JP6778768B2 - Manufacturing method of antifouling film - Google Patents

Description

The present invention relates to an antifouling film. More specifically, the present invention relates to an antifouling film having a nanometer-sized uneven structure.

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

Japanese Unexamined Patent Publication No. 2012-52125 International Publication No. 2007/040159 Japanese Unexamined Patent Publication No. 2012-141355

However, while such an optical film has excellent antireflection properties, due to the uneven structure of the surface thereof, when stains such as fingerprints (sebum) adhere to the film, the adhered stains easily spread and are further convex. It was sometimes difficult to wipe off the dirt that had entered between the parts. Further, the adhered dirt was easily visually recognized because its reflectance was significantly different from that of the optical film. Therefore, there has been a demand for a functional film (antifouling film) having a nanometer-sized uneven structure on the surface and having excellent wiping property against dirt (for example, fingerprint wiping property), that is, antifouling property.

On the other hand, as a result of studies by the present inventors, in the polymer layer constituting the uneven structure of the optical film, by devising the constituent material, antifouling property is enhanced in addition to antifouling property. It was found that a sex film can be realized. Specifically, it was found that the addition of a release agent as a constituent material of the polymer layer enhances the antifouling property, and the addition of a polyfunctional acrylate enhances the abrasion resistance. Furthermore, it was found that the abrasion resistance can be remarkably improved by increasing the crosslink density of the polymer layer and lowering the glass transition temperature.

However, as a result of further studies by the present inventors, it was found that, according to the polyfunctional acrylate, the crosslink density is increased, but at the same time, the glass transition temperature is likely to be increased, so that there is a limit to the improvement of the abrasion resistance. Further, in the polyfunctional acrylate, the crosslink density tends to increase as the number of functional groups increases, but at the same time, the molecular weight also increases and the viscosity tends to increase, so that the compatibility between the polyfunctional acrylate and the release agent is low, which is desired. It was found that it was difficult to obtain antifouling property and abrasion resistance. Furthermore, it was found that the adhesion between the polymer layer of the antifouling film and the base material was insufficient in the configuration in which the release agent and the polyfunctional acrylate were used in combination.

As described above, the conventional antifouling film has a problem of improving both antifouling property, abrasion resistance, and adhesion. However, no means for solving the above problems has been found. For example, in the inventions described in Patent Documents 1 to 3, antifouling property, abrasion resistance, and adhesion cannot be improved, and there is room for improvement.

The present invention has been made in view of the above situation, and an object of the present invention is to provide an antifouling film having excellent antifouling property, abrasion resistance, and adhesion.

The present inventors have studied various antifouling films having excellent antifouling property, abrasion resistance, and adhesion. As a result, the present inventors have conducted various studies on antifouling films having a predetermined number of ethylene oxide groups as a constituent material of the polymer layer. It has been found that the acrylate, the release agent, and 2- (2-vinyloxyethoxy) ethyl acrylate are blended in a predetermined ratio. As a result, the present invention has been reached with the idea that the above problems can be solved brilliantly.

That is, one aspect of the present invention comprises a base material and a polymer layer having a surface having a concavo-convex structure in which a plurality of convex portions are provided on the surface of the base material at a pitch equal to or lower than the wavelength of visible light. The provided antifouling film, the polymer layer is a cured product of a polymerizable composition, and the polymerizable composition has 3 to 9 ethylene oxide groups per functional group in terms of active ingredients. Even an antifouling film containing 25 to 55% by weight of a polyfunctional acrylate, 0.5 to 10% by weight of a release agent, and 10 to 60% by weight of 2- (2-vinyloxyethoxy) ethyl acrylate. Good.

The release agent may contain a fluorine-containing compound as an active ingredient.

The fluorine-containing compound may have a perfluoropolyether group.

The polymerizable composition may further contain a monofunctional amide monomer.

The monofunctional amide monomer may contain N, N-dimethylacrylamide.

The contact angle of water with respect to the surface of the polymer layer may be 130 ° or more, and the contact angle of hexadecane may be 30 ° or more.

The thickness of the polymer layer may be 5.0 to 20.0 μm.

The average pitch of the plurality of convex portions may be 100 to 400 nm.

The average height of the plurality of convex portions may be 50 to 600 nm.

The average aspect ratio of the plurality of convex portions may be 0.8 to 1.5.

According to the present invention, it is possible to provide an antifouling film having excellent antifouling property, abrasion resistance, and adhesion.

It is sectional drawing which shows the antifouling film of an embodiment. It is a plan schematic diagram which shows the polymer layer in FIG. It is sectional drawing for demonstrating 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, but the present invention is not limited to this embodiment. In addition, each configuration of the embodiment may be appropriately combined or modified without departing from the gist of the present invention.

In the present specification, "XY" means "X or more, Y or less".

[Embodiment]
The antifouling film of the embodiment will be described below with reference to FIGS. 1 and 2. FIG. 1 is a schematic cross-sectional view showing an antifouling film of the embodiment. FIG. 2 is a schematic plan view showing the polymer layer in FIG.

The antifouling film 1 includes a base material 2 and a polymer layer 3 arranged on the surface of the base material 2.

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 base material 2 (the surface on the polymer layer 3 side) may be subjected to an easy-adhesion treatment (for example, a primer treatment), and for example, a triacetyl cellulose film which has been subjected to the easy-adhesion treatment may be used. it can. Further, the surface of the base material 2 (the surface on the polymer layer 3 side) may be saponified, and for example, a saponified triacetyl cellulose film can be used. When the antifouling film 1 is attached to a display device including a polarizing plate such as a liquid crystal display device, the base material 2 may form a part of the polarizing plate.

The thickness of the base material 2 is preferably 50 to 100 μm from the viewpoint of ensuring transparency and processability.

The polymer layer 3 has a concavo-convex structure in which a plurality of convex portions (projections) 4 are provided at a pitch (distance between vertices of adjacent convex portions 4) P of visible light wavelength (780 nm) or less, that is, a moth eye structure (moth). It has a mesh-like structure) on its surface. Therefore, the antifouling film 1 can exhibit excellent antireflection property (low reflectivity) due to the moth-eye structure.

