JP6550434B2 - Method for producing antifouling film - Google Patents

Description

The present invention relates to a method of producing an antifouling film. More specifically, the present invention relates to a method for producing an antifouling film having a concavo-convex structure of nanometer size.

Various optical films having anti-reflection properties have been studied (see, for example, Patent Documents 1 and 2). In particular, it is known that an optical film having a concavo-convex structure (nanostructure) of nanometer size has excellent antireflective properties. According to such a concavo-convex structure, it is possible to dramatically reduce the reflected light because the refractive index changes continuously from the air layer to the base material.

JP, 2013-39711, A JP, 2013-252689, A

However, such an optical film, while having excellent anti-reflection properties, tends to spread the attached dirt if dirt such as fingerprints (sebum) is attached due to the uneven structure of the surface, and further, it is convex. It was sometimes difficult to wipe off dirt that got in between the parts. Moreover, the attached dirt was easy to be recognized because the reflectance thereof was largely different from the reflectance of the optical film. Therefore, there is a demand for a functional film (antifouling film) having a nanometer-sized uneven structure on the surface and having excellent wiping properties against stains (for example, fingerprint wiping properties), that is, excellent antifouling properties.

On the other hand, when the present inventors examined, in the polymer layer which constitutes the concavo-convex structure of the optical film, it was found that the antifouling property is enhanced if a fluorine-based release agent is blended as the constituent material thereof. . Furthermore, when a monofunctional amide monomer is blended, the compatibility with the fluorine-based release agent is enhanced, and the active component in the fluorine-based release agent is easily oriented on the surface of the polymer layer, so the antifouling property is improved. Was found to be effective.

However, according to the inventors of the present invention, when a mold is used to form the concavo-convex structure of the polymer layer, when a monofunctional amide monomer is blended as a constituent material of the polymer layer, It was found that as the number of transfers increased, the releasability of the polymer layer and the mold tended to decrease, and as a result, the stain resistance of the obtained antifouling film tended to decrease. In addition, it was found that when the blending amount of the monofunctional amide monomer is large, the crosslink density of the polymer layer does not easily increase, and as a result, the abrasion resistance is easily reduced.

As described above, in the conventional production of an antifouling film, the antifouling property and the antifouling property are suppressed while suppressing the decrease in the releasability of the polymer layer and the mold even if the number of times of transfer of the mold increases. There is a problem of improving the abrasion resistance. However, no means has been found to solve the above problems. For example, Patent Documents 1 and 2 described above do not describe the decrease in the releasability of the polymer layer and the mold as the number of times of transfer of the mold increases, and the above problems are not solved.

The present invention was made in view of the above-mentioned present situation, and even if the number of times of transfer of the mold increases, the stain resistance and the abrasion resistance are suppressed while suppressing the decrease in the releasability of the polymer layer and the mold. It is an object of the present invention to provide a method for producing an antifouling film that enhances

The present inventors have produced a method for producing an antifouling film that enhances antifouling property and abrasion resistance while suppressing a decrease in releasability of the polymer layer and the mold even if the number of times of transfer of the mold increases. After various examinations were made on the surface of the mold, the first resin was applied on the surface of the mold, and the second resin was applied on the surface of the base, and then the method of integrating both the resins was focused on. Then, a fluorine-based mold release agent and 2- (2-vinyloxyethoxy) ethyl acrylate instead of a monofunctional amide monomer are blended in the first resin to give acrylic acid 2- (2-vinyloxyethoxy) It was found that the blending amount of ethyl was within the predetermined range. Thus, the present invention has been achieved in consideration of the fact that the above-mentioned problems can be solved in a remarkable manner.

That is, one aspect of the present invention includes a substrate, and a polymer layer having a concavo-convex structure disposed on the surface of the substrate and provided with a plurality of convex portions at a pitch equal to or less than the wavelength of visible light. A method for producing an antifouling film, comprising: a process (1) of applying a first resin on the surface of a mold; and a process (2) of applying a second resin on the surface of the substrate A process (3) of pressing the base material against the mold while sandwiching the first resin and the second resin, thereby forming a resin layer having the uneven structure on the surface; Curing the layer and forming the polymer layer (4), wherein the first resin comprises at least one fluorine-based release agent, 2- (2-vinyloxyethoxy) ethyl acrylate and Containing, and in terms of active ingredient, the above-mentioned acrylic acid 2- (2-vinylo) Shietokishi) ethyl or a process for the preparation of the antifouling film containing 40 to 95 wt%.

