WO2018151060A1

WO2018151060A1 - Antifouling film

Info

Publication number: WO2018151060A1
Application number: PCT/JP2018/004764
Authority: WO
Inventors: 芝井　康博; 賢厚母; 健一郎中松
Original assignee: シャープ株式会社
Priority date: 2017-02-17
Filing date: 2018-02-13
Publication date: 2018-08-23
Also published as: JPWO2018151060A1; JP6778768B2

Abstract

The present invention provides an antifouling film excellent in each of antifouling properties, abrasion resistance, and adhesion. This antifouling film is provided with a substrate and a polymer layer that is disposed on the surface of the substrate and that has an uneven structure on the surface thereof in which a plurality of protruding parts are provided at a pitch equal to or smaller than the wavelength of visible light, the polymer layer being a cured material of a polymerizable composition, and the polymerizable composition containing, in terms of active ingredients, 25-55 wt% of a polyfunctional acrylate having 3-9 ethylene oxide groups for each functional group, 0.5-10 wt% of a release agent, and 10-60 wt% of 2-(2-vinyloxyethoxy)ethyl acrylate.

Description

Antifouling film

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 (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 2012-52125 A International Publication No. 2007/040159 JP 2012-141355 A

However, in such an optical film, while having excellent antireflection properties, due to the uneven structure on the surface, if dirt such as fingerprints (sebum) adheres, the attached dirt tends to spread, and further, convex It may be difficult to wipe off dirt that has entered between the sections. Further, the adhered dirt was easily visually recognized because its reflectance is 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 wipeability against dirt (for example, fingerprint wiping), that is, excellent antifouling property.

On the other hand, when the present inventors examined, in the polymer layer which comprises the uneven structure of an optical film, by devising the constituent material, in addition to antifouling property, various characteristics also improved. It was found that a conductive film can be realized. Specifically, it has been found that if a release agent is blended as a constituent material of the polymer layer, the antifouling property is enhanced, and if a polyfunctional acrylate is blended, the abrasion resistance is enhanced. Furthermore, it was found that if the crosslink density of the polymer layer is increased and the glass transition temperature is lowered, the abrasion resistance can be remarkably increased.

However, as a result of further investigation by the present inventors, it has been 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 in improving the abrasion resistance. In polyfunctional acrylates, the crosslink density tends to increase as the number of functional groups increases, but at the same time, the molecular weight increases and the viscosity tends to increase, so the compatibility between the polyfunctional acrylate and the release agent is low, and the desired It turned out that antifouling property and abrasion resistance are hard to be obtained. Furthermore, in the structure which uses a mold release agent and polyfunctional acrylate together, it turned out that the adhesiveness of the polymer layer of an antifouling film and a base material is inadequate.

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

This invention is made | formed in view of the said present condition, and it aims at providing the antifouling film excellent in both antifouling property, abrasion resistance, and adhesiveness.

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

That is, according to one embodiment of the present invention, there is provided a base material, and a polymer layer that is provided on the surface of the base material and has a concavo-convex structure provided on the surface with a plurality of convex portions provided at a pitch equal to or less than the wavelength of visible light. An antifouling film provided, wherein the polymer layer is a cured product of the 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 polymer layer may have a thickness of 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.

ADVANTAGE OF THE INVENTION According to this invention, the antifouling film excellent in both antifouling property, abrasion resistance, and adhesiveness can be provided.

It is a cross-sectional schematic diagram which shows the antifouling film of embodiment. FIG. 2 is a schematic plan view showing a polymer layer in FIG. 1. It is a cross-sectional schematic diagram for demonstrating the example of the manufacturing method of the antifouling film of embodiment.

Embodiments will be described below, and the present invention will be described in more detail with reference to the drawings. However, the present invention is not limited to these embodiments. Moreover, each structure of embodiment may be suitably combined in the range which does not deviate from the summary of this invention, and may be changed.

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 with reference to FIGS. 1 and 2. FIG. 1 is a schematic cross-sectional view showing the 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 disposed on the surface of the base material 2.

