JP2019195753A - Manufacturing method of antifouling property film - Google Patents

Abstract

To provide a manufacturing method of an antifouling property film for enhancing an antifouling property while restraining reduction in releasability of a polymer layer and a metal mold even if a transfer frequency of the metal mold increases.SOLUTION: A manufacturing method of an antifouling property film includes a process (1) of coating resin on a surface of a base material, a process (2) of coating a fluorine-based solvent on a surface of a metal mold coated with a release treatment agent, a process (3) of forming a resin layer having an uneven structure on the surface by pushing the base material against the surface of the metal mold coated with the fluorine-based solvent in a state of sandwiching the resin in-between and a process (4) of forming the polymer layer by hardening a resin layer, wherein the resin includes a perfluoroalkyl-based monomer, and the perfluoroalkyl-based monomer has an acryloyl group or a methacryloyl group by one per one molecule, and the fluorine atom concentration is 50-60 wt.%, and a boiling point of the fluorine-based solvent is 50°C or more.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for producing an antifouling film.

Various optical films having antireflection properties have been studied (for example, see Patent Documents 1 and 2). 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 2013-39711 A JP 2013-252689 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, when the fluorine-containing monomer was mix | blended as the constituent material in the polymer layer which comprises the uneven structure of an optical film, it turned out that antifouling property increases. Furthermore, if a monofunctional amide monomer is blended, compatibility with the fluorine-containing monomer is increased, and fluorine atoms in the fluorine-containing monomer are likely to be unevenly distributed on the surface of the polymer layer, which is effective in improving antifouling properties. I found out.

However, as a result of further studies by the present inventors, when a mold is used when forming the concavo-convex structure of the polymer layer, if a monofunctional amide monomer is blended as a constituent material of the polymer layer, It has been found that as the number of transfers increases, the releasability of the polymer layer and the mold tends to decrease, and as a result, the antifouling property of the resulting antifouling film tends to decrease.

As described above, conventionally, when producing an antifouling film, even if the number of times of transfer of the mold is increased, the antifouling property is suppressed while suppressing a decrease in the releasability of the polymer layer and the mold. There was a problem of raising. However, no means for solving the above problem has been found. For example, the above Patent Documents 1 and 2 do not describe the decrease in the releasability of the polymer layer and the mold accompanying the increase in the number of times of transfer of the mold, and did not solve the above problem.

The present invention has been made in view of the above situation, and even if the number of times of transfer of the mold is increased, the antifouling property is improved while suppressing the deterioration of the release property of the polymer layer and the mold. It aims at providing the manufacturing method of an adhesive film.

The present inventors have studied various methods for producing an antifouling film that enhances the antifouling property while suppressing a decrease in the releasability of the polymer layer and the mold even when the number of times of transfer of the mold is increased. However, after applying the resin on the surface of the base material and applying a fluorinated solvent on the surface of the mold on which the release agent is applied, the base material is placed in the mold with the resin sandwiched therebetween. Focused on the method of pressing. Then, if a perfluoroalkyl monomer having a predetermined structure is blended in the resin and the boiling point of the fluorinated solvent is set within a predetermined range, even if the number of times of transfer of the mold increases, the polymer layer and the mold It has been found that the antifouling property can be enhanced while suppressing a decrease in releasability. 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 disposed 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. A process for producing an antifouling film comprising: a process (1) for applying a resin on the surface of the substrate; and a process for applying a fluorinated solvent on the surface of a mold to which a release treatment agent is applied (2) and a process of forming a resin layer having the concavo-convex structure on the surface by pressing the substrate against the surface of the mold on which the fluorinated solvent is applied with the resin sandwiched therebetween ( 3) and a process (4) for curing the resin layer to form the polymer layer, wherein the resin contains a perfluoroalkyl monomer, and the perfluoroalkyl monomer is an acryloyl group. Or 1 minute methacryloyl group Having one per and fluorine atom concentration is 50 to 60 wt%, the boiling point of the fluorinated solvent may be a method for producing the antifouling film is 50 ° C. or higher.

According to the present invention, there is provided a method for producing an antifouling film that enhances the antifouling property while suppressing a decrease in release properties of the polymer layer and the die even when the number of times of transfer of the die is increased. Can do.

It is a cross-sectional schematic diagram for demonstrating the manufacturing method of the antifouling film of embodiment. It is a perspective schematic diagram which shows the polymer layer in FIG.1 (e).

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 manufacturing method of the antifouling film of the embodiment will be described below with reference to FIG. FIG. 1 is a schematic cross-sectional view for explaining a method for producing an antifouling film according to an embodiment.

(A) Application of resin (process (1))
As shown in FIG. 1A, the resin 6 is applied on the surface of the substrate 2.

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

When the resin 6 contains a solvent (a component other than the active ingredient), a heat treatment (drying treatment) for removing the solvent may be performed after the resin 6 is applied. This heat treatment is preferably performed at a temperature equal to or higher than the boiling point of the solvent.

(B) Application of fluorinated solvent (process (2))
As shown in FIG. 1B, a fluorine-based solvent 8 is applied on the surface of the mold 5 to which the mold release treatment agent 7 is applied.

Examples of the method for applying the fluorine-based solvent 8 include the same method as the method for applying the resin 6 as described above, potting, and the like.