The at least one fluorine-based release agent may be a plurality of fluorine-based release agents.

The at least one fluorine-based release agent may contain at least one of a fluorine-based release agent having a perfluoropolyether group and a fluorine-based release agent having a perfluoroalkyl group.

The second resin may contain at least one of the at least one fluorine-based release agent.

The second resin may contain a monofunctional amide monomer.

The surface of the mold may be subjected to a release treatment with a release treatment agent.

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

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

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

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

According to the present invention, even if the number of times of transfer of the mold is increased, the method for producing the antifouling film enhancing the antifouling property and the abrasion resistance while suppressing the decrease in the releasability of the polymer layer and the mold. Can be provided.

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

Hereinafter, the present invention will be described in more detail with reference to the drawings. However, the present invention is not limited to this embodiment. In addition, each configuration of the embodiments may be appropriately combined or changed without departing from the scope of the present invention.

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

[Embodiment]
The method for producing the antifouling film of the embodiment will be described below with reference to FIG. FIG. 1: is a cross-sectional schematic diagram for demonstrating the manufacturing method of the antifouling film of embodiment.

(A) Application of first resin (process (1))
As shown in FIG. 1A, the first resin 6 is applied on the surface of the mold 5.

Examples of the method of applying the first resin 6 include a method of applying using a spray method, a gravure method, a slot die method, a bar coating method, or the like. Among them, 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.

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

(B) Application of second resin (process (2))
As shown in FIG. 1 (b), the second resin 7 is applied onto the surface of the substrate 2.

As a method of applying the second resin 7, for example, the same method as the method of applying the first resin 6 as described above may be mentioned.

When the second resin 7 contains a solvent (component other than the active ingredient), after the application of the second resin 7, heat treatment (drying treatment) may be performed to remove the solvent. The heat treatment is preferably performed at a temperature equal to or higher than the boiling point of the solvent.

The application of the first resin 6 (the above (a)) and the application of the second resin 7 (the above (b)) may be performed at the same timing or may be performed at different timings.

(C) Formation of resin layer (process (3))
The base material 2 is pressed against the mold 5 with the first resin 6 and the second resin 7 interposed therebetween. As a result, the first resin 6 and the second resin 7 are integrated, and as shown in FIG. 1C, the resin layer 8 having a concavo-convex structure on the surface (surface opposite to the base 2) is formed. Be done. In the resin layer 8, the first resin 6 and the second resin 7 are integrated, and the interface between both resins does not exist.

(D) Formation of polymer layer (process (4))
The resin layer 8 is cured. As a result, as shown in FIG. 1D, a polymer layer 3 is formed.

Examples of the method for curing the resin layer 8 include methods by irradiation of active energy rays, heating, and the like. In the present specification, "active energy ray" refers to ultraviolet light, visible light, infrared light, plasma and the like. Curing of the resin layer 8 is preferably performed by irradiation with active energy rays, and more preferably by irradiation with ultraviolet light. The irradiation of the active energy ray may be performed from the side of the base material 2 of the resin layer 8 or may be performed from the side of the mold 5 of the resin layer 8. Further, the number of times of irradiation of the active energy ray to the resin layer 8 may be only once or may be multiple times. The curing of the resin layer 8 (the above (d)) may be performed at the same timing as the formation of the concavo-convex structure (the above (c)).

(E) Peeling of Mold 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 the present embodiment, for example, when the base material 2 is formed into a roll, the above (a) to (e) can be performed continuously and efficiently. In the present specification, a series of processes such as the above (a) to (e) are also referred to as "mold transfer".

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

The polymer layer 3 has a convex-concave structure in which a plurality of convex portions (protrusions) 4 are provided at a pitch (the distance between the apexes of adjacent convex portions 4) P of the visible light wavelength (780 nm) or less. Eye-like structure) on the surface. Therefore, the antifouling film 1 can exhibit the excellent antireflection property (low reflectivity) by the moth-eye structure.

The thickness T of the polymer layer 3 is small from the viewpoint of orienting the active ingredient in the fluorine-based release agent described later on the surface of the polymer layer 3 (the surface opposite to the substrate 2) at a high concentration preferable. 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.

The shape of the plurality of convex portions 4 is, for example, a shape (bell shape) constituted by a columnar lower portion and a hemispherical upper portion, a cone shape (cone shape, cone shape), etc. Shape (taper shape) is mentioned. In FIG. 1 (e), the base of the gap between the adjacent convex portions 4 has an inclined shape, but 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 in a 1 μm square area of the planar photograph taken by the scanning electron microscope (FIG. 1 (e) It refers to the average value of).

