manufacturing method example, when the antifouling film 1 is manufactured continuously, the above (A) may be performed at least once at the first stage (before the first transfer), and thereafter, the above (B) to (B). E) may be repeated. For example, (A), (B), (C), (D), (E), (B), (C), (D), (E), (B), (C), (D), As in the order of (E),..., The above (A) does not have to be performed each time during the second and subsequent transfer. Also, (A), (B), (C), (D), (E), (B), (C), (D), (E), (A), (B), (C), (A) may be appropriately performed at the time of the second and subsequent transfer (in this example, at the time of the third transfer) in the order of (D), (E),.... In the transfer of such a mold, for example, if the base material 2 is formed into a roll shape, the above (B) to (E) can be performed continuously and efficiently.

<Mold>
As the mold 5, for example, a mold produced by the following method can be used. First, aluminum as a material of the mold 5 is formed on the surface of the supporting substrate by a sputtering method. Next, anodizing and etching are alternately repeated on the formed aluminum layer, whereby a female mold (die 5) having a moth-eye structure can be manufactured. At this time, the uneven structure of the mold 5 can be changed by adjusting the time for performing anodic oxidation and the time for performing etching.

Examples of the material of the supporting substrate include glass; metals such as stainless steel and nickel; polypropylene, polymethylpentene, and cyclic olefin polymers (typically, norbornene-based resins and the like, "ZEONOR" manufactured by Zeon Corporation). (Registered trademark) "and" Arton (registered trademark) "manufactured by JSR Corporation); polycarbonate resins; resins such as polyethylene terephthalate, polyethylene naphthalate, and triacetyl cellulose. Further, instead of the aluminum film formed on the surface of the supporting substrate, an aluminum substrate may be used.

Examples of the shape of the mold 5 include a flat plate shape and a roll shape.

<Release agent>
The release agent 7 is used for the purpose of releasing the surface of the mold 5. According to the release treatment agent 7, the releasability (for example, water repellency) of the mold 5 is enhanced, and the mold 5 can be easily peeled from the polymer layer 3. Further, since the surface free energy of the mold 5 is reduced, when the substrate 2 is pressed against the mold 5, the fluorine atoms in the fluorine-based compound blended in the polymerizable composition 6 are removed from the polymerizable composition 6. It can be uniformly distributed on the surface (the surface opposite to the substrate 2). Further, before the polymerizable composition 6 is cured, it is possible to prevent the fluorine atoms from separating from the surface of the polymerizable composition 6 (the surface on the side opposite to the substrate 2). As a result, in the antifouling film 1, the fluorine atoms can be uniformly distributed on the surface of the polymer layer 3 (the surface opposite to the substrate 2).

Examples of the release agent 7 include a fluorine-based release agent, a silicon-based release agent, and a phosphate-based release agent, and among them, a fluorine-based release agent is preferable. As the fluorine-based release agent, a perfluoropolyether-based release agent is preferably used. Examples of known examples thereof include "Optool (registered trademark) DSX", "Optool UD509", and "Optool" manufactured by Daikin Industries, Ltd. AES4 ".

In this example of the manufacturing method, the releasability of the mold 5 may decrease with an increase in the number of times the mold 5 is transferred. This is because the release agent 7 deteriorates or the components in the polymerizable composition 6 adhere (accumulate) to the surface of the mold 5 (the surface to which the release agent 7 is applied). . When the releasability of the mold 5 is reduced as described above, the antifouling property of the obtained antifouling film 1 is reduced in the related art. On the other hand, in the present embodiment, as already described with reference to FIG. 3, the fluorine atom (R) and the block copolymer (S) contained in the polymerizable composition 6 interact to form a fluorine atom. Are densely distributed on the surface of the polymer layer 3 (the surface on the side opposite to the base material 2), so that it can be obtained even if the number of transfers of the mold 5 is increased (even if manufactured continuously for a long period of time). The antifouling property of the antifouling film 1 is maintained high.

[Examples and Comparative Examples]
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

In Examples and Comparative Examples, the materials used for producing the antifouling film are as follows.