The application of the resin 6 (above (a)) and the application of the fluorinated solvent 8 (above (b)) may be performed at the same timing or may be performed at different timings.

(C) Formation of resin layer (process (3))
With the resin 6 sandwiched therebetween, the base material 2 is pressed against the surface of the mold 5 on which the fluorine-based solvent 8 is applied. As a result, as shown in FIG. 1C, a resin layer 9 having a concavo-convex structure on the surface (the surface opposite to the substrate 2) is formed.

(D) Formation of polymer layer (process (4))
The resin layer 9 is cured. As a result, a polymer layer 3 is formed as shown in FIG.

Examples of the method for curing the resin layer 9 include a method using irradiation with active energy rays, heating, and the like. In the present specification, “active energy rays” mean ultraviolet rays, visible rays, infrared rays, plasma, and the like. The resin layer 9 is preferably cured 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 resin layer 9 or may be performed from the mold 5 side of the resin layer 9. Moreover, the frequency | count of irradiation of the active energy ray with respect to the resin layer 9 may be only once, and may be multiple times. The curing of the resin layer 9 (above (d)) may be performed at the same timing as the formation of the concavo-convex structure (above (c)).

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

In this embodiment, for example, if the base material 2 is formed into a roll shape, the above (a) to (e) can be performed continuously and efficiently. In the present specification, a series of processes as described in the above (a) to (e) is also referred to as “mold transfer”.

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

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 such that fluorine atoms in a fluorine-containing monomer containing a perfluoroalkyl-based monomer (R) described later are highly concentrated on the surface of the polymer layer 3 (the surface on the side opposite to the substrate 2). From the viewpoint of uneven distribution, it is preferably small. Specifically, the thickness T of the polymer layer 3 is preferably 5 to 20 μm, more preferably 8 to 12 μm.

As the shape of the plurality of convex portions 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 becomes narrower toward the tip. A shape (tapered shape) is mentioned. In FIG. 1 (e), 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 pitch of all adjacent convex portions (P in FIG. 1E) in a 1 μm square region of a planar photograph taken with a scanning electron microscope. ) Means the average value.

The average height of the plurality of convex portions 4 is preferably 50 to 600 nm, and more preferably 100 to 300 nm, from the viewpoint of making it compatible with a preferable average aspect ratio of the plurality of convex portions 4 described later. Specifically, the average height of the plurality of convex portions 4 is the height of ten consecutive convex portions (H in FIG. 1E) in a cross-sectional photograph taken with a scanning electron microscope. ) Means the average value. However, when selecting ten convex portions, the convex portion having a defect or a deformed portion (such as a portion that has been 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 smaller 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 deteriorated, sticking occurs, and the transfer condition when forming the concavo-convex structure is deteriorated (mold) 5 may become 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 plurality of convex portions 4 may be randomly arranged or periodically (regular). When the plurality of convex portions 4 are periodically arranged, unnecessary diffracted light may be generated due to the periodicity. Therefore, the plurality of convex portions 4 are randomly arranged as shown in FIG. It is preferable. FIG. 2 is a schematic perspective view showing the polymer layer in FIG.

From the viewpoint of antifouling properties, the contact angle of water is 110 ° or more and the contact angle of hexadecane is 60 ° 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 is attached to the inside or the outside of the display device, thereby contributing to an improvement in visibility.

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.

Then, each member used when manufacturing the antifouling film 1 is demonstrated below.

<Base material>
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 base material 2 is preferably 50 to 100 μm from the viewpoint of ensuring transparency and workability.

<Resin>
The resin 6 contains a perfluoroalkyl monomer (R). The perfluoroalkyl-based monomer (R) has one acryloyl group or methacryloyl group per molecule and has a fluorine atom concentration of 50 to 60% by weight. In the present specification, the “perfluoroalkyl monomer” means a fluorine-containing monomer having a perfluoroalkyl group. When the perfluoroalkyl monomer (R) is blended with the resin 6, fluorine atoms are unevenly distributed on the surface of the polymer layer 3 (surface opposite to the substrate 2), and the surface free energy of the polymer layer 3. Since it becomes low, antifouling property increases. Further, since the perfluoroalkyl-based monomer (R) has a low molecular weight, it tends to be unevenly distributed (transferred) to the surface of the polymer layer 3 (the surface on the side opposite to the substrate 2), and can be prevented even if the blending amount is small. The antifouling property of the dirty film is likely to increase. Further, since the perfluoroalkyl monomer (R) is highly compatible with the resin 6, it is compared with the case where only the perfluoropolyether monomer is blended as the fluorine-containing monomer instead of the perfluoroalkyl monomer (R). Therefore, the transparency of the antifouling film is likely to increase. From the viewpoint of obtaining such an effect, the perfluoroalkyl-based monomer (R) blended in the resin 6 has only a perfluoroalkyl group as a fluorine-containing portion and contains other fluorine such as a perfluoropolyether group. It is preferable not to have a site.