The average height of the plurality of projections 4 is preferably 50 to 600 nm, more preferably 100 to 300 nm, from the viewpoint of achieving compatibility with the preferable average aspect ratio of the plurality of projections 4 described later. Specifically, the average heights of the plurality of convex portions 4 are the heights of ten convex portions aligned in a row (FIG. 1 (e)) in a cross-sectional photograph taken with a scanning electron microscope It refers to the average value of). However, when selecting 10 convex parts, the convex part in which there is a missing part or a deformed part (a part which has been deformed when preparing the sample for measurement, etc.) is excluded.

The average aspect ratio of the plurality of projections 4 is preferably 0.8 to 1.5, and more preferably 1.0 to 1.3. When the average aspect ratio of the plurality of convex portions 4 is smaller than 0.8, the occurrence of optical phenomena such as moire and rainbow unevenness can not be sufficiently prevented, and excellent antireflective 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 decreases, sticking occurs, or the transfer condition at the time of forming the concavo-convex structure deteriorates (die 5 may get clogged or rolled around, etc.). The average aspect ratio of the plurality of projections 4 indicates the ratio (height / pitch) of the average height to the average pitch of the plurality of projections 4 described above.

The plurality of convex portions 4 may be arranged randomly or periodically (regularly). 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. Is preferred. FIG. 2 is a schematic perspective view showing the polymer layer in FIG. 1 (e).

From the viewpoint of antifouling property, 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 (the surface opposite to the substrate 2). Is preferred.

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

The antifouling property of the antifouling film 1 may mean that the stain attached to the surface of the polymer layer 3 (the surface on the opposite side to the substrate 2) can be easily removed, and the polymer layer 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 that of a conventional antifouling film (for example, a fluorine-containing film) having a normal surface such as a flat surface can be obtained by the effect of the moth-eye structure.

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

<First resin>
The first resin 6 contains at least one fluorine-based release agent and 2- (2-vinyloxyethoxy) ethyl acrylate, and in terms of active ingredient, 2- (2-vinyloxy acrylate) It contains 40 to 95% by weight of ethoxy) ethyl. In the present specification, the "active ingredient" refers to a component that becomes a constituent component of the polymer layer 3 after curing, excluding components (for example, solvent) that do not contribute to the curing reaction (polymerization reaction).

Each component in the first resin 6 will be described below.

(Fluorinated release agent)
The fluorine-based release agent contains a compound containing a fluorine atom in the molecule (a fluorine-containing compound) as an active ingredient. According to the fluorine-based release agent, the active ingredient in the fluorine-based release agent is oriented on the surface of the polymer layer 3 (the surface opposite to the substrate 2), and the surface free energy of the polymer layer 3 is low. Therefore, the antifouling property is enhanced. Furthermore, the slipperiness of the surface of the polymer layer 3 (the surface opposite to the substrate 2) is enhanced, and as a result, the abrasion resistance is enhanced. In this embodiment, since the first resin 6 mainly constituting the surface of the resin layer 8 (the surface on the opposite side to the base material 2) contains a fluorine-based release agent, it is effective in the fluorine-based release agent The components are easily oriented on the surface of the resin layer 8 (surface opposite to the substrate 2). Therefore, according to the present embodiment, the active ingredient in the fluorine-based release agent is efficiently oriented on the surface of the polymer layer 3 (the surface opposite to the substrate 2), that is, the antifouling property and the resistance Rubbing can be efficiently enhanced.

The first resin 6 may contain one kind of fluorine-based release agent, or may contain plural kinds of fluorine-based release agents, but from the viewpoint of antifouling property, plural kinds of fluorine It is preferable to contain a system release agent. As a result, the active components in the plurality of fluorine-based release agents are oriented at a high concentration on the surface of the polymer layer 3 (the surface on the opposite side to the base material 2), so the antifouling property is further enhanced.