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

The polymer layer 3 has a concavo-convex structure in which a plurality of convex portions (projections) 4 are provided with a pitch P (distance between vertices of adjacent convex portions 4) P or less of the wavelength (780 nm) of visible light, that is, a moth-eye structure (アイOf the structure) 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 preferably thin from the viewpoint of orienting active ingredients in the release agent described later at a high concentration on the surface of the polymer layer 3 (surface opposite to the substrate 2). 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 indicates the distance from the surface on the base 2 side to the apex of the convex portion 4.

As the shape of the convex portion 4, for example, a shape (bell shape) constituted by a columnar lower portion and a hemispherical upper portion, a cone shape (cone shape, conical shape), or the like that narrows toward the tip ( Taper shape). In FIG. 1, the bottom of the gap between 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 of all adjacent convex portions (P in FIG. 1) in a 1 μm square region of a planar photograph taken with a scanning electron microscope. Points to the value.

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

The average aspect ratio of the plurality of convex portions 4 is preferably 0.8 to 1.5, more preferably 1.0 to 1.3. When the average aspect ratio of the plurality of convex portions 4 is less than 0.8, the occurrence of optical phenomena such as moire and rainbow unevenness cannot be sufficiently prevented, 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 processability of the concavo-convex structure is reduced, sticking occurs, or the transfer condition when forming the concavo-convex structure is deteriorated (described later). The mold 6 may be clogged or wound. The average aspect ratio of the plurality of convex portions 4 refers to the ratio (height / pitch) between 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 regularly (periodically). The arrangement of the protrusions 4 may be periodic, but due to the advantage that unnecessary diffracted light is not generated due to the periodicity, the arrangement of the protrusions 4 is periodic as shown in FIG. 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 indicates ultraviolet rays, visible rays, infrared rays, 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 comprises 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) in terms of active ingredient, and a release agent (hereinafter referred to as component). 0.5-10% by weight) and 2- (2-vinyloxyethoxy) ethyl acrylate (hereinafter also referred to as Component C) 10-60% by weight.

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

The polymerizable composition may contain other components as long as it contains components A to C in the proportions described above.

Components A to C will be described below.

<Component A>
According to Component A, the crosslinking density of the polymer layer 3 is increased, and appropriate hardness (elasticity) is imparted, so that the abrasion resistance is increased. Furthermore, since the interaction with the base material 2 is enhanced by the high polarity of the ethylene oxide group, the adhesion is enhanced. The abrasion resistance is considered to correlate with the crosslinking density and glass transition temperature of the polymer layer 3, and if the crosslinking density is increased and the glass transition temperature is lowered, the abrasion resistance can be remarkably enhanced. For example, if the polymerizable composition contains a polyfunctional acrylate having a propylene oxide group, the glass transition temperature will be higher than when a polyfunctional acrylate having an ethylene oxide group is contained. This is because molecular motion is constrained by the branched —CH ₃ of the propylene oxide group. In addition, the propylene oxide group (the same applies to the hydrocarbon group) has a lower polarity than the ethylene oxide group, and the interaction with the substrate 2 is reduced, so that the adhesion is reduced. Therefore, in this embodiment, an 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.

Component A has 2 or more functional groups. When there are too many functional groups of component A, since molecular weight will increase, compatibility with the component B will fall and the transparency of polymeric composition and the antifouling film 1 may fall. Moreover, adhesiveness may also fall by the cure shrinkage etc. of polymeric composition. From such a viewpoint, the preferable upper limit of the number of functional groups of Component A is 9. Here, the number of functional groups of component A refers to the number of acryloyl groups per molecule.

The number of ethylene oxide groups of component A is 3 to 9, preferably 3 to 7, more preferably 4 to 5, per functional group. 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 (number of ethylene oxide groups per molecule) / (number of acryloyl groups per molecule).

The content of component A in the polymerizable composition is 25 to 55% by weight, preferably 30 to 50% by weight, more preferably 35 to 45% by weight, in terms of active ingredient. When the content of component A in the polymerizable composition is less than 25% by weight in terms of active ingredient, the elasticity of the polymer layer 3 is insufficient (because the hardness becomes too high), resulting in a decrease in abrasion resistance. To do. Moreover, since the interaction with the base material 2 by an ethylene oxide group becomes inadequate, adhesiveness falls. When the content of component A in the polymerizable composition is higher than 55% by weight in terms of active ingredient, the crosslink density of the polymer layer 3 becomes too low, so that the abrasion resistance is lowered. When a polymeric composition contains multiple types of component A, the sum total of the content rate of several component A should just be in the said range in conversion of an active ingredient.