The perfluoroalkyl monomer (R) has one acryloyl group or methacryloyl group per molecule. In the perfluoroalkyl monomer (R), the acryloyl group or methacryloyl group functions as a polymerizable functional group that reacts with other components by external energy such as light and heat. According to such a perfluoroalkyl-based monomer having no polymerizable functional group, no antifouling property can be obtained for a long time because it does not crosslink in the resin 6. In addition, according to the perfluoroalkyl-based monomer having two or more acryloyl groups or methacryloyl groups per molecule, the molecular weight is increased, so that the compatibility with other components in the resin 6 is decreased. The transparency of the antifouling film 1 (polymer layer 3) decreases (whitens). Furthermore, perfluoroalkyl monomers having two or more acryloyl groups or methacryloyl groups per molecule constitute the main skeleton or branch in the polymer layer 3 and are easily incorporated into the crosslinked structure. Compared to the monomer (R), it is less likely to be unevenly distributed on the surface of the polymer layer 3 (the surface opposite to the substrate 2).

The fluorine atom concentration in the perfluoroalkyl monomer (R) is 50 to 60% by weight. When the fluorine atom concentration in the perfluoroalkyl-based monomer (R) is lower than 50% by weight, the amount of fluorine atoms unevenly distributed on the surface of the polymer layer 3 (the surface opposite to the substrate 2) is reduced. Antifouling property decreases. When the fluorine atom concentration in the perfluoroalkyl monomer (R) is higher than 60% by weight, the polymer layer 3 becomes soft, so that the abrasion resistance is lowered, and the phase with other components in the resin 6 is reduced. Since the solubility is lowered, the transparency of the antifouling film 1 (polymer layer 3) is lowered (whitening).

The content of the perfluoroalkyl monomer (R) in the resin 6 is preferably 0.5 to 5% by weight, more preferably 2 to 4% by weight in terms of active ingredient. When the content of the perfluoroalkyl monomer (R) is lower than 0.5% by weight in terms of active ingredient, the amount of fluorine atoms unevenly distributed on the surface of the polymer layer 3 (surface opposite to the substrate 2) May decrease and the antifouling property may decrease. When the content of the perfluoroalkyl monomer (R) is higher than 5% by weight in terms of the active ingredient, the polymer layer 3 becomes soft and the abrasion resistance may be lowered. When the resin 6 contains a plurality of perfluoroalkyl monomers (R), the total content of the plurality of perfluoroalkyl monomers (R) is preferably within the above range in terms of active ingredients. In this specification, the “active ingredient” refers to a component that becomes a constituent component of the polymer layer 3 after curing, and excludes a component (for example, a solvent) that does not contribute to the curing reaction (polymerization reaction).

Examples of the perfluoroalkyl monomer (R) include 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 2H, 2H-tridecafluorooctyl acrylate, and the like. Can be mentioned.

Known examples of 1H, 1H, 5H-octafluoropentyl acrylate include “Biscoat 8F” manufactured by Osaka Organic Chemical Industry Co., Ltd. Known examples of 1H, 1H, 5H-octafluoropentyl methacrylate include “Biscoat 8FM” manufactured by Osaka Organic Chemical Industry Co., Ltd. Known examples of 1H, 1H, 2H, 2H-tridecafluorooctyl acrylate include “Biscoat 13F” manufactured by Osaka Organic Chemical Industry Co., Ltd.

The resin 6 preferably further contains a perfluoropolyether monomer separately from the perfluoroalkyl monomer (R). In the present specification, the “perfluoropolyether monomer” means a fluorine-containing monomer having a perfluoropolyether group. By using the perfluoropolyether monomer together with the perfluoroalkyl monomer (R), more fluorine atoms are unevenly distributed on the surface of the polymer layer 3 (the surface opposite to the substrate 2), and the antifouling property is improved. Increase more. Further, since the perfluoropolyether monomer is easy to move, the slipperiness of the surface of the polymer layer 3 (the surface opposite to the substrate 2) is likely to increase, and as a result, the rub resistance is likely to increase. From the viewpoint of obtaining such an effect, the perfluoropolyether-based monomer blended in the resin 6 has only a perfluoropolyether group as the fluorine-containing moiety, and other fluorine-containing moieties such as a perfluoroalkyl group. It is preferable not to have it.

From the viewpoint of further improving the antifouling property, the content of the perfluoropolyether monomer in the resin 6 is preferably 0.5 to 3% by weight, more preferably 1 to 2% by weight in terms of active ingredient. When the resin 6 contains a plurality of perfluoropolyether monomers, the total content of the plurality of perfluoropolyether monomers is preferably within the above range in terms of active ingredients.

Known examples of perfluoropolyether monomers include active ingredients (perfluoropolyether derivatives) contained in Solvay's “Fomblin (registered trademark) MT70”, “Fluorolink (registered trademark) AD1700” and the like. It is done.

The resin 6 may further contain a monofunctional amide monomer. In the present specification, the “monofunctional amide monomer” means a monomer having an amide group and one acryloyl group per molecule. When the monofunctional amide monomer is blended with the resin 6, the compatibility with the fluorine-containing monomer including the perfluoroalkyl-based monomer (R) increases, so that the fluorine atom in the fluorine-containing monomer is removed from the surface of the polymer layer 3 ( It becomes easy to be unevenly distributed on the surface opposite to the substrate 2, and the antifouling property is further increased. Moreover, since the curing shrinkage of the resin layer 9 is suppressed and the cohesive force with the base material 2 is increased, the adhesion between the polymer layer 3 and the base material 2 is increased. On the other hand, when a monofunctional amide monomer is blended in the resin 6, when the mold 5 is transferred, the monofunctional amide monomer penetrates into the mold 5 and is compatible with the mold release treatment agent 7. There is a concern that the release agent 7 may be easily peeled off from the mold 5. On the other hand, in this embodiment, due to the effect of the fluorine-based solvent 8 described later, even when the monofunctional amide monomer is blended in the resin 6, the mold release treatment agent by permeation of the monofunctional amide monomer. 7 is prevented from peeling off. Therefore, even if the number of times of transfer of the mold 5 is increased, a decrease in the releasability of the polymer layer 3 and the mold 5 is suppressed, and the antifouling property of the resulting antifouling film 1 is maintained high.