<Substrate>
“TAC-TD80U” manufactured by Fuji Film Co., Ltd. was used and its thickness was 80 μm.

<Mold>
The one produced by the following method was used. First, aluminum as a material for a mold was formed on a 10 cm square glass substrate by a sputtering method. The thickness of the formed aluminum layer was 1.0 μm. Next, anodization and etching are alternately repeated on the formed aluminum layer, so that a number of minute holes (the distance between the bottom points of adjacent holes (concave portions) is equal to or less than the wavelength of visible light). Was formed to form an anodized layer. Specifically, an aluminum layer is formed by sequentially performing anodizing, etching, anodizing, etching, anodizing, etching, anodizing, etching, and anodizing (anodic oxidation: 5 times, etching: 4 times). A large number of minute holes (concave portions) having a shape (tapered shape) tapering inward were formed, and as a result, a mold having an uneven structure was obtained. Anodization was performed using oxalic acid (concentration: 0.03% by weight) under the conditions of a liquid temperature of 5 ° C. and an applied voltage of 80 V. The time for performing one anodic oxidation was 25 seconds. The etching was performed using phosphoric acid (concentration: 1 mol / l) at a liquid temperature of 30 ° C. The time for performing one etching was 25 minutes. When the mold was observed with a scanning electron microscope, the depth of the recess was 290 nm.

<Release agent>
"OPTOOL DSX" manufactured by Daikin Industries, Ltd. was used, and the active ingredient concentration was 0.1% by weight.

<Polymerizable composition>
Polymerizable compositions A1 to A13 and B1 to B9 having compositions (active ingredient amounts) as shown in Tables 1 to 5 were used. Abbreviations of each component are as follows.

(Perfluoropolyether oligomer (R1))
・ "MT70"
“Fomblin MT70” manufactured by Solvay
Active ingredient concentration: 80% by weight
・ "1203E"
"KY-1203E" manufactured by Shin-Etsu Chemical Co., Ltd.
Active ingredient concentration: 20% by weight

(Perfluoroalkyl oligomer (R2))
・ "RS-90"
DIC's MegaFac RS-90
Active ingredient concentration: 10% by weight
・ “E8110”
"EBECRYL8110" manufactured by Daicel Ornex
Active ingredient concentration: about 50% by weight

(Block copolymer (S))
・ "F606"
"MODIPER F606" manufactured by NOF Corporation
Active ingredient concentration: 100% by weight
Perfluoroalkyl group: having (meth) acryloyl group: not having

(Perfluoroalkyl monomer)
・ "FAAC-6"
"CHEMINOX FAAC-6" manufactured by Unimatec
Active ingredient concentration: 100% by weight

(Monofunctional amide monomer)
・ "AC"
"ACMO" manufactured by KJ Chemicals
Active ingredient concentration: 100% by weight

(Polyfunctional acrylate)
・ "M282"
"MIRAMER M282" manufactured by MIWON
Active ingredient concentration: 100% by weight
Number of ethylene oxide groups: 4 per molecule. "M300"
"MIRAMER M300" manufactured by MIWON
Active ingredient concentration: 100% by weight
Number of ethylene oxide groups: 0

(Polymerization initiator)
・ "TPO"
"IRGACURE TPO" manufactured by IGM Resins
Active ingredient concentration: 100% by weight

Tables 6 to 10 show the content (effective component conversion) of each component in the polymerizable compositions A1 to A13 and B1 to B9.

<Example 1>
The antifouling film of Example 1 was produced by the following method.

(A) Mold release treatment A release treatment agent was applied on the surface of the mold. The thickness of the release treatment agent was 5 nm. The contact angle of water (static contact angle) with respect to the surface of the mold on which the release agent was applied was 160 ° or more.

(B) Application of polymerizable composition The polymerizable composition A1 was applied on the surface of a substrate. The thickness of the polymerizable composition A1 was 35 μm.

(C) Formation of Concavo-convex Structure With the polymerizable composition A1 interposed therebetween, the substrate was pressed against the surface of the mold to which the release agent was applied. As a result, an uneven structure was formed on the surface of the polymerizable composition A1 (the surface on the side opposite to the substrate).