The thickness T of the polymer layer 3 is preferably thin from the viewpoint of orienting the active ingredient in the release agent described later on the surface of the polymer layer 3 (the surface opposite to the base material 2) at a high concentration. Specifically, the thickness T of the polymer layer 3 is preferably 5.0 to 20.0 μm, more preferably 8.0 to 12.0 μm. As shown in FIG. 1, the thickness T of the polymer layer 3 refers to the distance from the surface on the base material 2 side to the apex of the convex portion 4.

The shape of the convex portion 4 is, for example, a shape composed of a columnar lower portion and a hemispherical upper portion (bell shape), a cone shape (cone shape, conical shape), and the like that taper toward the tip (conical shape). (Tapered shape). In FIG. 1, the base of the gap between the adjacent convex portions 4 has an inclined shape, but it may have a horizontal shape without being inclined.

The average pitch of the plurality of convex portions 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 moire and rainbow unevenness. Specifically, the average pitch of the plurality of convex portions 4 is the average of the pitches (P in FIG. 1) of all the adjacent convex portions within a 1 μm square region of the plane photograph taken by the scanning electron microscope. Point to a value.

The average height of the plurality of convex portions 4 is preferably 50 to 600 nm, more preferably 100 to 300 nm, from the viewpoint of making the plurality of convex portions 4 compatible with the preferable average aspect ratio described later. Specifically, the average height of the plurality of convex portions 4 is the average height of 10 consecutive convex portions (H in FIG. 1) in a cross-sectional photograph taken by a scanning electron microscope. Point to a value. However, when selecting the 10 convex portions, the convex portions having defects or deformed parts (such as the parts deformed when preparing the measurement sample) are excluded.

The average aspect ratio of the plurality of convex portions 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 convex portions 4 is less than 0.8, it may not be possible to sufficiently prevent the occurrence of optical phenomena such as moire and rainbow unevenness, and excellent antireflection properties may not be obtained. .. When the average aspect ratio of the plurality of convex portions 4 is larger than 1.5, the workability of the concave-convex structure is lowered, sticking occurs, and the transfer condition when forming the concave-convex structure is deteriorated (described later). The mold 6 may be clogged or wrapped around). The average aspect ratio of the plurality of convex portions 4 refers to the ratio (height / pitch) of the average height and the average pitch of the plurality of convex portions 4 described above.

The convex portions 4 may be arranged randomly or may be arranged regularly (periodically). The arrangement of the convex portions 4 may have periodicity, but as shown in FIG. 2, the arrangement of the convex portions 4 has periodicity due to advantages such as no unnecessary diffracted light due to the periodicity. It is preferable that there is no (random).

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. Here, the active energy ray refers to ultraviolet rays, visible rays, infrared rays, plasma, and 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 contains 25 to 55% by weight of a polyfunctional acrylate having 3 to 9 ethylene oxide groups per functional group (hereinafter, also referred to as component A) and a release agent (hereinafter, component) in terms of active ingredient. It also contains 0.5 to 10% by weight of B) and 10 to 60% by weight of 2- (2-vinyloxyethoxy) ethyl acrylate (hereinafter, also referred to as component C).

The active ingredient of the polymerizable composition (active ingredient of components A to C) refers to a component that becomes a constituent component of the polymer layer 3 after curing, and excludes components (for example, solvent) that do not contribute to the curing reaction (polymerization reaction). ..

The polymerizable composition may contain other components as long as it contains the components A to C in the above-mentioned ratios.

The components A to C will be described below.

<Ingredient A>
According to the component A, the crosslink density of the polymer layer 3 is increased, and an appropriate hardness (elasticity) is imparted, so that the abrasion resistance is enhanced. Further, the high polarity of the ethylene oxide group enhances the interaction with the base material 2, so that the adhesion is enhanced. The abrasion resistance is considered to correlate with the cross-linking density of the polymer layer 3 and the glass transition temperature, and if the cross-linking density is increased and the glass transition temperature is lowered, the abrasion resistance can be remarkably improved. For example, if the polymerizable composition contains a polyfunctional acrylate having a propylene oxide group, the glass transition temperature will be higher than in the case where the polymerizable composition contains a polyfunctional acrylate having an ethylene oxide group. This is because the molecular motion is constrained by the branched -CH ₃ of the propylene oxide group. Further, the propylene oxide group (similar to the hydrocarbon group) has a lower polarity than the ethylene oxide group, and the interaction with the base material 2 is lowered, so that the adhesion is lowered. Therefore, in the present embodiment, the ethylene oxide group is selected from the viewpoint of abrasion resistance and adhesion. Here, the polyfunctional acrylate refers to an acrylate having two or more acryloyl groups per molecule.

The number of functional groups of component A is 2 or more. If the number of functional groups of the component A is too large, the molecular weight increases, so that the compatibility with the component B decreases, and the transparency of the polymerizable composition and the antifouling film 1 may decrease. In addition, the adhesion may be lowered due to curing shrinkage of the polymerizable composition. From this point of view, the preferable upper limit of the number of functional groups of the component A is 9. Here, the number of functional groups of the component A refers to the number of acryloyl groups per molecule.

The number of ethylene oxide groups of the component A is 3 to 9 per functional group, preferably 3 to 7, and more preferably 4 to 5. When the number of ethylene oxide groups is less than 3 per functional group, the elasticity of the polymer layer 3 is insufficient (because the hardness becomes too high), so that the abrasion resistance is lowered. When the number of ethylene oxide groups is more than 9 per functional group, the crosslink density of the polymer layer 3 becomes too low, so that the abrasion resistance is lowered. Here, the number of ethylene oxide groups per functional group refers to (the number of ethylene oxide groups per molecule) / (the number of acryloyl groups per molecule).