The content of the monofunctional amide monomer in the resin 6 is preferably 1 to 14% by weight, more preferably 1.5 to 10% by weight in terms of active ingredient. When the content of the monofunctional amide monomer is lower than 1% by weight in terms of active ingredient, the adhesion between the polymer layer 3 and the substrate 2 may not be sufficiently increased. When the content of the monofunctional amide monomer is higher than 14% by weight in terms of the active ingredient, the crosslinking density of the polymer layer 3 does not increase, and as a result, the abrasion resistance may decrease. When the resin 6 contains a plurality of types of monofunctional amide monomers, the total content of the plurality of types of monofunctional amide monomers is preferably within the above range in terms of active ingredients.

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

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

The resin 6 may further contain a polyfunctional acrylate. In the present specification, the “polyfunctional acrylate” means an acrylate having two or more acryloyl groups per molecule. When the polyfunctional acrylate is blended in the resin 6, the crosslinking density of the polymer layer 3 is increased, and appropriate elasticity (hardness) is imparted, so that the abrasion resistance is increased.

The number of functional groups of the polyfunctional acrylate is 2 or more, preferably 4 or more, more preferably 6 or more. In the present specification, “the number of functional groups of the polyfunctional acrylate” means the number of acryloyl groups per molecule. If the number of functional groups of the polyfunctional acrylate is too large, the molecular weight increases, so the compatibility with other components in the resin 6 (for example, the perfluoroalkyl-based monomer (R)) decreases, and as a result, The transparency of the dirty film 1 (polymer layer 3) may be reduced (whitened). Moreover, the adhesiveness of the polymer layer 3 and the base material 2 may be lowered due to curing shrinkage or the like of the resin layer 9. From such a viewpoint, the preferable upper limit of the number of functional groups of the polyfunctional acrylate is 10.

The polyfunctional acrylate preferably contains at least one polyfunctional acrylate having an ethylene oxide group. Thereby, since moderate elasticity (hardness) by the polymer layer 3 is provided, the abrasion resistance is further increased.

The content of the polyfunctional acrylate in the resin 6 is preferably 75 to 98% by weight, more preferably 80 to 97.5% by weight in terms of active ingredient. When the content of the polyfunctional acrylate is lower than 75% by weight in terms of active ingredient, the polymer layer 3 becomes hard, and as a result, the abrasion resistance may decrease. When the content of the polyfunctional acrylate is higher than 98% by weight in terms of active ingredients, the crosslinking density of the polymer layer 3 is not increased, and as a result, the abrasion resistance may be lowered. When resin 6 contains multiple types of polyfunctional acrylate, it is preferable that the sum total of the content rate of multiple types of polyfunctional acrylate is in the said range in conversion of an active ingredient.

Examples of the polyfunctional acrylate include polyethylene glycol (200) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, and urethane acrylate.

Known examples of polyethylene glycol (200) diacrylate include “NK Ester A-200” manufactured by Shin-Nakamura Chemical Co., Ltd. Known examples of polyethylene glycol (400) diacrylate include “NK Ester A-400” manufactured by Shin-Nakamura Chemical Co., Ltd. Known examples of polyethylene glycol (600) diacrylate include “NK Ester A-600” manufactured by Shin-Nakamura Chemical Co., Ltd. Known examples of urethane acrylate include “U-10HA” manufactured by Shin-Nakamura Chemical Co., Ltd.

The resin 6 may further contain a polymerization initiator. When the polymerization initiator is blended with the resin 6, the curability of the resin layer 9 is increased.

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 a photopolymerization initiator 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) - acyl phosphine oxide 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 resin 6 may further contain a solvent. In this case, the solvent may be contained together with the active ingredient in each component of the resin 6 or may be contained independently of each component.

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). 3-8: For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, dibutyl ketone, cyclohexanone, etc.), ester or ether ester (carbon number 4-10: eg, ethyl acetate, butyl acetate, ethyl lactate, etc.), γ- Butyrolactone, ethylene glycol monomethyl acetate, propylene glycol monomethyl acetate, ether (carbon number 4 to 10: for example, EG monomethyl ether (methyl cellosorb), EG monoethyl ether (ethyl cellosorb)), diethylene glycol Butyl ether (butyl cellosolob), propylene glycol monomethyl ether, etc., aromatic hydrocarbon (C6-C10: for example, benzene, toluene, xylene, etc.), amide (C3-C10: for example, dimethylformamide, dimethylacetamide, N -Methylpyrrolidone, etc.), halogenated hydrocarbons (C1-C2: for example, methylene dichloride, ethylene dichloride, etc.), petroleum solvents (for example, petroleum ether, petroleum naphtha, etc.), and the like.