(D) Formation of Polymer Layer The polymerizable composition A1 was cured by irradiating ultraviolet rays (irradiation amount: 1 J / cm ² ) from the substrate side. As a result, a polymer layer was formed.

(E) Release of the mold The mold was peeled from the polymer layer. As a result, an antifouling film was completed. The thickness of the polymer layer was 12 μm.

The surface specifications of the antifouling film were as follows.
Shape of convex part: average pitch of bell-shaped convex part: 200 nm
Average height of projections: 200 nm
Average aspect ratio of projection: 1.0

The surface specifications of the antifouling film were evaluated using a scanning electron microscope “S-4700” manufactured by Hitachi High-Technologies Corporation. At the time of evaluation, using an osmium coater “Neoc-ST” manufactured by Meiwa Forsys Co., Ltd., an osmium oxide VIII (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) on the surface of the polymer layer (the surface opposite to the base material) was used. (Thickness: 5 nm).

Thereafter, transfer of the mold (a series of processes (B) to (E)) was repeated 500 times. Hereinafter, "Specification 1" indicates that the number of transfer times of the mold is the first time, "Specification 2" indicates that the number of transfer times of the mold is 200, and "Specification 2" indicates that the number of transfer times of the mold is 500. Specification 3 ". That is, the antifouling film obtained by the first transfer of the mold was referred to as “spec 1 antifouling film”, and the antifouling film obtained by the 200th transfer of the mold was referred to as “spec 2 antifouling film”. Film ", and the antifouling film obtained by the 500th transfer of the mold is called" specification 3 antifouling film ".

<Examples 2 to 13 and Comparative Examples 1 to 9>
Except having changed to the manufacturing conditions as shown in Tables 11-15, it carried out similarly to Example 1, and manufactured the antifouling film of each example.

[Evaluation]
The following evaluation was performed for each example. The results are shown in Tables 11 to 15.

<Transparency>
As the transparency, the transparency of the polymerizable composition was evaluated. Specifically, the polymerizable composition was placed in a transparent test tube, and the state was visually observed under an environment of illuminance 100 lx (fluorescent lamp). The criteria were as follows.
：: Transparent or very slightly cloudy.
Δ: slightly cloudy, but no sediment was observed even after standing for one day.
×: Cloudy, sediment was observed after standing for one day.
Here, it was determined that the higher the transparency of the polymerizable composition, the higher the compatibility of each component in the polymerizable composition.

<Anti-reflective property>
As the antireflection property, the reflectance of the antifouling film was measured. Specifically, first, for each of the antifouling films of specifications 1 to 3, on the surface on the side opposite to the polymer layer of the base material, via an optical adhesive layer, black color manufactured by Mitsubishi Rayon Co., Ltd. An acrylic plate “Acrylite (registered trademark) EX-502” was attached. Then, with respect to the antifouling film of each specification, the surface of the polymer layer (the surface on the side opposite to the substrate) is irradiated with light from a C light source from a direction of a polar angle of 5 ° and reflected at an incident angle of 5 ° The ratio (specular reflectance, unit:%) was measured. The measurement of the reflectance was performed using a spectrophotometer “V-560” manufactured by JASCO Corporation in a wavelength region of 250 to 850 nm. In this evaluation, the reflectance at a wavelength of 750 nm (visual reflectance: Y value) was used as an evaluation index for antireflection properties. The criteria were as follows.
◎: “Reflectance” ≦ 0.1
：: 0.1 <“reflectance” ≦ 0.3
Δ: 0.3 <“reflectance” ≦ 0.5
×: “Reflectance”> 0.5
Here, when the judgment was ◎, ○, or Δ, it was judged that the antireflection property was excellent.

<Antifouling property>
As the antifouling property, water repellency, oil repellency, and fingerprint wiping properties of the antifouling film were evaluated.

(Water repellency)
For each of the antifouling films of specifications 1 to 3, water (approximately 10 μl droplets) was dropped on the surface of the polymer layer (the surface opposite to the substrate), and contact was made 1 second after the dropping. The angle (static contact angle) was measured. In Tables 11 to 15, "No droplets" indicates a state in which the contact angle is extremely large (for example, 160 ° or more) and the water repellency is extremely high.