The content of the component A in the polymerizable composition is 25 to 55% by weight, preferably 30 to 50% by weight, and more preferably 35 to 45% by weight in terms of the active ingredient. When the content of the component A in the polymerizable composition is less than 25% by weight in terms of the active ingredient, the elasticity of the polymer layer 3 is insufficient (because the hardness becomes too high), so that the abrasion resistance is lowered. To do. In addition, the interaction of the ethylene oxide group with the base material 2 becomes insufficient, so that the adhesion is lowered. When the content of the component A in the polymerizable composition is higher than 55% by weight in terms of the active ingredient, the crosslink density of the polymer layer 3 becomes too low, so that the abrasion resistance is lowered. When the polymerizable composition contains a plurality of types of component A, the total content of the plurality of component A may be within the above range in terms of active ingredient.

Examples of the component A include polyethylene glycol (300) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, ethoxylated pentaerythritol tetraacrylate, and ethoxylated polyglycerin polyacrylate. As a known example of polyethylene glycol (300) diacrylate, "New Frontier (registered trademark) PE-300" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. (number of functional groups: 2, number of ethylene oxide groups: 3 per functional group) And so on. Known examples of polyethylene glycol (400) diacrylate include "NK ester A-400" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (number of functional groups: 2, number of ethylene oxide groups: 4.5 per functional group). Can be mentioned. Known examples of polyethylene glycol (600) diacrylate include "NK ester A-600" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (number of functional groups: 2, number of ethylene oxide groups: 7 per functional group) and the like. .. Known examples of ethoxylated pentaerythritol tetraacrylate include "NK ester ATM-35E" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (number of functional groups: 4, number of ethylene oxide groups: 8.75 per functional group). Be done. Known examples of ethoxylated polyglycerin polyacrylate include "NK Economy (registered trademark) A-PG5054E" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (number of functional groups: 9, number of ethylene oxide groups: 6 per functional group) and the like. Can be mentioned.

<Component B>
According to the component B, the active ingredient in the component B is oriented toward the surface of the polymer layer 3 (the surface opposite to the base material 2), and the surface free energy of the polymer layer 3 is lowered, so that the antifouling property is obtained. Will increase. In addition, the slipperiness is increased, and as a result, the abrasion resistance is increased.

The content of the component B in the polymerizable composition is 0.5 to 10% by weight, preferably 1 to 5% by weight, and more preferably 1.5 to 3% by weight in terms of the active ingredient. When the content of component B in the polymerizable composition is less than 0.5% by weight in terms of active ingredient, the amount of active ingredient oriented toward the surface of the polymer layer 3 (the surface opposite to the base material 2). Is too small, so the antifouling property is reduced. In addition, slipperiness is reduced, and as a result, abrasion resistance is reduced. When the content of the component B in the polymerizable composition is higher than 10% by weight in terms of the active ingredient, the compatibility with the components A and C becomes too low, and the active ingredient in the component B is the polymer layer 3. Since it is not uniformly oriented on the surface of the substrate (the surface opposite to the base material 2), the antifouling property and the abrasion resistance are lowered. Further, along with this, the active ingredient in the component B is easily distributed on the base material 2 side of the polymer layer 3, so that the adhesion is lowered. Further, it is easy to bleed out in a high temperature / high humidity environment, and the optical characteristics are deteriorated. When the polymerizable composition contains a plurality of types of component B, the total content of the plurality of component Bs may be within the above range in terms of active ingredient.

The component B preferably contains a fluorine-containing compound (a compound containing a fluorine atom in the molecule) as an active ingredient. That is, the component B preferably contains a fluorine-based release agent. Examples of the component B include a silicon-based mold release agent, a phosphoric acid ester-based mold release agent, and the like in addition to the fluorine-based mold release agent, but according to the fluorine-based mold release agent, other types of mold release agents are used. Compared with the agent, the antifouling property and the abrasion resistance are further enhanced.

The fluorine-containing compound (active ingredient in the fluorine-based mold release agent) may have a perfluoropolyether group or a perfluoroalkyl group, but may have a perfluoropolyether group. preferable. According to the release agent having a perfluoropolyether group, a release agent having no perfluoropolyether group (for example, a release agent having a perfluoroalkyl group, a silicon-based release agent, a phosphate ester-based release agent) Antifouling property and rubbing resistance are further enhanced as compared with mold release material).

Known examples of fluorine-based release agents include Solvay's "Fonbrin (registered trademark) MT70" and "Fonbrin AD1700", Daikin Industries, Ltd. "Optur (registered trademark) DAC", and "Optur DAC-HP". , "Mega Fuck (registered trademark) RS-76-NS" manufactured by DIC, "CHEMINOX (registered trademark) FAAC-4" manufactured by Unimatec, "CHEMINOX FAAC-6" and the like.

Known examples of silicon-based mold release agents include "BYK (registered trademark) -UV3500", "BYK-UV3570", "BYK-UV3575", "BYK-UV3576", manufactured by Big Chemie Japan, and Daicel Ornex. "EBECRYL (registered trademark) 350" and the like can be mentioned.

Known examples of the phosphoric acid ester-based release agent include "NIKKOL (registered trademark) TDP-2" manufactured by Nikko Chemicals Co., Ltd.

<Component C>
Component C is a heterogeneous polymerizable monomer in which a vinyl ether group and an acryloyl group coexist in the molecule, the number of functional groups thereof is 2, and the number of ethylene oxide groups is 1 per functional group. Since the component C has a smaller molecular weight and a lower glass transition temperature than a normal monomer (for example, a polyfunctional acrylate), the crosslink density of the polymer layer 3 is increased by adding the component C to the polymerizable composition. And it becomes easy to control the glass transition temperature in a wide range. However, as examined by the present inventors, the glass transition temperature of the polymer layer 3 is not sufficiently lowered and the abrasion resistance is enhanced only by adding a normal polyfunctional acrylate and the component C to the polymerizable composition. It turned out that the effect was difficult to obtain. On the other hand, in the present embodiment, the glass transition temperature is increased while increasing the crosslink density of the polymer layer 3 by using the component A and the component C, which have a relatively low glass transition temperature among the polyfunctional acrylates. Since it can be lowered, the abrasion resistance is remarkably increased. On the other hand, since the component C has a low viscosity, it has high compatibility with the components A and B (particularly, the component B), and also functions as a compatibilizer. Further, since the component C has a low viscosity, it has a high penetrating power into the base material 2, and the adhesion is remarkably enhanced by the anchor effect. Therefore, if the components A, B, and C are blended in the polymerizable composition as in the present embodiment, an antifouling film 1 having remarkably excellent antifouling property and adhesion as well as scratch resistance is realized. can do. In particular, in terms of adhesion, a remarkable effect can be obtained even when a triacetyl cellulose film that has not been subjected to surface treatment (for example, easy adhesion treatment) is used as the base material 2.