The thickness T1 of the resin 6 is preferably 5 to 15 μm, more preferably 7 to 12 μm. When the thickness T1 of the resin 6 is smaller than 5 μm, the amount of fluorine atoms in the polymer layer 3 (resin layer 9) decreases, and the antifouling property may be lowered. When the thickness T1 of the resin 6 is larger than 15 μm, the physical property balance of the polymer layer 3 (resin layer 9) is lost, and as a result, the abrasion resistance may be lowered.

The viscosity of the resin 6 is preferably lower than 30 cP at 25 ° C. When the viscosity of the resin 6 is 30 cP or more, the fluidity of the perfluoroalkyl-based monomer (R) in the resin 6 is lowered, and the fluorine atom is on the surface of the polymer layer 3 (the surface opposite to the substrate 2). It may become difficult to be unevenly distributed.

<Mold>
As the mold 5, for example, one produced by the following method can be used. First, aluminum used as the material of the mold 5 is formed on the surface of the support base by sputtering. Next, a female mold (mold 5) 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 5 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 5 include a flat plate shape and a roll shape.

<Release treatment agent>
The mold release treatment agent 7 is used for the purpose of mold release treatment of the surface of the mold 5. According to the mold release treatment agent 7, the mold releasability (for example, water repellency) of the mold 5 is enhanced, and the mold 5 can be easily peeled from the polymer layer 3. Further, since the surface free energy of the mold 5 becomes low, the fluorine atom in the fluorine-containing monomer containing the perfluoroalkyl monomer (R) when the substrate 2 is pressed against the mold 5 ((c) above). Can be evenly distributed on the surface of the resin layer 9 (the surface opposite to the substrate 2). Furthermore, before the resin layer 9 is cured, it is possible to prevent the fluorine atoms from separating from the surface of the resin layer 9 (the surface opposite to the substrate 2). As a result, in the antifouling film 1, fluorine atoms can be uniformly distributed on the surface of the polymer layer 3 (the surface opposite to the substrate 2).

Examples of the mold release treatment agent 7 include fluorine-based materials, silicon-based materials, and phosphate ester-based materials. As the fluorine-based material, a perfluoropolyether-based material is preferably used, and known examples thereof include “OPTOOL (registered trademark) DSX” and “OPTOOL AES4” manufactured by Daikin Industries, Ltd.

<Fluorine solvent>
The fluorine-based solvent 8 has a boiling point of 50 ° C. or higher, and for the purpose of improving the antifouling property of the antifouling film 1 obtained while preventing the release agent 7 from peeling off due to the transfer of the mold 5. It is used. By applying a fluorinated solvent 8 on the surface of the mold 5 to which the mold release treatment agent 7 is applied (above (b)), the fluorinated solvent 8 is applied to the concavo-convex structure (at least between the convex portions) of the mold 5. In the state which remains, the base material 2 can be pressed against the metal mold | die 5 and the resin layer 9 which has an uneven structure on the surface can be formed (above (c)). Therefore, when the base material 2 is pressed against the mold 5, the resin 6 and the mold release treatment agent 7 are prevented from coming into physicochemical contact, and as a result, the mold release process accompanying the transfer of the mold 5. Peeling of the agent 7 is prevented. Therefore, even if the number of times of transfer of the mold 5 is increased, a decrease in the releasability of the polymer layer 3 and the mold 5 is suppressed, and the antifouling property of the resulting antifouling film 1 is maintained high. Further, when the substrate 2 is pressed against the mold 5, the fluorine-based solvent 8 remains in the uneven structure (at least between the protrusions) of the mold 5. The fluorine-containing monomer containing the fluoroalkyl monomer (R) is likely to be attracted to the surface of the resin layer 9 (the surface opposite to the substrate 2). As a result, in the antifouling film 1, fluorine atoms can be unevenly distributed at a high concentration on the surface of the polymer layer 3 (the surface opposite to the substrate 2).

The boiling point of the fluorinated solvent 8 is 50 ° C. or higher. When the boiling point of the fluorine-based solvent 8 is lower than 50 ° C., the fluorine-based solvent 8 is likely to volatilize, so that the residual amount of the fluorine-based solvent 8 when the substrate 2 is pressed against the mold 5 is reduced, and the above-mentioned The effect of the fluorinated solvent 8 cannot be obtained. On the other hand, if the boiling point of the fluorinated solvent 8 is too high, the residual amount of the fluorinated solvent 8 when the substrate 2 is pressed against the mold 5 is too large (for example, the fluorinated solvent 8 does not volatilize at all). As a result, the transparency of the antifouling film 1 (polymer layer 3) may be reduced (whitened). From such a viewpoint, the preferable upper limit of the boiling point of the fluorinated solvent 8 is 160 ° C.

The thickness T2 of the fluorinated solvent 8 is preferably 0.05 to 1 μm, more preferably 0.1 to 0.6 μm. When the thickness T2 of the fluorinated solvent 8 is smaller than 0.05 μm, the residual amount of the fluorinated solvent 8 when the base material 2 is pressed against the mold 5 is reduced, and the above-described effects of the fluorinated solvent 8 are obtained. It may be difficult to get it. When the thickness T2 of the fluorinated solvent 8 is larger than 1 μm, the residual amount of the fluorinated solvent 8 when the substrate 2 is pressed against the mold 5 increases, and as a result, the antifouling film 1 (polymer layer) 3) Transparency may decrease (whiten).