(Oil repellency)
For each of the antifouling films of specifications 1 to 3, hexadecane (approximately 10 μl droplet) was dropped on the surface of the polymer layer (the surface opposite to the substrate), and contact was made 1 second after the dropping. The angle (static contact angle) was measured.

As the contact angle, using a portable contact angle meter “PCA-1” manufactured by Kyowa Interface Science Co., Ltd., the θ / 2 method (θ / 2 = arctan (h / r), θ: contact angle, r: droplet (Radius, h: height of the droplet). Here, as the first measurement point, the central portion of the antifouling film was selected, and as the second and third measurement points, the distance from the first measurement point was 20 mm or more, and Two points that are point-symmetric with respect to the first measurement point were selected.

(Fingerprint wiping properties)
First, for each of the antifouling films of specifications 1 to 3, a black acrylic plate "Acrylite" manufactured by Mitsubishi Rayon Co., Ltd. was provided on the surface opposite to the polymer layer of the substrate via an optical adhesive layer. EX-502 ”was pasted. Next, assuming a fingerprint, 0.1 ml of an artificial contaminated liquid manufactured by Isehisa was immersed in "Bencott (registered trademark) S-2" manufactured by Asahi Kasei Fibers, and then rubber gloves were worn. Attached to finger. Then, 10 minutes after the artificially contaminated liquid was applied to the surface of the polymer layer (the surface opposite to the base material) with a finger against the antifouling film of each specification, "Bencott" manufactured by Asahi Kasei Fibers Corp. S-2 "was rubbed 10 times, and whether or not the artificial contaminated liquid was wiped was visually observed under an environment of illuminance of 100 lx (fluorescent lamp). The criteria were as follows.
：: The artificial contaminated liquid was completely wiped off, and no residue after wiping was visible.
Δ: The artificial contaminated liquid was inconspicuous, but when a fluorescent lamp was reflected, a slight wiping residue was visible.
X: The artificial contaminated liquid was not wiped off at all.
Here, when the judgment was "O" or "△", it was judged that the fingerprint wiping property was excellent.

As shown in Tables 11 to 13, in Examples 1 to 13, the antifouling property of the antifouling film is maintained high even if the number of times of transfer of the mold is increased (even if the mold is continuously manufactured for a long time). I was In Examples 1 to 13, the antireflection properties of the antifouling film remained excellent even when the number of times of transfer of the mold was increased (even when the mold was manufactured continuously).

On the other hand, as shown in Tables 14 and 15, in Comparative Examples 1 to 9, when the number of times of transfer of the mold was increased, an antifouling film having excellent antifouling properties could not be produced.

In Comparative Example 1, since the fluorine-based compound was not blended in the polymerizable composition, the antifouling property of the antifouling film was low at the stage of specification 1. Further, when the number of times of transfer of the mold was increased, at the time of the 50th transfer of the mold, the mold was hardly peeled off from the polymer layer, and the production of the antifouling film became difficult. .

In Comparative Example 2, the antifouling film was whitened at the stage of specification 2 (the antireflection property was reduced). Therefore, subsequent evaluation was discontinued. The present inventors consider the mechanism of whitening of the antifouling film as follows. In Comparative Example 2, in addition to the fluorine-based oligomer (R) (perfluoropolyether-based oligomer (R1)), not the block copolymer (S) but the perfluoroalkyl-based monomer “FAAC-6” was polymerized as the fluorine-based compound. Was contained in the acidic composition. Since “FAAC-6” is a low molecule, it migrated to the surface of the mold (the surface to which the release agent was applied) during the transfer of the mold, and accumulated in a polymerized state. When the number of times of transfer of the mold increases in such a state, a part of the polymer derived from “FAAC-6” accumulated on the surface of the mold becomes part of the surface of the polymer layer (the opposite side to the base material). As a result, the antifouling film turned white.

In Comparative Example 3, the antifouling film was whitened at the stage of specification 2 (the antireflection property was reduced). Therefore, subsequent evaluation was discontinued. The present inventors consider the mechanism of whitening of the antifouling film in the same manner as in Comparative Example 2.