The fluorine-based release agent preferably contains at least one of a fluorine-based release agent having a perfluoropolyether group and a fluorine-based release agent having a perfluoroalkyl group. According to the fluorine-based release agent having a perfluoropolyether group, the active component (fluorine-containing compound) is easily moved, and the slipperiness of the surface of the polymer layer 3 (the surface on the opposite side to the substrate 2) is easily increased. As a result, the abrasion resistance tends to increase. On the other hand, according to the fluorine-based release agent having a perfluoroalkyl group, the molecular weight is small, so that it is easy to align (transfer) to the surface of the polymer layer 3 (the surface on the opposite side to the substrate 2) Even if the amount is less, desired stain resistance and abrasion resistance can be easily obtained. According to such a fluorine-based release agent, compared with other types of release agents (for example, silicone-based release agent, phosphate ester-based release agent, etc.), the antifouling property and the abrasion resistance are improved. More expensive.

The first resin 6 may contain at least one fluorine-based release agent having a perfluoropolyether group, and may contain at least one fluorine-based release agent having a perfluoroalkyl group, At least one of both fluorine-based release agents may be contained.

The content of the fluorine-based release agent in the first resin 6 is preferably 5 to 50% by weight, more preferably 20 to 40% by weight, in terms of the active ingredient. When the content of the fluorine-based release agent in the first resin 6 is lower than 5% by weight in terms of the active ingredient, an active ingredient that is oriented on the surface of the polymer layer 3 (the surface opposite to the substrate 2) May reduce the antifouling properties. When the content of the fluorine-based release agent in the first resin 6 is higher than 50% by weight in terms of the active ingredient, the polymer layer 3 may be soft and the abrasion resistance may be reduced. When the first resin 6 contains a plurality of types of fluorine-based release agents, it is preferable (more preferable) that the total content of the plurality of types of fluorine-based release agents be in the above range in terms of active ingredient.

Well-known examples of the fluorine-based mold release agent include "Foblin (registered trademark) MT70" manufactured by Solvay, "Fluorolink (registered trademark) AD1700", "Optool (registered trademark) DAC" manufactured by Daikin Industries, Ltd., " Optool DAC-HP, "Megafuck (registered trademark) RS-76-NS" manufactured by DIC Corporation, "CHEMINOX (registered trademark) FAAC-4" manufactured by Unimatec, "CHEMINOX FAAC-6" and the like.

(Acrylic acid 2- (2-vinyloxyethoxy) ethyl)
2- (2-vinyloxyethoxy) ethyl acrylate is a heteropolymerizable monomer in which a vinyl ether group and an acryloyl group coexist in the molecule. According to 2- (2-vinyloxyethoxy) ethyl acrylate, the compatibility with the fluorine-based release agent is enhanced due to the low viscosity, and as a result, the active component in the fluorine-based release agent becomes the polymer layer Since it becomes easy to orientate on the surface of 3, antifouling property and abrasion resistance increase. In addition, according to acrylic acid 2- (2-vinyloxyethoxy) ethyl, the compatibility between the first resin 6 and the second resin 7 is enhanced, and the adhesion between both resins is enhanced.

In this embodiment, since the first resin 6 coated on the surface of the mold 5 contains 2- (2-vinyloxyethoxy) ethyl acrylate instead of the monofunctional amide monomer, the mold Even if the number of transfer times of 5 increases, the decrease in the releasability of the polymer layer 3 and the mold 5 is suppressed. As a result, the stain resistance of the obtained stain resistant film 1 is maintained high. On the other hand, when the first resin 6 does not contain 2- (2-vinyloxyethoxy) ethyl acrylate and the other monomer (for example, a multifunctional acrylate), the polymer layer has low reactivity. The crosslinking density of 3 does not increase, and as a result, the abrasion resistance is reduced.

The content of 2- (2-vinyloxyethoxy) ethyl acrylate in the first resin 6 is 40 to 95% by weight, preferably 40 to 80% by weight, more preferably 60 to 50% by weight in terms of active ingredient. It is 80% by weight. When the content of 2- (2-vinyloxyethoxy) ethyl acrylate in the first resin 6 is lower than 40% by weight in terms of the active ingredient, the content of the fluorine-based release agent is relatively increased, and the weight is heavy Since the combined layer 3 becomes too soft, the abrasion resistance is reduced. When the content of 2- (2-vinyloxyethoxy) ethyl acrylate in the first resin 6 is higher than 95% by weight in terms of the active ingredient, the content of the fluorine-based release agent relatively decreases, Since the amount of the active ingredient to be oriented to the surface of the polymer layer 3 (the surface opposite to the substrate 2) is too small, the antifouling property is lowered.

Examples of publicly known 2- (2-vinyloxyethoxy) ethyl acrylate include "VEEA" manufactured by Nippon Shokubai Co., Ltd., and the like.