Known examples of the fluorinated solvent 8 include, for example, “Nevec (registered trademark) 7100”, “Novec7300”, “Fluorinert FC-72”, “Fluorinert FC-770”, and “Fluorinert FC-40” manufactured by 3M Japan. Asahi Glass (registered trademark) AE-3000 manufactured by Asahi Glass Co., 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>
“TAC-TD80U” manufactured by FUJIFILM Corporation was used, and its thickness was 80 μm.

<Resin>
Resins A1 to A9 having compositions (active ingredient amounts) as shown in Tables 1 and 2 were used. Abbreviations for each component are as follows.

(Perfluoroalkyl monomer (R))
・ "V8F"
“Viscoat 8F” manufactured by Osaka Organic Chemical Industry Co., Ltd. (active ingredient: 100% by weight)
Perfluoroalkyl group: perfluoropolyether group: not present acryloyl group or methacryloyl group: present (one acryloyl group per molecule)
Fluorine atom concentration: 53.1% by weight
・ "V8FM"
“Viscoat 8FM” manufactured by Osaka Organic Chemical Industry Co., Ltd. (active ingredient: 100% by weight)
Perfluoroalkyl group: perfluoropolyether group: not present acryloyl group or methacryloyl group: present (one methacryloyl group per molecule)
Fluorine atom concentration: 50.6% by weight
・ "V13F"
“Biscoat 13F” manufactured by Osaka Organic Chemical Industry Co., Ltd. (active ingredient: 100% by weight)
Perfluoroalkyl group: perfluoropolyether group: not present acryloyl group or methacryloyl group: present (one acryloyl group per molecule)
Fluorine atom concentration: 59.1% by weight

(Perfluoroalkyl monomers other than perfluoroalkyl monomers (R))
・ "V3F"
“Viscoat 3F” manufactured by Osaka Organic Chemical Industry Co., Ltd. (active ingredient: 100% by weight)
Perfluoroalkyl group: perfluoropolyether group: not present acryloyl group or methacryloyl group: present (one acryloyl group per molecule)
Fluorine atom concentration: 37% by weight
・ "V4F"
“Viscoat 4F” manufactured by Osaka Organic Chemical Industry Co., Ltd. (active ingredient: 100% by weight)
Perfluoroalkyl group: perfluoropolyether group: not present acryloyl group or methacryloyl group: present (one acryloyl group per molecule)
Fluorine atom concentration: 40.8% by weight
・ "C10A"
“C10ACRY” manufactured by Exfluor (active ingredient: 100% by weight)
Perfluoroalkyl group: perfluoropolyether group: not present acryloyl group or methacryloyl group: present (one acryloyl group per molecule)
Fluorine atom concentration: 65% by weight

(Perfluoropolyether monomer)
・ "MT70"
Perfluoropolyether derivative perfluoroalkyl group in Solvay's “fomblin MT70” (active ingredient: 80% by weight): perfluoropolyether group not present: possessed

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

(Polyfunctional acrylate)
・ "A-200"
“NK Ester A-200” manufactured by Shin-Nakamura Chemical Co., Ltd. (active ingredient: 100% by weight)
Number of functional groups: 2 Number of ethylene oxide groups: 4 per molecule ・ "A-400"
“NK Ester A-400” manufactured by Shin-Nakamura Chemical Co., Ltd. (active ingredient: 100% by weight)
Number of functional groups: 2 Number of ethylene oxide groups: 9 per molecule "A-600"
“NK Ester A-600” manufactured by Shin-Nakamura Chemical Co., Ltd. (active ingredient: 100% by weight)
Number of functional groups: 2 Number of ethylene oxide groups: 14 per molecule "U-10"
“U-10HA” manufactured by Shin-Nakamura Chemical Co., Ltd. (active ingredient: 100% by weight)
Functional group number: 10

(Polymerization initiator)
・ "819"
“IRGACURE 819” manufactured by IGM Resins (active ingredient: 100% by weight)

Tables 3 and 4 show the content of each component in the resins A1 to A9 (in terms of active ingredients).

<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. Thereafter, “OPTOOL AES4” manufactured by Daikin Industries, Ltd. was applied as a mold release treatment agent to the mold surface, and a mold release treatment was performed in advance. Then, oxygen plasma cleaning (output: 100 W) is performed for 20 seconds on the surface of the mold subjected to the release treatment so that the contact angle of water (contact angle immediately after dropping) is 125 to 130 °. It was adjusted. Such adjustment was performed for the purpose of intentionally degrading the mold and aligning the initial mold release property among the examples.

<Fluorine solvent>
Abbreviations of the respective fluorine-based solvents are as follows.
・ "N7100"
“Novec7100” manufactured by 3M Japan
Boiling point: 61 ° C
・ "N7300"
"Novec7300" manufactured by 3M Japan
Boiling point: 98 ° C
・ FC-72
"Florinart FC-72" manufactured by 3M Japan
Boiling point: 56 ° C
・ "FC-770"
“Florinart FC-770” manufactured by 3M Japan
Boiling point: 95 ° C
・ "FC-40"
"Florinart FC-40" manufactured by 3M Japan
Boiling point: 155 ° C
・ "N7000"
"Novec7000" manufactured by 3M Japan
Boiling point: 34 ° C

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

(A) Application of resin Resin A1 was applied on the surface of the substrate. The thickness of the resin A1 was 10 μm.