In Comparative Example 4, since only the fluorine-based oligomer (R) (perfluoropolyether-based oligomer (R1)) was compounded in the polymerizable composition as the fluorine-based compound, the antifouling property of the antifouling film hardly increased, As the number of transfer times of the mold increased, the antifouling property of the antifouling film decreased.

In Comparative Example 5, since only the fluorine-based oligomer (R) (perfluoroalkyl-based oligomer (R2)) was blended in the polymerizable composition as the fluorine-based compound, the antifouling property of the antifouling film hardly increased, and As the number of transfer times of the mold increased, the antifouling property of the antifouling film decreased.

In Comparative Example 6, since the content of the fluorine-based oligomer (R) (perfluoropolyether-based oligomer (R1)) in the polymerizable composition was higher than 12.5% by weight in terms of the effective component, the polymerizable composition The compatibility with other components in the film was reduced, and the antifouling film was whitened at the stage of specification 1 (the antireflection property was reduced). Therefore, subsequent evaluation was discontinued.

In Comparative Example 7, since the content of the fluorine-based oligomer (R) (perfluoropolyether-based oligomer (R1)) in the polymerizable composition was lower than 2.5% by weight in terms of the effective component, the transfer of the mold was performed. As the number of times increased, the antifouling property of the antifouling film decreased.

In Comparative Example 8, since the content of the block copolymer (S) in the polymerizable composition was higher than 10% by weight in terms of the effective component, the compatibility with other components in the polymerizable composition was reduced, and The stained film was whitened at the stage of specification 1 (the antireflection property was reduced). Therefore, subsequent evaluation was discontinued.

In Comparative Example 9, since the content of the block copolymer (S) in the polymerizable composition was lower than 1% by weight in terms of the effective component, the antifouling property of the antifouling film increased when the number of times of transfer of the mold increased. Dropped.

[Appendix]
One embodiment of the present invention provides a prevention method including a base material, and a polymer layer provided on a surface of the base material and having a concave-convex structure on the surface, in which a plurality of protrusions are provided at a pitch equal to or less than a wavelength of visible light. In a fouling film, the polymer layer is a cured product of a polymerizable composition, and the polymerizable composition has a fluorine-based oligomer having a (meth) acryloyl group of 2.5 to 12.5% by weight, 1 to 10% by weight of a block copolymer comprising a fluorine segment and a non-fluorine segment, and the fluorine-based oligomer includes at least one of a perfluoropolyether-based oligomer and a perfluoroalkyl-based oligomer And an antifouling film. According to this aspect, an antifouling film that maintains high antifouling properties even when manufactured continuously for a long period of time is realized.

In one embodiment of the present invention, the polymerizable composition may contain 5 to 10% by weight of the fluorine-based oligomer in terms of an active ingredient. Thereby, the antifouling property of the antifouling film is further enhanced. Further, the compatibility with other components in the polymerizable composition is increased, and as a result, the transparency of the antifouling film (the polymer layer) is further increased.

In one embodiment of the present invention, the polymerizable composition may contain 3 to 8% by weight of the block copolymer in terms of an active ingredient. Thereby, the antifouling property of the antifouling film is further enhanced. Further, the compatibility with other components in the polymerizable composition is increased, and as a result, the transparency of the antifouling film (the polymer layer) is further increased.

In one embodiment of the present invention, the polymerizable composition may further contain a monofunctional amide monomer. This increases the compatibility with the fluorine-based compound including the fluorine-based oligomer and the block copolymer, so that the fluorine atoms in the fluorine-based compound are located on the surface of the polymer layer (the surface opposite to the base). It tends to be unevenly distributed, and the antifouling property of the antifouling film is further enhanced. Further, curing shrinkage during curing of the polymerizable composition is suppressed, and the cohesive force with the base material is increased, so that the adhesion between the polymer layer and the base material is increased.

In one embodiment of the present invention, the thickness of the polymer layer may be 5 to 20 μm. As a result, fluorine atoms in the fluorine-based compound including the fluorine-based oligomer and the block copolymer are unevenly distributed at a high concentration on the surface of the polymer layer (the surface on the side opposite to the base).