The content of the component C in the polymerizable composition is 10 to 60% by weight, preferably 15 to 55% by weight, and more preferably 20 to 50% by weight in terms of the active ingredient. When the content of the component C in the polymerizable composition is less than 10% by weight in terms of the active ingredient, the compatibility with the components A and B (particularly, the component B) becomes too low, and the effective component B is effective. Since the components are not uniformly oriented on the surface of the polymer layer 3 (the surface opposite to the base material 2), the antifouling property and the abrasion resistance are lowered. Further, the component B is easily insolubilized and the polymer layer 3 becomes cloudy, so that the haze of the polymer layer 3 increases and the transparency decreases. When the content of the component C in the polymerizable composition is higher than 60% by weight in terms of the active ingredient, the content of the component A in the polymerizable composition is relatively low, so that the abrasion resistance is lowered.

Known examples of the component C include "VEEA" (molecular weight: 186, glass transition temperature: 39 ° C., viscosity: 3.65 cP) manufactured by Nippon Shokubai Co., Ltd.

The polymerizable composition may further contain a monofunctional amide monomer. Like component C, the monofunctional amide monomer has high compatibility with components A and B, and is therefore preferably used as a compatibilizer. Further, according to the monofunctional amide monomer, the curing shrinkage of the polymerizable composition is suppressed, and the cohesive force with the base material 2 is enhanced, so that the adhesion is further enhanced. However, when the polymerizable composition contains a monofunctional amide monomer, the crosslink density of the polymer layer 3 is low and the glass transition temperature is likely to be high, so that the abrasion resistance is likely to be low. On the other hand, in the present embodiment, by blending the component C with the polymerizable composition, the crosslink density of the polymer layer 3 is increased and the glass transition temperature is raised while ensuring compatibility with the components A and B. Can be lowered. Therefore, even when the polymerizable composition contains a monofunctional amide monomer, the antifouling film 1 having excellent antifouling property and adhesiveness can be realized without impairing the abrasion resistance. Here, the monofunctional amide monomer refers to a monomer having an amide group and having one acryloyl group per molecule.

Examples of the monofunctional amide monomer include N, N-dimethylacrylamide, N-acryloylmorpholine, N, N-diethylacrylamide, N- (2-hydroxyethyl) acrylamide, diacetoneacrylamide, Nn-butoxymethylacrylamide and the like. Can be mentioned. Known examples of N, N-dimethylacrylamide include "DMAA (registered trademark)" manufactured by KJ Chemicals. Known examples of N-acryloyl morpholine include "ACMO (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 Nihon Kasei Corporation. Known examples of Nn-butoxymethylacrylamide include "NBMA" manufactured by MRC Unitech.

When the polymerizable composition contains a monofunctional amide monomer, the monofunctional amide monomer preferably contains N, N-dimethylacrylamide. According to such a configuration, the viscosity of the monofunctional amide monomer is lowered, and the compatibility with the components A and B is further enhanced.

The polymerizable composition may further contain a polymerization initiator. This enhances the curability of the polymerizable composition.

Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, and among them, the photopolymerization initiator is preferable. The photopolymerization initiator is active with respect to active energy rays and is added to initiate a polymerization reaction for polymerizing a monomer.

Examples of the photopolymerization initiator include radical polymerization initiators, anionic polymerization initiators, cationic polymerization initiators and the like. 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, 2-isopropylthioxanthone; benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. Benzoyl ethers; benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide Acylphosphine oxides such as; alkylphenylones such as 1-hydroxy-cyclohexyl-phenyl-ketone, etc., 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 (a component other than the active ingredient). In this case, the solvent may be contained in the components A to C together with the active ingredient, or may be contained separately from the components A to C.

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.) and ketones (carbon atoms). 3-8: For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, dibutyl ketone, cyclohexanone, etc.), ester or ether ester (carbon number 4 to 10:, for example, ethyl acetate, butyl acetate, ethyl lactate, etc.), γ- Butyrolactone, ethylene glycol monomethyl acetate, propylene glycol monomethyl acetate, ether (carbon number 4-10: for example, EG monomethyl ether (methyl cellosolve), EG monoethyl ether (ethyl cellosolve), diethylene glycol monobutyl ether (butyl cellosolve), propylene glycol monomethyl ether, etc.) , Aromatic hydrocarbons (6 to 10 carbon atoms: for example, benzene, toluene, xylene, etc.), amides (3 to 10 carbon atoms: for example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.), halogenated hydrocarbons (, for example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.) Carbon number 1-2: For example, methylene dichloride, ethylene dichloride, etc.), petroleum-based solvent (for example, petroleum ether, petroleum naphtha, etc.) and the like can be mentioned.

From the viewpoint of antifouling property, the contact angle of water with respect to the surface of the polymer layer 3 (the surface opposite to the base material 2) is 130 ° or more, and the contact angle of hexadecane is 30 ° or more. Is preferable.

The use of the antifouling film 1 is not particularly limited as long as it utilizes its excellent antifouling property, and may be used for an optical film such as an antireflection film. By attaching such an antireflection film to the inside or the outside of the display device, it contributes to the improvement of visibility.

Antifouling property The antifouling property of the film 1 may mean that the dirt adhering to the surface of the polymer layer 3 (the surface opposite to the base material 2) can be easily removed, and the polymer layer may be used. It may mean that dirt does not easily adhere to the surface of 3 (the surface opposite to the base material 2). Further, according to the antifouling film 1, due to the effect of the moth-eye structure, higher antifouling property can be obtained as compared with the conventional antifouling film (for example, a fluorine-containing film) having a normal surface such as a flat surface.