Examples of component A include polyethylene glycol (300) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, ethoxylated pentaerythritol tetraacrylate, and ethoxylated polyglycerin polyacrylate. Known examples of polyethylene glycol (300) diacrylate include “New Frontier (registered trademark) PE-300” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (number of functional groups: 2, number of ethylene oxide groups: 3 per functional group) Etc. Known examples of polyethylene glycol (400) diacrylate include “NK Ester A-400” (number of functional groups: 2, number of ethylene oxide groups: 4.5 per functional group) manufactured by Shin-Nakamura Chemical Co., Ltd. Can be mentioned. Known examples of polyethylene glycol (600) diacrylate include “NK Ester A-600” (number of functional groups: 2, number of ethylene oxide groups: 7 per functional group) manufactured by Shin-Nakamura Chemical Co., Ltd. . Known examples of ethoxylated pentaerythritol tetraacrylate include “NK ester ATM-35E” (number of functional groups: 4, number of ethylene oxide groups: 8.75 per functional group) manufactured by Shin-Nakamura Chemical Co., Ltd. It is done. Known examples of ethoxylated polyglycerin polyacrylate include “NK Economer (registered trademark) A-PG5054E” (number of functional groups: 9, number of ethylene oxide groups: 6 per functional group) manufactured by Shin-Nakamura Chemical Co., Ltd. Is mentioned.

<Component B>
According to Component B, the active component in Component B is oriented on the surface of the polymer layer 3 (the surface on the side opposite to the substrate 2), and the surface free energy of the polymer layer 3 is reduced. Will increase. Furthermore, the slipping property is increased, and as a result, the abrasion resistance is increased.

The content of component B in the polymerizable composition is 0.5 to 10% by weight, preferably 1 to 5% by weight, more preferably 1.5 to 3% by weight, in terms of 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 that is oriented on the surface of polymer layer 3 (surface opposite to substrate 2) Therefore, the antifouling property decreases. Further, the slipperiness is lowered, and as a result, the abrasion resistance is lowered. When the content of component B in the polymerizable composition is higher than 10% by weight in terms of active ingredient, the compatibility with components A and C becomes too low, and the active ingredient in component B is polymer layer 3 Therefore, the antifouling property and the abrasion resistance are deteriorated. Further, along with this, the active ingredient in the component B is likely to be distributed on the base material 2 side of the polymer layer 3, so that the adhesion is lowered. Furthermore, bleeding out easily occurs 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 components B may be within the above range in terms of effective components.

Component B preferably contains a fluorine-containing compound (a compound containing a fluorine atom in the molecule) as an active ingredient. That is, component B preferably contains a fluorine-based mold release agent. Component B includes, in addition to the fluorine-based mold release agent, for example, a silicon-type mold release agent, a phosphate ester-type mold release agent, and the like. Compared with the agent, the antifouling property and abrasion resistance are further increased.

The fluorine-containing compound (the 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 a release agent having a perfluoropolyether group, a release agent having no perfluoropolyether group (for example, a release agent having a perfluoroalkyl group, a silicon release agent, a phosphate ester release agent). As compared with molds and the like, antifouling properties and abrasion resistance are further increased.

Known examples of fluorine-based mold release agents include “Fomblin (registered trademark) MT70” and “Fomblin AD1700” manufactured by Solvay, “Optool (registered trademark) DAC” and “Optool DAC-HP” manufactured by Daikin Industries, Ltd. "Megafac (registered trademark) RS-76-NS" manufactured by DIC, "CHEMINOX (registered trademark) FAAC-4", "CHEMINOX FAAC-6" manufactured by Unimatec.

Known examples of silicone release agents include “BYK (registered trademark) -UV3500”, “BYK-UV3570”, “BYK-UV3575”, “BYK-UV3576” manufactured by Big Chemie Japan, manufactured by Daicel Ornex Corporation. "EBECRYL (registered trademark) 350" and the like.

As a known example of the phosphoric ester release agent, “NIKKOL (registered trademark) TDP-2” manufactured by Nikko Chemicals, Inc., and the like can be given.