The first resin 6 preferably contains no monofunctional amide monomer. In the present specification, "monofunctional amide monomer" refers to a monomer having an amide group and one acryloyl group per molecule. When the monofunctional amide monomer is blended in the first resin 6 applied on the surface of the mold 5, the mold 5 is transferred (the mold 5 and the first resin 6 (resin layer 8) When contacting, the monofunctional amide monomer may penetrate the surface of the mold 5. Here, for example, in the case where the surface of the mold 5 has been subjected to a mold release treatment with a mold release treatment agent in advance, the impregnated monofunctional amide monomer is compatible with the mold release treatment agent. The release treatment agent is easily peeled off. Therefore, as the number of times of transfer of the mold 5 increases, the releasability of the polymer layer 3 and the mold 5 tends to decrease, and as a result, the antifouling property of the obtained antifouling film 1 decreases. It will be easier.

On the other hand, in the present embodiment, as described above, 2- (2-vinyloxyethoxy) ethyl acrylate is a monofunctional amide monomer in the first resin 6 applied on the surface of the mold 5. Since it is compounded instead, even if the number of times of transfer of the mold 5 increases, the decrease in the releasability of the polymer layer 3 and the mold 5 is suppressed. As a result, the stain resistance of the obtained stain resistant film 1 is maintained high.

The first resin 6 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 each component (for example, a fluorine-based release agent), or may be contained independently of each component.

As the solvent, for example, alcohol (C1-C10: 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 (C4-10 carbon atoms: eg ethyl acetate, butyl acetate, ethyl lactate etc.), γ- Butyrolactone, ethylene glycol monomethyl acetate, propylene glycol monomethyl acetate, ether (with 4 to 10 carbon atoms: eg EG monomethyl ether (methyl cello lob), EG mono ethyl ether (ethyl cello lob), diethylene glycol mo Butyl ether (Butyl cellophorb), Propylene glycol monomethyl ether, etc.), Aromatic hydrocarbon (C 6-10, eg, benzene, toluene, xylene etc.), Amide (C 3-10, eg: Dimethylformamide, dimethylacetamide, N -Methyl pyrrolidone and the like), halogenated hydrocarbons (C1 to C2: for example, methylene dichloride, ethylene dichloride and the like), petroleum solvents (for example, petroleum ether, petroleum naphtha and the like) and the like.

The thickness T1 of the first resin 6 is preferably 0.5 to 3 μm, more preferably 1 to 2 μm. When the thickness T1 of the first resin 6 is smaller than 0.5 μm, the amount of the active ingredient in the fluorine-based release agent present in the polymer layer 3 (the resin layer 8) decreases, and the antifouling property decreases. There is something to do. If the thickness T1 of the first resin 6 is larger than 3 μm, the physical property balance of the polymer layer 3 (resin layer 8) may be lost, and as a result, the abrasion resistance may be reduced.

The viscosity of the first resin 6 is preferably less than 30 cP, more preferably less than 20 cP, at 25 ° C. When the viscosity of the first resin 6 is 30 cP or more, the compatibility between the first resin 6 and the second resin 7 may be reduced, and the adhesion between the two resins may be reduced.

<Second resin>
The second resin 7 preferably contains at least one of at least one fluorine-based release agent in the first resin 6. As a result, the same fluorine-based release agent is blended in the first resin 6 and the second resin 7, so that when the two resins are integrated, the fluorine-based release agent in the second resin 7 It becomes easy to be attracted to the fluorine-based release agent in the resin 6 of one. As a result, the active ingredient in the fluorine-based release agent is oriented at a high concentration on the surface of the polymer layer 3 (the surface on the opposite side to the substrate 2), so the antifouling property is further enhanced.

The content of the fluorine-based release agent in the second resin 7 is preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight, in terms of the active ingredient. If the content of the fluorine-based release agent in the second resin 7 is within the above range in terms of the active ingredient, the anti-soiling property is further enhanced while the abrasion resistance is maintained. When 2nd resin 7 contains multiple types of fluorine-type release agent, it is preferable that the sum total of the content rate of multiple types of fluorine-type release agent is in the said range in active ingredient conversion (more preferable).