The antifouling film 1 is manufactured by, for example, the following manufacturing method. FIG. 3 is a schematic cross-sectional view for explaining an example of a method for producing an antifouling film according to an embodiment.

(Process 1)
As shown in FIG. 3A, the polymerizable composition 5 is applied onto the surface of the base material 2.

Examples of the coating method of the polymerizable composition 5 include a spray method, a gravure method, a slot die method, a bar coating method, and the like. As a coating method of the polymerizable composition 5, a method of coating by a gravure method or a slot die method is preferable from the viewpoint of making the film thickness uniform and improving the productivity.

The polymerizable composition 5 contains at least the components A to C in the above-mentioned proportions. Here, when the polymerizable composition 5 further contains a solvent (a component other than the active ingredient), a heat treatment (drying treatment) for removing the solvent may be performed after the application of the polymerizable composition 5. The heat treatment is preferably performed at a temperature equal to or higher than the boiling point of the solvent.

(Process 2)
As shown in FIG. 3B, the base material 2 is pressed against the mold 6 with the polymerizable composition 5 sandwiched between them. As a result, an uneven structure is formed on the surface of the polymerizable composition 5 (the surface opposite to the base material 2).

(Process 3)
The polymerizable composition 5 having an uneven structure on the surface is cured. As a result, the polymer layer 3 is formed as shown in FIG. 3 (c).

Examples of the curing method of the polymerizable composition 5 include a method of irradiating with active energy rays, heating, and the like. The curing of the polymerizable composition 5 is preferably carried out by irradiation with active energy rays, and more preferably by irradiation with ultraviolet rays. Irradiation of the active energy rays may be performed from the base material 2 side of the polymerizable composition 5, or may be performed from the mold 6 side of the polymerizable composition 5. Further, the number of times of irradiation of the polymerizable composition 5 with the active energy rays may be only once or may be a plurality of times. The curing of the polymerizable composition 5 (process 3 above) may be performed at the same timing as the formation of the uneven structure on the polymerizable composition 5 (process 2 above).

(Process 4)
As shown in FIG. 3D, the mold 6 is peeled from the polymer layer 3. As a result, the antifouling film 1 is completed.

In this production method example, for example, if the base material 2 is rolled, the above processes 1 to 4 can be continuously and efficiently performed.

Regarding the above processes 1 and 2, in the present production method example, after the polymerizable composition 5 is applied on the surface of the base material 2, the base material 2 is placed in the mold 6 with the polymerizable composition 5 sandwiched between them. Although the process of pressing the polymerizable composition 5 against the mold 6 is shown, the process of pressing the base material 2 against the mold 6 with the polymerizable composition 5 sandwiched between the coating composition 5 on the surface of the mold 6 is shown. It may be.

As the mold 6, for example, a mold manufactured by the following method can be used. First, aluminum, which is the material of the mold 6, is formed on the surface of the supporting base material by a sputtering method. Next, a female mold (mold 6) having a moth-eye structure can be produced by alternately repeating anodizing and etching on the formed aluminum layer. At this time, the uneven structure of the mold 6 can be changed by adjusting the time for performing anodization and the time for performing etching.

Examples of the material of the supporting base material include glass; metals such as stainless steel and nickel; polypropylene, polymethylpentene, cyclic olefin-based polymers (typically, norbornene-based resins and the like, "Zeonoa" manufactured by Nippon Zeon Co., Ltd. (Registered trademark) ", JSR's" Arton (registered trademark) ") and other polyolefin resins; polycarbonate resins; polyethylene terephthalates, polyethylene naphthalates, triacetyl cellulose and other resins, and the like. Further, an aluminum base material may be used instead of the aluminum film formed on the surface of the support base material.

Examples of the shape of the mold 6 include a flat plate shape and a roll shape.

The surface of the mold 6 is preferably subjected to a mold release treatment. As a result, the mold 6 can be easily peeled off from the polymer layer 3. Further, since the surface free energy of the mold 6 becomes low, when the base material 2 is pressed against the mold 6 in the above process 2, the active ingredient in the component B is applied to the surface of the polymerizable composition 5 (base material 2). It can be evenly oriented to the surface on the opposite side). Further, it is possible to prevent the active ingredient in the component B from being separated from the surface of the polymerizable composition 5 (the surface opposite to the base material 2) before the polymerizable composition 5 is cured. As a result, in the antifouling film 1, the active ingredient in the component B can be uniformly oriented on the surface of the polymer layer 3 (the surface opposite to the base material 2).

Examples of the material used for the mold release treatment of the mold 6 include a fluorine-based material, a silicon-based material, and a phosphoric acid ester-based material. Known examples of the fluorine-based material include "Optur DSX" and "Optur AES4" manufactured by Daikin Industries, Ltd.

[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.

The materials used to produce the antifouling film in Examples and Comparative Examples are as follows.

<Base material>
Two types of substrates were used. The abbreviations for each base material are as follows.
・ "TAC1"
"TAC-TD80U" manufactured by FUJIFILM Corporation
Thickness: 80 μm
・ "TAC2"
"TAC-TF80UL" manufactured by FUJIFILM (triacetyl cellulose film with primer treatment on the surface)
Thickness: 80 μm

<Mold>
The one prepared by the following method was used. First, aluminum, which is 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, by alternately repeating anodizing and etching on the formed aluminum layer, a large number of minute holes (the distance between the base points of adjacent holes (recesses) is equal to or less than the wavelength of visible light). Formed an anodized layer provided with. Specifically, the aluminum layer is formed by performing anodizing, etching, anodizing, etching, anodizing, etching, anodizing, etching, and anodizing in order (anodizing: 5 times, etching: 4 times). A large number of minute holes (recesses) having a shape (tapered shape) that narrowed toward the inside of the aluminum were formed, and as a result, a mold having an uneven structure was obtained. Anodization was carried out 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 anodizing was 25 seconds. Etching was performed using phosphoric acid (concentration: 1 mol / l) under the condition of 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. The surface of the mold was previously subjected to a mold release treatment by "Optool AES4" manufactured by Daikin Industries, Ltd.