In one embodiment of the present invention, the average pitch of the plurality of protrusions may be 100 to 400 nm. As a result, the occurrence of optical phenomena such as moiré and rainbow unevenness is sufficiently prevented.

In one embodiment of the present invention, the average height of the plurality of protrusions may be 50 to 600 nm. Thereby, it is possible to achieve both of the above-mentioned plurality of convex portions and the preferable average aspect ratio.

In one embodiment of the present invention, an average aspect ratio of the plurality of protrusions may be 0.8 to 1.5. Accordingly, the occurrence of optical phenomena such as moiré and rainbow unevenness is sufficiently prevented, and excellent antireflection properties can be realized. Further, the occurrence of sticking due to the reduction in workability of the uneven structure and the deterioration of the transfer condition when forming the uneven structure are sufficiently prevented.

Another aspect of the present invention is that, in terms of an active ingredient, 2.5 to 12.5% by weight of a fluorine-based oligomer having a (meth) acryloyl group, and 1 to 10% by weight of a block copolymer composed of a fluorine segment and a non-fluorine segment. %, And the fluorine-based oligomer may be a polymerizable composition containing at least one of a perfluoropolyether-based oligomer and a perfluoroalkyl-based oligomer. According to this aspect, a polymerizable composition capable of forming the polymer layer of the antifouling film according to one aspect of the present invention is realized.

In another embodiment of the present invention, the polymerizable composition may contain 5 to 10% by weight of the fluorine-based oligomer in terms of an active ingredient.

In another embodiment of the present invention, the polymerizable composition may contain 3 to 8% by weight of the block copolymer in terms of an active ingredient.

In another aspect of the present invention, the polymerizable composition may further contain a monofunctional amide monomer.

1: Antifouling film 2: Base material 3: Polymer layer 4: Convex part 5: Mold 6: Polymerizable composition 7: Release agent 10: Fluorine oligomer (R)
20: Block copolymer (S)
21: Fluorine segment 22: Non-fluorine segment P: Pitch of projection H: Height of projection T: Thickness of polymer layer

Claims (9)

A substrate,
A polymer layer having a concave-convex structure on the surface, which is disposed on the surface of the base material and has a plurality of convex portions provided at a pitch equal to or less than the wavelength of visible light, comprising:
The polymer layer is a cured product of the polymerizable composition,
The polymerizable composition contains 2.5 to 12.5% by weight of a fluorine-based oligomer having a (meth) acryloyl group and 1 to 10% by weight of a block copolymer composed of a fluorine segment and a non-fluorine segment in terms of an active ingredient. And
The antifouling film, wherein the fluorine-based oligomer contains at least one of a perfluoropolyether-based oligomer and a perfluoroalkyl-based oligomer. The antifouling film according to claim 1, wherein the polymerizable composition contains 5 to 10% by weight of the fluorine-based oligomer in terms of an active ingredient. The antifouling film according to claim 1, wherein the polymerizable composition contains 3 to 8% by weight of the block copolymer in terms of an active ingredient. The antifouling film according to any one of claims 1 to 3, wherein the polymerizable composition further contains a monofunctional amide monomer. The antifouling film according to claim 1, wherein the thickness of the polymer layer is 5 to 20 μm. The antifouling film according to any one of claims 1 to 5, wherein an average pitch of the plurality of protrusions is 100 to 400 nm. The antifouling film according to any one of claims 1 to 6, wherein the average height of the plurality of protrusions is 50 to 600 nm. The antifouling film according to any one of claims 1 to 7, wherein an average aspect ratio of the plurality of projections is 0.8 to 1.5. In terms of an active ingredient, it contains 2.5 to 12.5% by weight of a fluorine-based oligomer having a (meth) acryloyl group, and 1 to 10% by weight of a block copolymer composed of a fluorine segment and a non-fluorine segment,
The polymerizable composition, wherein the fluorine-based oligomer includes at least one of a perfluoropolyether-based oligomer and a perfluoroalkyl-based oligomer.

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