The second resin 7 preferably contains a monofunctional amide monomer. When the monofunctional amide monomer is blended in the second resin 7 applied on the surface of the base material 2, the curing shrinkage of the resin layer 8 is suppressed and the cohesion with the base material 2 is enhanced, so the polymer The adhesion between the layer 3 and the substrate 2 is enhanced. Further, according to the monofunctional amide monomer, since the compatibility between the first resin 6 and the second resin 7 is enhanced, the adhesion between both resins is enhanced. In the case where the monofunctional amide monomer is blended in the second resin 7, the monofunctional amide monomer is less likely to penetrate the surface of the mold 5 as compared to the case where it is blended in the first resin 6. Even if the number of times of transfer of the mold 5 increases, the releasability of the polymer layer 3 and the mold 5 does not easily decrease.

The content of the monofunctional amide monomer in the second resin 7 is preferably 1 to 14% by weight, more preferably 1.5 to 10% by weight, in terms of the active ingredient. If the content of the monofunctional amide monomer in the second resin 7 is lower than 1% by weight in terms of the active ingredient, the adhesion between the polymer layer 3 and the substrate 2 may not be sufficiently improved. When the content of the monofunctional amide monomer in the second resin 7 is higher than 14% by weight in terms of the active ingredient, the crosslink density of the polymer layer 3 does not increase, and as a result, the abrasion resistance decreases. is there. When 2nd resin 7 contains multiple types of monofunctional amide monomers, it is preferable that the sum total of the content rate of multiple types of monofunctional amide monomers is in said range in conversion of an active ingredient (more preferable).

Examples of monofunctional amide monomers include N-acryloyl morpholine, N, N-dimethyl acrylamide, N, N-diethyl acrylamide, N- (2-hydroxyethyl) acrylamide, diacetone acrylamide, N-n-butoxy methyl acrylamide, etc. Can be mentioned.

Examples of known N-acryloyl morpholine include "ACMO (registered trademark)" manufactured by KJ Chemicals. Examples of known N, N-dimethyl acrylamide include "DMAA (registered trademark)" manufactured by KJ Chemicals. Examples of known N, N-diethylacrylamide include "DEAA (registered trademark)" manufactured by KJ Chemicals. Examples of known N- (2-hydroxyethyl) acrylamide include "HEAA (registered trademark)" manufactured by KJ Chemicals. Examples of publicly known diacetone acrylamide include "DAAM (registered trademark)" manufactured by Nippon Kasei Co., Ltd. Examples of known N-n-butoxymethyl acrylamide include "NBMA" manufactured by MRC Unitech Co., and the like.

The second resin 7 may contain a multifunctional acrylate. According to the polyfunctional acrylate, the crosslink density of the polymer layer 3 is increased, and appropriate elasticity (hardness) is imparted, so that the abrasion resistance is enhanced. In the present specification, “polyfunctional acrylate” refers to an acrylate having at least an acryloyl group and having a total of two or more of an acryloyl group and a polymerizable functional group other than an acryloyl group per molecule. The polymerizable functional group other than acryloyl group refers to at least one functional group selected from the group consisting of methacryloyl group, vinyl group, vinyl ether group, and allyl group.

The number of functional groups of the multifunctional acrylate is 2 or more, preferably 4 or more, more preferably 6 or more. If the number of functional groups of the polyfunctional acrylate is too large, the molecular weight increases and the compatibility with other components (for example, a fluorine-based release agent) decreases, and the transparency of the antifouling film 1 (polymer layer 3) May decrease. In addition, the adhesion between the polymer layer 3 and the base material 2 may be reduced due to curing shrinkage of the resin layer 8 or the like. From such a viewpoint, a preferable upper limit value of the number of functional groups of the polyfunctional acrylate is ten. In the present specification, “the number of functional groups of the multifunctional acrylate” refers to the total number per molecule of an acryloyl group and a polymerizable functional group other than an acryloyl group (one or more acryloyl groups).

The polyfunctional acrylate preferably contains at least one polyfunctional acrylate having an ethylene oxide group. As a result, the polymer layer 3 imparts appropriate elasticity (hardness), so that the abrasion resistance is further enhanced.

The content of the multifunctional acrylate in the second resin 7 is preferably 75 to 98% by weight, more preferably 80 to 97.5% by weight, in terms of the active ingredient. When the content of the polyfunctional acrylate in the second resin 7 is lower than 75% by weight in terms of the active ingredient, the polymer layer 3 may become hard and as a result, the abrasion resistance may be reduced. If the content of the polyfunctional acrylate in the second resin 7 is higher than 98% by weight in terms of the active ingredient, the crosslink density of the polymer layer 3 may not be increased, and as a result, the abrasion resistance may be reduced. . When 2nd resin 7 contains multiple types of polyfunctional acrylate, it is preferable that the sum total of the content rate of multiple types of multifunctional acrylate is in the said range in active ingredient conversion (more preferable).