<Polymerizable composition>
Polymerizable compositions R1 to R18 and r1 to r19 having the compositions shown in Tables 1 to 8 were used. The numerical values in Tables 1 to 8 indicate the blending amount (unit: parts by weight) of each component. The abbreviations for each component are as follows.

(Polyfunctional acrylate)
・ "PE-300"
"New Frontier PE-300" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
Cardinal number: 2
Number of ethylene oxide groups: 3 per functional group Active ingredient: 100% by weight
・ "A-400"
"NK Ester A-400" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
Cardinal number: 2
Number of ethylene oxide groups: 4.5 per functional group Active ingredient: 100% by weight
・ "A-600"
"NK Ester A-600" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
Cardinal number: 2
Number of ethylene oxide groups: 7 per functional group Active ingredient: 100% by weight
・ "ATM-35E"
"NK Ester ATM-35E" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
Cardinal number: 4
Number of ethylene oxide groups: 8.75 per functional group Active ingredient: 100% by weight
・ "A-PG5054E"
"NK Economer A-PG5054E" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
Cardinal number: 9
Number of ethylene oxide groups: 6 per functional group Active ingredient: 100% by weight
・ "A-200"
"NK Ester A-200" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
Cardinal number: 2
Number of ethylene oxide groups: 2 per functional group Active ingredient: 100% by weight
・ "SR499"
"SR499" made by Sartmer
Cardinal number: 3
Number of ethylene oxide groups: 2 per functional group Active ingredient: 100% by weight
・ "DPEA-12"
"KAYARAD (registered trademark) DPEA-12" manufactured by Nippon Kayaku Co., Ltd.
Cardinal number: 6
Number of ethylene oxide groups: 2 per functional group Active ingredient: 100% by weight
・ "A-1000"
"NK Ester A-1000" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
Cardinal number: 2
Number of ethylene oxide groups: 11.5 per functional group Active ingredient: 100% by weight
・ "A-DPH"
"NK Ester A-DPH" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
Cardinal number: 6
Number of ethylene oxide groups: 0 (not present)
Active ingredient: 100% by weight
・ "U-10"
"U-10HA" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
Cardinal number: 10
Number of ethylene oxide groups: 0 (not present)
Active ingredient: 100% by weight
・ "U-15"
"U-15HA" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
Cardinal number: 15
Number of ethylene oxide groups: 0 (not present)
Active ingredient: 100% by weight
・ "APG-100"
"NK Ester APG-100" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
Cardinal number: 2
Number of ethylene oxide groups: 0 (not present)
Active ingredient: 100% by weight
・ "A-NOD-N"
"NK Ester A-NOD-N" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
Cardinal number: 2
Number of ethylene oxide groups: 0 (not present)
Active ingredient: 100% by weight
・ "SR444"
"SR444" manufactured by Sartmer
Cardinal number: 3
Number of ethylene oxide groups: 0 (not present)
Active ingredient: 100% by weight

(Release agent)
・ "MT70"
Solvay's "Fonbrin MT70" (fluorine-based release agent)
Perfluoropolyether group: Active ingredient: 80% by weight (perfluoropolyether derivative)
Solvent: 20% by weight (methyl ethyl ketone)
・ "DAC"
"Optur DAC-HP" manufactured by Daikin Industries, Ltd. (fluorine-based release agent)
Perfluoropolyether group: Active ingredient: 20% by weight (perfluoropolyether derivative)
Solvent: 80% by weight (1,1,2,2,3,3,4-heptafluorocyclopentane and propylene glycol monomethyl ether)
・ "FAAC-6"
"CHEMINOX FAAC-6" manufactured by Unimatec (fluorine-based release agent)
Perfluoropolyether group: Not present (has a perfluoroalkyl group)
Active ingredient: 100% by weight
・ "UV3500"
"BYK-UV3500" manufactured by Big Chemie Japan (silicon release agent)
Active ingredient: 100% by weight

(2- (2-Vinyloxyethoxy) ethyl acrylate)
・ "VE"
"VEEA" manufactured by Nippon Shokubai Co., Ltd.
Active ingredient: 100% by weight

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

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

The content of components A to C in the polymerizable composition converted into an active ingredient (in the table, "content rate of component A", "content rate of component B", and "content rate of component C") is used. , Tables 9-16.

(Example 1)
The antifouling film of Example 1 was produced by the method described in the above-mentioned production method example.

(Process 1)
The polymerizable composition R1 was applied in a band shape on the surface of the base material 2 (“TAC2”). Then, using a bar coater, the polymerizable composition R1 was spread over the entire surface of the base material 2. Then, the surface of the base material 2 coated with the polymerizable composition R1 was placed in an oven and heat-treated at a temperature of 80 ° C. for 1 minute to volatilize the solvent from the polymerizable composition R1.

(Process 2)
The base material 2 was pressed against the mold 6 with a hand roller with the polymerizable composition R1 (after the solvent volatilized) sandwiched between them. As a result, an uneven structure was formed on the surface of the polymerizable composition R1 (the surface opposite to the base material 2).

(Process 3)
The polymerizable composition R1 having an uneven structure on its surface was cured by irradiating it with ultraviolet rays (irradiation amount: 1 J / cm ² ) from the base material 2 side. As a result, the polymer layer 3 was formed.

(Process 4)
The mold 6 was peeled off from the polymer layer 3. As a result, the antifouling film 1 was completed. The thickness T of the polymer layer 3 was 9.0 μm.

The surface specifications of the antifouling film 1 were as follows.
Shape of convex portion 4: Average pitch of bell-shaped convex portion 4: 200 nm
Average height of convex portion 4: 200 nm
Average aspect ratio of convex part 4: 1.0

The surface specifications of the antifouling film 1 were evaluated using a scanning electron microscope "S-4700" manufactured by Hitachi High-Technologies Corporation. At the time of evaluation, an osmium coater "Neoc-ST" manufactured by Meiwaforsis Co., Ltd. was used on the surface of the polymer layer 3 (the surface opposite to the base material 2), and osmium oxide VIII manufactured by Wako Pure Chemical Industries, Ltd. (Thickness: 5 nm) was applied.