<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 is 2, and the number of ethylene oxide groups is 1 per functional group. Component C has a lower molecular weight and a lower glass transition temperature than ordinary monomers (for example, polyfunctional acrylates). Therefore, by blending Component C in the polymerizable composition, the crosslinking density of the polymer layer 3 is increased. And it becomes easy to control the glass transition temperature over a wide range. However, as a result of investigations by the present inventors, the glass transition temperature of the polymer layer 3 is not sufficiently lowered and the abrasion resistance is improved only by blending the usual polyfunctional acrylate and component C into the polymerizable composition. It turned out that an effect was hard to be acquired. On the other hand, in this embodiment, the glass transition temperature is increased while increasing the crosslinking density of the polymer layer 3 by using the component A having a relatively low glass transition temperature among the polyfunctional acrylates and the component C in combination. Since it can be lowered, the abrasion resistance is remarkably increased. On the other hand, since component C has a low viscosity, it has high compatibility with components A and B (particularly component B), and also functions as a compatibilizing agent. In addition, since Component C has a low viscosity, the penetrating power to the base material 2 is high, and the adhesion is remarkably increased by the anchor effect. Therefore, if the components A, B, and C are added to the polymerizable composition as in the present embodiment, the antifouling film 1 not only having excellent abrasion resistance but also excellent antifouling properties and adhesion is realized. can do. In particular, in terms of adhesion, even when a triacetyl cellulose film that has not been subjected to surface treatment (for example, easy adhesion treatment) is used as the substrate 2, a remarkable effect is obtained.

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

Known examples of 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. The monofunctional amide monomer is preferably used as a compatibilizing agent because it has high compatibility with the components A and B as in the case of the component C. Moreover, according to the monofunctional amide monomer, the curing shrinkage of the polymerizable composition is suppressed, and the cohesive force with the substrate 2 is increased, so that the adhesion is further increased. However, when the polymerizable composition contains a monofunctional amide monomer, the crosslinking density of the polymer layer 3 becomes low and the glass transition temperature tends to be high, so that the abrasion resistance tends to be lowered. On the other hand, in this embodiment, by blending component C in the polymerizable composition, the crosslink density of polymer layer 3 is increased while ensuring compatibility with components A and B, and the glass transition temperature is increased. Can be lowered. Therefore, even when the polymerizable composition contains a monofunctional amide monomer, the antifouling film 1 having excellent antifouling properties and adhesion can be realized without impairing the abrasion resistance. Here, the monofunctional amide monomer refers to a monomer having an amide group and one acryloyl group per molecule.

Examples of the monofunctional amide monomer include N, N-dimethylacrylamide, N-acryloylmorpholine, N, N-diethylacrylamide, N- (2-hydroxyethyl) acrylamide, diacetone acrylamide, Nn-butoxymethylacrylamide and the like. Is mentioned. A known example of N, N-dimethylacrylamide is “DMAA (registered trademark)” manufactured by KJ Chemicals. Known examples of N-acryloylmorpholine 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 Nippon Kasei Co., Ltd. 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 reduced, and the compatibility with components A and B is further increased.

The polymerizable composition may further contain a polymerization initiator. Thereby, the sclerosis | hardenability of polymeric composition increases.

As a polymerization initiator, a photoinitiator, a thermal polymerization initiator, etc. are mentioned, for example, Among these, a photoinitiator is preferable. The photopolymerization initiator is active with respect to active energy rays, and is added to initiate a polymerization reaction for polymerizing the monomer.

Examples of the photopolymerization initiator include radical polymerization initiators, anionic polymerization initiators, and cationic polymerization initiators. Examples of such photopolymerization initiators include acetophenones such as p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, 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. Benzoin ethers; benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl 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 (component other than the active ingredient). In this case, the solvent may be contained together with the active ingredient in the components A to C, or may be contained separately from the components A to C.

Examples of the solvent include alcohol (carbon number: 1 to 10: for example, methanol, ethanol, n- or i-propanol, n-, sec-, or t-butanol, benzyl alcohol, octanol, etc.), ketone (carbon number). 3 to 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 (4 to 10 carbon atoms: eg EG monomethyl ether (methyl cellosorb), EG monoethyl ether (ethyl cellosorb)), diethylene glycol Butyl ether (butyl cellosolob), propylene glycol monomethyl ether, etc.), aromatic hydrocarbon (carbon number 6-10: for example, benzene, toluene, xylene, etc.), amide (carbon number 3-10: for example, dimethylformamide, dimethylacetamide, N -Methylpyrrolidone, etc.), halogenated hydrocarbons (C1-2: for example, methylene dichloride, ethylene dichloride, etc.), petroleum solvents (for example, petroleum ether, petroleum naphtha, etc.) and the like.