(B) Application of fluorinated solvent A fluorinated solvent “N7100” was applied onto the surface of the mold on which the release agent was applied. The thickness of the fluorinated solvent was 0.2 μm.

(C) Formation of Resin Layer With the resin A1 sandwiched therebetween, the substrate was pressed against the surface of the mold coated with the fluorinated solvent. As a result, a resin layer having a concavo-convex structure on the surface (surface opposite to the base material) was formed.

(D) Formation of polymer layer The resin layer was cured by irradiation with ultraviolet rays (irradiation amount: 1 J / cm ² ) from the substrate side. As a result, a polymer layer was formed.

(E) Mold release The mold was released from the polymer layer. As a result, an antifouling film was completed. The thickness of the polymer layer was 10 μm.

The surface specification of the antifouling film was as follows.
Convex part shape: average pitch of bell-shaped convex part: 200 nm
Average height of protrusions: 200 nm
Average aspect ratio of protrusions: 1.0

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

Thereafter, the above (a) to (e) (transfer of the mold) were repeated 20 times. Hereinafter, the case where the number of times of transfer of the mold is the first is referred to as “specification 1”, and the case where the number of times of transfer of the mold is the 20th is referred to as “specification 2”. In other words, the antifouling film obtained by the first mold transfer is referred to as “spec 1 antifouling film”, and the antifouling film obtained by the 20th mold transfer is designated “spec 2 antifouling. It is called “reactive film”. The mold after the first transfer is referred to as “spec 1 mold”, and the mold after the 20th transfer is referred to as “spec 2 mold”.

(Examples 2-7 and Comparative Examples 1-5)
An antifouling film of each example was produced in the same manner as in Example 1 except that the conditions were changed to those shown in Tables 5 to 7.

[Evaluation]
The following evaluation was performed about the antifouling film and metal mold | die of each case. The results are shown in Tables 5-7.

<Transparency>
About the antifouling film of the specification 2, haze (unit:%) was measured using the Nippon Denshoku Industries Co., Ltd. haze meter "NDH7000." In addition, it means that transparency is so high that haze is small. Judgment criteria were as follows.
○: “Haze” ≦ 0.5
Δ: 0.5 <“Haze” <1.0
×: “Haze” ≧ 1.0
Here, when the determination was “good”, it was determined that the transparency was excellent.

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

(Water repellency)
About each of the antifouling film of the specifications 1 and 2, water was dripped with respect to the surface (surface on the opposite side to a base material) of a polymer layer, and the contact angle immediately after dripping was measured.

(Oil repellency)
About each of the antifouling film of the specifications 1 and 2, hexadecane was dripped with respect to the surface (surface on the opposite side to a base material) of a polymer layer, and the contact angle immediately after dripping 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, the central part of the antifouling film is selected as the first measurement point, the second and third measurement points are separated from the first measurement point by 20 mm or more, and 1 Two points that are point-symmetric with respect to the second measurement point were selected.

(Fingerprint wiping property)
First, a black acrylic plate was attached to the antifouling film of specification 2 on the surface of the substrate opposite to the polymer layer via an optical adhesive layer. And after making a fingerprint adhere to the surface (surface on the opposite side to a base material) of the polymer layer of the antifouling film of the specification 2, "Bencot (registered trademark) S-2" manufactured by Asahi Kasei Corporation is used. 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, when the determination was ○ or Δ, it was determined that the fingerprint wiping property was excellent.

<Releasability>
As the releasability, the water repellency of the mold was evaluated.

(Water repellency)
First, about each of the metal mold | die of specifications 1 and 2, water was dripped with respect to the surface (surface in which the mold release process was performed), and the contact angle immediately after dripping was measured. And the change rate (unit:%) of the contact angle of water was computed from the contact angle (unit: degree) of the water in the metal mold | die of specifications 1 and 2 based on following formula (X).
“Change rate of contact angle of water” = 100 × (“contact angle of water in mold of specification 1” − “contact angle of water in mold of specification 2”) / “contact of water in mold of specification 1” Corner "(X)
Judgment criteria were as follows.
○: “Change rate of water contact angle” <5
Δ: 5 ≦ “change rate of water contact angle” <10
×: “Change rate of contact angle of water” ≧ 10
Here, when the determination was “◯” or “Δ”, it was determined that the mold releasability (water repellency) was maintained high even if the number of times the mold was transferred was increased.

As shown in Tables 5 and 6, in Examples 1 to 7, even if the number of times of transfer of the mold was increased, the antifouling property was excellent while suppressing a decrease in the release property of the polymer layer and the mold. An antifouling film could be produced.

On the other hand, as shown in Table 7, in Comparative Examples 1 to 5, when the number of times of transfer of the mold is increased, the deterioration of the release property of the polymer layer and the mold is not suppressed, and the antifouling having excellent antifouling property Could not be produced.