(Examples 2 to 18 and Comparative Examples 1 to 19)
Antifouling films of each example were produced in the same manner as in Example 1 except that the materials were changed to those shown in Tables 17 to 24.

[Evaluation]
The antifouling film of each example was evaluated as follows. The results are shown in Tables 17-24.

<Transparency>
As the transparency, the transparency of the polymerizable composition and the transparency of the antifouling film were evaluated.

(Transparency of polymerizable composition)
The polymerizable composition (state before heat treatment) used in each example was placed in a transparent test tube, and the state was visually observed in an environment with an illuminance of 100 lp (fluorescent lamp). The judgment criteria were as follows.
◯: It was transparent or slightly cloudy.
Δ: Slightly cloudy, but no sediment was observed even after being left for 1 day.
X: Although it was cloudy, no sediment was observed even after being left for 1 day.
XX: It was cloudy and sediment was observed after being left for 1 day.
Here, it was determined that the higher the transparency of the polymerizable composition, the higher the compatibility of each component (particularly, component B) in the polymerizable composition.

(Transparency of antifouling film)
The haze "Z" (unit:%) of the antifouling film of each example was measured using a haze meter "NDH7000" manufactured by Nippon Denshoku Kogyo Co., Ltd. The judgment criteria were as follows.
⊚: Z ≦ 0.5
◯: 0.5 <Z ≦ 0.8
Δ: 0.8 <Z <1.0
X: Z ≧ 1.0
Here, the case where the judgment is ⊚, ◯, or Δ is judged to be an acceptable level (the transparency of the antifouling film is excellent).

<Anti-fouling property>
As the antifouling property, water repellency, oil repellency, and fingerprint wiping property were evaluated.

(Water repellency)
Water was dropped on the surface of the polymer layer of the antifouling film of each example (the surface opposite to the base material), and the contact angle 10 seconds after the dropping was measured.

(Oil repellency)
Hexadecane was added dropwise to the surface of the polymer layer of the antifouling film of each example (the surface opposite to the base material), and the contact angle 10 seconds after the addition was measured.

As the contact angle, a portable contact angle meter "PCA-1" manufactured by Kyowa Interface Science Co., Ltd. was used, and the θ / 2 method (θ / 2 = arctan (h / r), θ: contact angle, r: droplets. The average value of the contact angles at three points measured by radius (h: height of droplet) was shown. Here, the central portion of the antifouling film of each example is selected as the first measurement point, and the second and third measurement points are separated from the first measurement point by 20 mm or more. In addition, two points that are point-symmetrical to the first measurement point were selected.

(Fingerprint wiping property)
First, a black acrylic plate was attached to the antifouling film of each example on the surface of the base material opposite to the polymer layer via an optical adhesive layer. Then, after attaching fingerprints to the surface of the polymer layer of the antifouling film of each example (the surface opposite to the base material), "Bencot (registered trademark) S-2" manufactured by Asahi Kasei Fibers Co., Ltd. is used for 10 Whether or not the fingerprints could be wiped off by rubbing back and forth was visually observed in an environment with an illuminance of 100 lp (fluorescent lamp). The judgment criteria were as follows.
◯: Fingerprints were completely wiped off, and no unwiped residue was visible.
Δ: Fingerprints were inconspicuous, but when a fluorescent lamp was reflected, a slight amount of wiping residue was visible.
X: Fingerprints could not be wiped off at all.
Here, the case where the judgment is ◯ or Δ is judged to be an acceptable level (excellent fingerprint wiping property).

<Abrasion resistance>
As the abrasion resistance, the steel wool resistance was evaluated.

(Steel wool resistant)
First, the surface of the polymer layer of the antifouling film of each example (the surface opposite to the base material) was rubbed with a load of 400 g applied to steel wool "# 0000" manufactured by Nippon Steel Wool Co., Ltd. Then, while visually observing in an environment with an illuminance of 100 lp (fluorescent lamp), the number of scratches "N" (the surface opposite to the base material) of the polymer layer of the antifouling film of each example was attached. Unit: book) was counted. When rubbing with steel wool, a surface measuring machine "HEIDON-14FW" manufactured by Shinto Kagaku Co., Ltd. was used as a testing machine, the stroke width was 30 mm, the speed was 100 mm / s, and the number of rubbing was 10 reciprocations. The judgment criteria were as follows.
⊚: N = 0
◯: N = 1-3
Δ: N = 4 to 10
X: N = 11 to 20
XX: N ≧ 21
Here, the case where the judgment is ⊚, ◯, or Δ is judged to be an acceptable level (excellent steel wool resistance).

<Adhesion>
First, with a cutter knife, 11 vertical and 11 horizontal cuts are made in a grid pattern on the surface of the polymer layer of the antifouling film of each example (the surface opposite to the base material) at 1 mm intervals. It was put in and 100 square squares (1 mm square) were carved. Then, after the polyester adhesive tape "No. 31B" manufactured by Nitto Denko Corporation was pressure-bonded to the squares, the adhesive tape was peeled off at a speed of 100 mm / s in the direction of 90 ° with respect to the surface of the squares. Then, the peeled state of the polymer layer on the base material was visually observed, and the number of squares "M" (unit: pieces) remaining without peeling off the polymer layer on the base material was counted. The judgment criteria were as follows.
◯: M = 100
Δ: M = 95 to 99
×: M = 0 to 94
Here, the case where the judgment is ◯ or Δ is judged to be an acceptable level (excellent adhesion).

As shown in Tables 17 to 20, in Examples 1 to 18, antifouling films having excellent antifouling property, abrasion resistance, and adhesion were realized. In particular, in Examples 3 to 18, the adhesiveness was excellent even when a base material (“TAC1”) that had not been subjected to an easy adhesion treatment such as a primer treatment was used. Further, in Examples 1 to 18, the transparency was also excellent.