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

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

The antifouling property of the antifouling film 1 may mean that the dirt adhering to the surface of the polymer layer 3 (the surface opposite to the substrate 2) can be easily removed. It may mean that dirt does not easily adhere to the surface 3 (surface opposite to the substrate 2). Moreover, according to the antifouling film 1, the antifouling property higher than the conventional antifouling film (for example, fluorine-containing film) which has normal surfaces, such as a flat surface, is acquired by the effect by a moth eye structure.

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

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

Examples of a method for applying the polymerizable composition 5 include a method in which the polymerizable composition 5 is applied by a spray method, a gravure method, a slot die method, a bar coating method, or 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 proportions described above. 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 therebetween. As a result, a concavo-convex structure is formed on the surface of the polymerizable composition 5 (the surface opposite to the substrate 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.

Examples of the curing method of the polymerizable composition 5 include a method by irradiation with active energy rays, heating, and the like. Curing of the polymerizable composition 5 is preferably performed by irradiation with active energy rays, and more preferably by irradiation with ultraviolet rays. Irradiation of the active energy ray may be performed from the base material 2 side of the polymerizable composition 5 or from the mold 6 side of the polymerizable composition 5. Moreover, the frequency | count of irradiation of the active energy ray with respect to the polymeric composition 5 may be only once, and multiple times may be sufficient as it. Curing of the polymerizable composition 5 (the above process 3) may be performed at the same timing as the formation of the concavo-convex structure on the polymerizable composition 5 (the above process 2).

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

In this example of the production method, for example, if the substrate 2 is formed into a roll, the above processes 1 to 4 can be performed continuously and efficiently.

With respect to the above processes 1 and 2, in the present production method example, after the polymerizable composition 5 is applied on the surface of the substrate 2, the substrate 2 is placed in the mold 6 with the polymerizable composition 5 sandwiched therebetween. The process of pressing the substrate 2 against the mold 6 with the polymerizable composition 5 sandwiched therebetween after the polymerizable composition 5 is applied on the surface of the mold 6 is shown. It may be.

As the mold 6, for example, one produced by the following method can be used. First, aluminum used as the material of the mold 6 is formed on the surface of the support substrate by sputtering. Next, a female mold (mold 6) having a moth-eye structure can be produced by alternately repeating anodic oxidation and etching on the formed aluminum layer. At this time, the concavo-convex structure of the mold 6 can be changed by adjusting the time for performing anodic oxidation and the time for performing etching.

Examples of the material for the supporting base include glass; metals such as stainless steel and nickel; polypropylene, polymethylpentene, and cyclic olefin-based polymers (typically, norbornene-based resins such as “Zeonor” manufactured by ZEON Corporation. (Registered Trademark) "," Arton (Registered Trademark) "manufactured by JSR Corporation) and the like; polycarbonate resins; polyethylene terephthalate, polyethylene naphthalate, resins such as triacetylcellulose, and the like. Moreover, you may use the base material made from aluminum instead of what formed the aluminum film on the surface of a 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. Thereby, the metal mold 6 can be easily peeled from the polymer layer 3. Further, since the surface free energy of the mold 6 becomes low, when the substrate 2 is pressed against the mold 6 in the process 2, the active ingredient in the component B is changed to the surface of the polymerizable composition 5 (substrate 2). Can be uniformly oriented on the opposite surface). Furthermore, before the polymerizable composition 5 is cured, it is possible to prevent the active ingredient in the component B from leaving the surface of the polymerizable composition 5 (the surface on the side opposite to the substrate 2). 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 on the side opposite to the substrate 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 phosphate ester-based material. Known examples of fluorine-based materials include “OPTOOL DSX” and “OPTOOL 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.

In the examples and comparative examples, the materials used for producing the antifouling film are as follows.