In Comparative Example 1, since the fluorine atom concentration of the perfluoroalkyl monomer blended in the resin was lower than 50% by weight and the boiling point of the fluorine solvent was lower than 50 ° C., the number of transfer times of the mold increased. The releasability of the coalesced layer and the mold was lowered, and as a result, the antifouling property of the antifouling film was lowered.

In Comparative Example 2, since the boiling point of the fluorinated solvent was lower than 50 ° C., when the number of times of transfer of the mold increased, the releasability of the polymer layer and the mold decreased, and as a result, the antifouling film Antifouling property decreased.

In Comparative Example 3, the antifouling property of the antifouling film was lowered because the fluorine atom concentration of the perfluoroalkyl monomer mixed in the resin was lower than 50% by weight.

In Comparative Example 4, since only the perfluoropolyether monomer as the fluorine-containing monomer was blended in the resin, it was difficult to increase the antifouling property of the antifouling film. Moreover, since the perfluoropolyether monomer was difficult to be compatible with other components in the resin, the transparency of the antifouling film was lowered as a result.

In Comparative Example 5, since the fluorine atom concentration of the perfluoroalkyl monomer mixed in the resin was higher than 60% by weight, the compatibility with the other components in the resin was lowered, and the antifouling film was whitened.

[Appendix]
One embodiment of the present invention includes a base material, and a polymer layer that is disposed on the surface of the base material and has a concavo-convex structure on the surface where a plurality of convex portions are provided at a pitch equal to or less than the wavelength of visible light. A process for producing a dirty film, which is a process (1) of applying a resin on the surface of the substrate and a process of applying a fluorinated solvent on the surface of a mold to which a release agent is applied (2) And a process of forming a resin layer having the concavo-convex structure on the surface thereof by pressing the base material against the surface of the mold on which the fluorinated solvent is applied, with the resin sandwiched in between (3) And a process (4) for curing the resin layer to form the polymer layer, wherein the resin contains a perfluoroalkyl monomer, and the perfluoroalkyl monomer is an acryloyl group or methacryloyl 1 group per molecule A, and the fluorine atom concentration is 50 to 60 wt%, the boiling point of the fluorinated solvent may be a method for producing the antifouling film is 50 ° C. or higher. According to this aspect, even when the number of times of transfer of the mold is increased, an antifouling film excellent in antifouling property is produced while suppressing a decrease in the release property of the polymer layer and the mold. be able to.

The resin may further contain a perfluoropolyether monomer in addition to the perfluoroalkyl monomer. Thereby, antifouling property increases more.

The resin may further contain a monofunctional amide monomer. As a result, the compatibility with the fluorine-containing monomer including the perfluoroalkyl-based monomer is increased, so that fluorine atoms in the fluorine-containing monomer are unevenly distributed on the surface of the polymer layer (the surface opposite to the substrate). It becomes easy and antifouling property increases more. Moreover, since the curing shrinkage of the resin layer is suppressed and the cohesive force with the base material is increased, the adhesion between the polymer layer and the base material is increased.

The polymer layer may have a thickness of 5 to 20 μm. Thereby, the fluorine atom in the fluorine-containing monomer containing the perfluoroalkyl-based monomer is unevenly distributed at a high concentration on the surface of the polymer layer (the surface on the side opposite to the substrate).

The average pitch of the plurality of convex portions may be 100 to 400 nm. This sufficiently prevents the occurrence of optical phenomena such as moire and rainbow unevenness.

The average height of the plurality of convex portions may be 50 to 600 nm. It can be made compatible with 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. Thereby, the occurrence 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: Base material 3: Polymer layer 4: Convex part 5: Mold 6: Resin 7: Mold release treatment agent 8: Fluorine solvent 9: Resin layer P: Convex part pitch H: Convex part Part height T: Polymer layer thickness T1: Resin thickness T2: Fluorine solvent thickness

Claims (7)

A method for producing an antifouling film comprising: a base material; and a polymer layer disposed on the surface of the base material and having a concavo-convex structure provided on the surface with a plurality of convex portions provided at a pitch equal to or less than a wavelength of visible light. There,
A process (1) of applying a resin on the surface of the substrate;
A process (2) of applying a fluorinated solvent on the surface of the mold to which the release agent is applied;
A process (3) of pressing the base material against the surface of the mold on which the fluorinated solvent is applied in a state of sandwiching the resin, and forming a resin layer having the concavo-convex structure on the surface;
Curing the resin layer and forming the polymer layer (4),
The resin contains a perfluoroalkyl monomer,
The perfluoroalkyl-based monomer has one acryloyl group or methacryloyl group per molecule, and has a fluorine atom concentration of 50 to 60% by weight,
The method for producing an antifouling film, wherein the fluorine-based solvent has a boiling point of 50 ° C. or higher. 2. The method for producing an antifouling film according to claim 1, wherein the resin further contains a perfluoropolyether monomer in addition to the perfluoroalkyl monomer. The method for producing an antifouling film according to claim 1 or 2, wherein the resin further contains a monofunctional amide monomer. The method for producing an antifouling film according to claim 1, wherein the polymer layer has a thickness of 5 to 20 μm. 5. The method for producing an antifouling film according to claim 1, wherein an average pitch of the plurality of convex portions is 100 to 400 nm. 6. The method for producing an antifouling film according to claim 1, wherein an 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 6, wherein an average aspect ratio of the plurality of convex portions is 0.8 to 1.5.

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