On the other hand, as shown in Tables 21 to 24, in Comparative Examples 1 to 19, an antifouling film having excellent antifouling property, abrasion resistance, and adhesion was not realized.

In Comparative Examples 1 to 10, since the component C was not blended in the polymerizable composition, at least one of the antifouling property, the abrasion resistance, and the adhesiveness was low. In Comparative Examples 2, 4 to 10, although the polymerizable composition contains a monofunctional amide monomer instead of the component C, it has excellent antifouling property, abrasion resistance, and adhesion. Could not be.

In Comparative Examples 11 to 15, at least one of the abrasion resistance and the adhesion was low because the component A was not blended in the polymerizable composition. In Comparative Example 11, since the polymerizable composition did not contain the component B, the antifouling property was also low.

In Comparative Examples 16 and 17, the content of the component C in the polymerizable composition was out of the range of 10 to 60% by weight in terms of the active ingredient, so that the abrasion resistance was low.

In Comparative Example 18, since the content of the component B in the polymerizable composition was less than 0.5% by weight in terms of the active ingredient, the antifouling property was low.

In Comparative Example 19, since the content of the component B in the polymerizable composition was higher than 10% by weight in terms of the active ingredient, the abrasion resistance and the adhesiveness were low. Further, since the component B was insolubilized, the transparency was low.

[Additional Notes]
One aspect of the present invention includes a base material and a polymer layer having a surface having a concavo-convex structure in which a plurality of convex portions are provided on the surface of the base material at a pitch equal to or lower than the wavelength of visible light. In the fouling film, the polymer layer is a cured product of the polymerizable composition, and the polymerizable composition is a polyfunctional product having 3 to 9 ethylene oxide groups per functional group in terms of active ingredients. An antifouling film containing 25 to 55% by weight of an acrylate, 0.5 to 10% by weight of a release agent, and 10 to 60% by weight of 2- (2-vinyloxyethoxy) ethyl acrylate may be used. According to this aspect, it is possible to realize an antifouling film having excellent antifouling property, abrasion resistance, and adhesion.

The release agent may contain a fluorine-containing compound as an active ingredient. With such a configuration, antifouling property and abrasion resistance are further enhanced.

The fluorine-containing compound may have a perfluoropolyether group. According to such a configuration, it is compared with a release agent having no perfluoropolyether group (for example, a release agent having a perfluoroalkyl group, a silicon-based release agent, a phosphate ester-based release agent, etc.). As a result, antifouling property and abrasion resistance are further enhanced.

The polymerizable composition may further contain a monofunctional amide monomer. According to such a configuration, the compatibility with the polyfunctional acrylate and the release agent is further enhanced. Further, the curing shrinkage of the polymerizable composition is suppressed, and the cohesive force with the substrate is increased, so that the adhesion is further enhanced.

The monofunctional amide monomer may contain N, N-dimethylacrylamide. According to such a configuration, the viscosity of the monofunctional amide monomer is lowered, and the compatibility with the polyfunctional acrylate and the mold release agent is further increased.

The contact angle of water with respect to the surface of the polymer layer may be 130 ° or more, and the contact angle of hexadecane may be 30 ° or more. With such a configuration, the antifouling property is further enhanced.

The thickness of the polymer layer may be 5.0 to 20.0 μm. According to such a configuration, the active ingredient in the release agent is oriented at a high concentration on the surface of the polymer layer (the surface opposite to the base material).

The average pitch of the plurality of convex portions may be 100 to 400 nm. According to such a configuration, the occurrence of optical phenomena such as moire and rainbow unevenness is sufficiently prevented.

The average height of the plurality of convex portions may be 50 to 600 nm. According to such a configuration, it is possible to make it compatible with the preferable average aspect ratio of the plurality of convex portions.

The average aspect ratio of the plurality of convex portions may be 0.8 to 1.5. According to such a configuration, the occurrence of optical phenomena such as moire and rainbow unevenness can be sufficiently prevented, and excellent antireflection properties can be realized. Further, the occurrence of sticking due to the deterioration of the workability of the uneven structure and the deterioration of the transfer condition when forming the uneven structure are sufficiently prevented.

1: Antifouling film 2: Base material 3: Polymer layer 4: Convex part 5: Polymerizable composition 6: Mold P: Convex part pitch H: Convex part height T: Polymer layer thickness

Claims (10)

With the base material
A method for producing an antifouling film , which comprises a polymer layer arranged on the surface of the base material and having a plurality of convex portions provided on the surface at a pitch equal to or lower than the wavelength of visible light.
The polymer layer is a cured product of the polymerizable composition.
The polymerizable composition contains 25 to 55% by weight of a polyfunctional acrylate having 3 to 9 ethylene oxide groups per functional group, 0.5 to 10% by weight of a release agent, and acrylic acid 2 in terms of active ingredients. A method for producing an antifouling film , which comprises 10 to 60% by weight of − (2-vinyloxyethoxy) ethyl. The method for producing an antifouling film according to claim 1, wherein the release agent contains a fluorine-containing compound as an active ingredient. The method for producing an antifouling film according to claim 2, wherein the fluorine-containing compound has a perfluoropolyether group. The method for producing an antifouling film according to any one of claims 1 to 3, wherein the polymerizable composition further contains a monofunctional amide monomer. The method for producing an antifouling film according to claim 4, wherein the monofunctional amide monomer contains N, N-dimethylacrylamide. The antifouling property according to any one of claims 1 to 5, wherein the contact angle of water with respect to the surface of the polymer layer is 130 ° or more, and the contact angle of hexadecane is 30 ° or more. How to make a film. The method for producing an antifouling film according to any one of claims 1 to 6, wherein the thickness of the polymer layer is 5.0 to 20.0 μm. The method for producing an antifouling film according to any one of claims 1 to 7, wherein the average pitch of the plurality of convex portions is 100 to 400 nm. The method for producing an antifouling film according to any one of claims 1 to 8, wherein the average height of the plurality of convex portions is 50 to 600 nm. The method for producing an antifouling film according to any one of claims 1 to 9, wherein the average aspect ratio of the plurality of convex portions is 0.8 to 1.5.

Images