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

<Mold>
What was produced by the following method was used. First, aluminum as a mold material 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 repeating anodization and etching alternately on the formed aluminum layer, a large number of minute holes (the distance between the bottom points of adjacent holes (recesses) is less than the wavelength of visible light) An anodized layer provided with was formed. Specifically, an anodization, etching, anodization, etching, anodization, etching, anodization, etching, and anodization are sequentially performed (anodization: 5 times, etching: 4 times) to form an aluminum layer. A large number of minute holes (concave portions) having a shape (tapered shape) that narrows toward the inside of the substrate were formed. As a result, a mold having an uneven structure was obtained. Anodization was performed using oxalic acid (concentration: 0.03% by weight) under conditions of a liquid temperature of 5 ° C. and an applied voltage of 80V. The time for one anodic oxidation was 25 seconds. Etching was performed using phosphoric acid (concentration: 1 mol / l) at a liquid temperature of 30 ° C. The time for performing one etching was set to 25 minutes. When the mold was observed with a scanning electron microscope, the depth of the recess was 290 nm. In addition, the mold surface was subjected to a mold release treatment in advance 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 amount of each component (unit: parts by weight). Abbreviations for each component are as follows.

(Polyfunctional acrylate)
・ "PE-300"
“New Frontier PE-300” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
Number of functional groups: 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 Co., Ltd.
Number of functional groups: 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 Co., Ltd.
Number of functional groups: 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 Co., Ltd.
Number of functional groups: 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 Co., Ltd.
Number of functional groups: 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 Co., Ltd.
Number of functional groups: 2
Number of ethylene oxide groups: 2 per functional group Active ingredient: 100% by weight
・ "SR499"
"SR499" manufactured by Sartomer
Number of functional groups: 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.
Number of functional groups: 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 Co., Ltd.
Number of functional groups: 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 Co., Ltd.
Number of functional groups: 6
Number of ethylene oxide groups: 0 (not included)
Active ingredient: 100% by weight
・ "U-10"
“U-10HA” manufactured by Shin-Nakamura Chemical Co., Ltd.
Functional group number: 10
Number of ethylene oxide groups: 0 (not included)
Active ingredient: 100% by weight
・ "U-15"
“U-15HA” manufactured by Shin-Nakamura Chemical Co., Ltd.
Number of functional groups: 15
Number of ethylene oxide groups: 0 (not included)
Active ingredient: 100% by weight
・ "APG-100"
“NK Ester APG-100” manufactured by Shin-Nakamura Chemical Co., Ltd.
Number of functional groups: 2
Number of ethylene oxide groups: 0 (not included)
Active ingredient: 100% by weight
・ "A-NOD-N"
“NK Ester A-NOD-N” manufactured by Shin-Nakamura Chemical Co., Ltd.
Number of functional groups: 2
Number of ethylene oxide groups: 0 (not included)
Active ingredient: 100% by weight
・ "SR444"
"SR444" manufactured by Sartomer
Number of functional groups: 3
Number of ethylene oxide groups: 0 (not included)
Active ingredient: 100% by weight

(Release agent)
・ "MT70"
"Fomblin MT70" (fluorine release agent) manufactured by Solvay
Perfluoropolyether group: Active ingredient: 80% by weight (perfluoropolyether derivative)
Solvent: 20% by weight (methyl ethyl ketone)
・ "DAC"
"OPTOOL DAC-HP" (fluorine release agent) manufactured by Daikin Industries
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" (fluorine release agent) manufactured by Unimatec
Perfluoropolyether group: not present (perfluoroalkyl group present)
Active ingredient: 100% by weight
・ "UV3500"
BYK-UV3500 (silicone mold release agent) manufactured by Big Chemie Japan
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" made by IGM Resins
Active ingredient: 100% by weight

What converted the content of components A to C in the polymerizable composition into active ingredients (in the table, “content of component A”, “content of component B”, and “content of component C”) Tables 9 to 16 show.

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

(Process 1)
The polymerizable composition R1 was applied in a band shape on the surface of the substrate 2 (“TAC2”). Then, the polymerizable composition R1 was spread over the entire surface of the substrate 2 using a bar coater. Then, the thing with the polymeric composition R1 apply | coated on the surface of the base material 2 was put into oven, and it heat-processed for 1 minute at the temperature of 80 degreeC, and volatilized the solvent from polymeric composition R1.