As polyfunctional acrylate, for example, urethane acrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, polyethylene glycol (200) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, dipropylene Glycol diacrylate etc. are mentioned.

As a well-known example of a urethane acrylate, "U-10 HA" (the number of functional groups: ten pieces) by Shin-Nakamura Chemical Co., Ltd., etc. are mentioned. Examples of publicly known 2- (2-vinyloxyethoxy) ethyl acrylate include "VEEA" (number of functional groups: 2 and number of ethylene oxide groups: 2 per molecule) manufactured by Nippon Shokuhin Co., Ltd. Publicly known examples of polyethylene glycol (200) diacrylate include "NK ester A-200" (number of functional groups: 2 and number of ethylene oxide groups: 4 per molecule) manufactured by Shin-Nakamura Chemical Co., Ltd. . Publicly known examples of polyethylene glycol (400) diacrylate include "NK ester A-400" (number of functional groups: 2 and number of ethylene oxide groups: 9 per molecule) manufactured by Shin-Nakamura Chemical Co., Ltd. . Publicly known examples of polyethylene glycol (600) diacrylate include "NK ester A-600" (number of functional groups: 2 and number of ethylene oxide groups: 14 per molecule) manufactured by Shin-Nakamura Chemical Co., Ltd. . Examples of known dipropylene glycol diacrylates include "NK ester APG-100" (number of functional groups: 2 and number of propylene oxide groups: 2 per molecule) manufactured by Shin-Nakamura Chemical Co., Ltd., and the like.

The second resin 7 may contain a polymerization initiator. According to the polymerization initiator, the curability of the resin layer 8 is enhanced.

As a polymerization initiator, a photoinitiator, a thermal-polymerization initiator etc. are mentioned, for example, Especially, a photoinitiator is preferable. The photopolymerization initiator is active to active energy rays, and is added to initiate a polymerization reaction for polymerizing monomers.

As a photoinitiator, a radical polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator etc. are mentioned, for example. As such a photopolymerization initiator, for example, acetophenones such as p-tert-butyltrichloroacetophenone, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one and the like; Ketones such as benzophenone, 4,4'-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, etc .; 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-trimethyl benzoyl-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.

Examples of known 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide include "LUCIRIN (registered trademark) TPO" and "IRGACURE (registered trademark) TPO" manufactured by IGM Resins. As a well-known example of bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide, "IRGACURE 819" by IGM Resins etc. is mentioned. Examples of known 1-hydroxy-cyclohexyl-phenyl-ketone include "IRGACURE 184" manufactured by IGM Resins.

Like the first resin 6, the second resin 7 may contain a solvent.

The thickness T2 of the second resin 7 is preferably 5 to 15 μm, more preferably 7 to 12 μm. When the thickness T2 of the second resin 7 is smaller than 5 μm, the abrasion resistance may be reduced. If the thickness T2 of the second resin 7 is larger than 15 μm, the adhesion between the polymer layer 3 and the substrate 2 may be reduced.

The viscosity of the second resin 7 is preferably less than 200 cP, more preferably less than 150 cP, at 25 ° C. When the viscosity of the second resin 7 is 200 cP or more, the compatibility between the first resin 6 and the second resin 7 may be reduced, and the adhesion between the two resins may be reduced.

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

The surface of the substrate 2 (the surface on the polymer layer 3 side) may be subjected to an easy adhesion treatment (for example, a primer treatment). For example, using a triacetyl cellulose film to which an easy adhesion treatment is applied it can. In addition, the surface of the substrate 2 (the surface on the polymer layer 3 side) may be subjected to a saponification treatment, and for example, a triacetyl cellulose film subjected to a saponification treatment can be used.

When the antifouling film 1 is attached to a display device provided with a polarizing plate such as a liquid crystal display device, the substrate 2 may constitute a part of the polarizing plate.

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

<Mold>
As the mold 5, for example, one produced by the following method can be used. First, aluminum to be the material of the mold 5 is deposited on the surface of the support base by sputtering. Next, by alternately repeating anodic oxidation and etching on the formed layer of aluminum, a female mold (mold 5) having a moth-eye structure can be manufactured. Under the present circumstances, the uneven structure of the metal mold | die 5 can be changed by adjusting the time which anodizes, and the time which performs an etching.