(Process 2)
The base material 2 was pressed against the mold 6 with a hand roller with the polymerizable composition R1 (after solvent volatilization) interposed therebetween. As a result, a concavo-convex structure was formed on the surface of the polymerizable composition R1 (the surface opposite to the substrate 2).

(Process 3)
The polymerizable composition R1 having a concavo-convex structure on the surface was cured by irradiation 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 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 specification of the antifouling film 1 was as follows.
Shape of convex portion 4: Average pitch of bell-shaped convex portion 4: 200 nm
Average height of convex part 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 Meiwa Forsys was used, and osmium oxide VIII manufactured by Wako Pure Chemical Industries, Ltd. was formed on the surface of the polymer layer 3 (surface opposite to the substrate 2). (Thickness: 5 nm) was applied.

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

[Evaluation]
The following evaluation was performed about the antifouling film of each example. 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 lx (fluorescent lamp). Judgment criteria were as follows.
○: Transparent or very slightly cloudy.
Δ: Slightly cloudy, but no sediment was observed even after standing for 1 day.
X: Although it became cloudy, the sediment was not seen even after leaving it to stand for 1 day.
XX: Cloudy and sediment was observed after standing for 1 day.
Here, 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 Industries Co., Ltd. Judgment criteria were as follows.
A: Z ≦ 0.5
○: 0.5 <Z ≦ 0.8
Δ: 0.8 <Z <1.0
×: Z ≧ 1.0
Here, when the judgment was ◎, ○, or Δ, it was judged as an acceptable level (the transparency of the antifouling film was excellent).

<Anti-fouling>
As 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 substrate), and the contact angle 10 seconds after the dropping was measured.

(Oil repellency)
Hexadecane was dropped onto the surface of the polymer layer of the antifouling film of each example (the surface opposite to the substrate), and the contact angle 10 seconds after the dropping was measured.

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

(Fingerprint wiping property)
First, the black acrylic board was affixed on the surface on the opposite side to the polymer layer of a base material through the optical adhesion layer with respect to the antifouling film of each example. Then, after attaching a fingerprint to the surface of the polymer layer of the antifouling film of each example (surface opposite to the base material), “Bencot (registered trademark) S-2” manufactured by Asahi Kasei Fibers Co., Ltd. Whether or not the fingerprint was removed by reciprocating rubbing was visually observed in an environment with an illuminance of 100 lx (fluorescent lamp). Judgment criteria were as follows.
○: The fingerprint was completely wiped off, and the remaining wipe was not visible.
Δ: Fingerprints are inconspicuous, but a slight amount of wiping residue was visible when a fluorescent lamp was reflected.
X: The fingerprint was not wiped off at all.
Here, the case where the determination was “◯” or “Δ” was determined to be an acceptable level (excellent fingerprint wiping property).

<Abrasion resistance>
As the abrasion resistance, 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 in a state where a load of 400 g was applied to steel wool “# 0000” manufactured by Nippon Steel Wool. Then, while visually observing in an environment with an illuminance of 100 lx (fluorescent lamp), the number “N” of scratches on the surface of the polymer layer of the antifouling film of each example (surface opposite to the base material) ( Unit: book) was counted. When rubbing with steel wool, a surface property 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 times of rubbing was 10 reciprocations. Judgment criteria were as follows.
A: N = 0
○: N = 1-3
Δ: N = 4-10
×: N = 11 to 20
XX: N ≧ 21
Here, the case where the determination was ◎, ○, or Δ was determined to be an acceptable level (excellent steel wool resistance).

<Adhesion>
First, with respect to the surface of the polymer layer of the antifouling film of each example (the surface opposite to the base material), with a cutter knife, 11 vertical cuts and 11 horizontal cuts were made at 1 mm intervals. 100 square squares (1 mm square) were chopped. Then, a polyester adhesive tape “No. 31B” manufactured by Nitto Denko Corporation was pressure-bonded to the mesh portion, and then the adhesive tape was peeled off at a speed of 100 mm / s in a direction of 90 ° with respect to the surface of the mesh portion. Thereafter, the peeled state of the polymer layer on the substrate was visually observed, and the number “M” (unit: piece) of the cells remaining without peeling the polymer layer on the substrate was counted. Judgment criteria were as follows.
○: M = 100
Δ: M = 95 to 99
×: M = 0 to 94
Here, the case where the determination was ○ or Δ was determined as an acceptable level (excellent adhesion).

As shown in Tables 17 to 20, in Examples 1 to 18, an antifouling film having excellent antifouling properties, abrasion resistance, and adhesion was realized. In particular, in Examples 3 to 18, even when a base material (“TAC1”) that was not subjected to easy adhesion treatment such as primer treatment was used, adhesion was excellent. 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 properties, abrasion resistance and adhesion was not realized.

In Comparative Examples 1 to 10, since Component C was not blended in the polymerizable composition, at least one of antifouling property, abrasion resistance, and adhesion was low. In Comparative Examples 2, 4 to 10, the polymerizable composition contains a monofunctional amide monomer instead of Component C, but has excellent antifouling properties, abrasion resistance, and adhesion. And could not.

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

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

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

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

[Appendix]
One embodiment of the present invention includes a base material, and a polymer layer that is provided on the surface of the base material and includes a polymer layer having a concavo-convex structure on the surface, in which a plurality of convex portions are provided at a pitch equal to or less than the wavelength of visible light. A soiling film, wherein the polymer layer is a cured product of a polymerizable composition, and the polymerizable composition has a polyfunctionality 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 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, an antifouling film having excellent antifouling properties, abrasion resistance, and adhesion can be realized.

The release agent may contain a fluorine-containing compound as an active ingredient. According to such a structure, antifouling property and abrasion resistance are further improved.

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 release agent, a phosphate ester release agent, etc.). Thus, the antifouling property and abrasion resistance are further increased.

The polymerizable composition may further contain a monofunctional amide monomer. According to such a structure, compatibility with the said polyfunctional acrylate and the said mold release agent increases more. Furthermore, the curing shrinkage of the polymerizable composition is suppressed, and the cohesive force with the substrate is increased, so that the adhesion is further increased.

The monofunctional amide monomer may contain N, N-dimethylacrylamide. According to such a configuration, the viscosity of the monofunctional amide monomer is decreased, and the compatibility with the polyfunctional acrylate and the 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. According to such a configuration, the antifouling property is further increased.

The polymer layer may have a thickness of 5.0 to 20.0 μm. According to such a structure, the active ingredient in the said mold release agent orientates with a high density | concentration by the surface (surface on the opposite side to the said base material) of the said polymer layer.

The average pitch of the plurality of convex portions may be 100 to 400 nm. According to such a configuration, 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 achieve both a 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, generation of optical phenomena such as moire and rainbow unevenness is sufficiently prevented, and excellent antireflection properties can be realized. Furthermore, the occurrence of sticking due to a decrease in the workability of the concavo-convex structure and the deterioration of the transfer condition when forming the concavo-convex structure are sufficiently prevented.

1: Antifouling film 2: Substrate 3: Polymer layer 4: Convex part 5: Polymerizable composition 6: Mold P: Convex part pitch H: Convex part height T: Thickness of polymer layer

Claims

A substrate;
An antifouling film provided on the surface of the base material, the polymer layer having a concavo-convex structure provided on the surface with a plurality of convex portions provided at a pitch equal to or less than the wavelength of visible light,
The polymer layer is a cured product of a 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. -An antifouling film characterized by containing 10 to 60% by weight of (2-vinyloxyethoxy) ethyl.
The antifouling film according to claim 1, wherein the release agent contains a fluorine-containing compound as an active ingredient.
The antifouling film according to claim 2, wherein the fluorine-containing compound has a perfluoropolyether group.
The antifouling film according to any one of claims 1 to 3, wherein the polymerizable composition further contains a monofunctional amide monomer.
5. The antifouling film according to claim 4, wherein the monofunctional amide monomer includes N, N-dimethylacrylamide.
The antifouling property according to any one of claims 1 to 5, wherein a contact angle of water is 130 ° or more and a contact angle of hexadecane is 30 ° or more with respect to the surface of the polymer layer. the film.
7. The antifouling film according to claim 1, wherein the polymer layer has a thickness of 5.0 to 20.0 μm.
The antifouling film according to any one of claims 1 to 7, wherein an average pitch of the plurality of convex portions is 100 to 400 nm.
The 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 antifouling film according to any one of claims 1 to 9, wherein an average aspect ratio of the plurality of convex portions is 0.8 to 1.5.