The material of the supporting substrate is, for example, glass; metals such as stainless steel and nickel; polypropylene, polymethylpentene, cyclic olefin polymers (typically, norbornene resins etc., manufactured by Nippon Zeon Co., Ltd. “Zeonor” (Registered trademark), polyolefin resins such as “Arton (registered trademark)” manufactured by JSR; polycarbonate resins; resins such as polyethylene terephthalate, polyethylene naphthalate, and triacetyl cellulose, and the like. Moreover, you may use the base material made from aluminum instead of what formed aluminum into a film on the surface of a support base material.

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

The surface of the mold 5 is preferably subjected to a release treatment with a release treatment agent. As a result, the releasability (for example, water repellency) of the mold 5 is enhanced, and the mold 5 can be easily peeled off from the polymer layer 3. In addition, since the surface free energy of the mold 5 is low, when pressing the substrate 2 against the mold 5 (above (c)), the active component in the fluorine-based release agent is the surface of the resin layer 8 (group It can be uniformly oriented on the surface opposite to the material 2). Furthermore, before the resin layer 8 is cured, it is possible to prevent the active ingredient in the fluorine-based release agent from separating from the surface of the resin layer 8 (the surface on the opposite side to the substrate 2). As a result, in the antifouling film 1, the active ingredient in the fluorine-based release agent can be uniformly oriented on the surface of the polymer layer 3 (the surface opposite to the substrate 2). According to the present embodiment, since peeling of the release processing agent due to penetration of the monofunctional amide monomer is prevented, the releasability of the mold 5 (for example, water repellency) even if the number of times of transfer of the mold 5 increases. ) Is kept high.

Examples of the release treatment agent used for the release treatment of the mold 5 include fluorine-based materials, silicon-based materials, and phosphate ester-based materials. As a well-known example of a fluorine-type material, "Optool DSX" by Daikin Industries, Ltd., "Optool AES4", etc. are mentioned.

[Examples and Comparative Examples]
Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited by these examples.

The materials used to produce the antifouling film in the examples and comparative examples are as follows.

<First resin>
The first resins A1 to A7 and a1 to a7 having the compositions shown in Tables 1 to 4 were used. The abbreviation of each component is as follows.

(Fluorinated release agent)
・ "MT70"
Solvay's Fomblin MT70
Perfluoropolyether group: having a perfluoroalkyl group: not having an active ingredient: 80% by weight (perfluoropolyether derivative)
Solvent: 20% by weight (methyl ethyl ketone)
・ "AD1700"
Solvay "Fluorolink AD1700"
Perfluoropolyether group: having a perfluoroalkyl group: not having an active ingredient: 70% by weight (perfluoropolyether derivative)
Solvent: 30% by weight (ethyl acetate (15% by weight) and butyl acetate (15% by weight))
・ "FAAC-6"
Unimatec CHEMINOX FAAC-6
Perfluoropolyether group: Perfluoroalkyl group not having: Active ingredient having: 100% by weight
・ "RS-76-NS"
"Megafuck RS-76-NS" manufactured by DIC Corporation
Perfluoropolyether group: Perfluoroalkyl group not having: Active ingredient: 100% by weight (fluorine group-containing oligomer (20% by weight) and dipropylene glycol diacrylate (80% by weight))

(Acrylic acid 2- (2-vinyloxyethoxy) ethyl)
・ "VE"
"VEEA" manufactured by Nippon Shokuhin Co., Ltd.
Active ingredient: 100% by weight

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

(Multifunctional acrylate)
・ "APG-100"
"NK ester APG-100" made by Shin-Nakamura Chemical Co., Ltd.
Active ingredient: 100% by weight

What converted into active ingredient the content rate of each component in 1st resin is shown to Tables 5-8.

<Second resin>
The second resins B1 to B6 and b1 to b4 having the compositions shown in Tables 9 to 11 were used. The abbreviation of each component is as follows.

(Fluorinated release agent)
・ "MT70"
Solvay's Fomblin MT70
Perfluoropolyether group: having a perfluoroalkyl group: not having an active ingredient: 80% by weight (perfluoropolyether derivative)
Solvent: 20% by weight (methyl ethyl ketone)
・ "FAAC-6"
Unimatec CHEMINOX FAAC-6
Perfluoropolyether group: Perfluoroalkyl group not having: Active ingredient having: 100% by weight

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

(Multifunctional acrylate)
・ "A-200"
"NK Ester A-200" manufactured by Shin-Nakamura Chemical Co., Ltd.
Active ingredient: 100% by weight
・ "A-400"
"NK Ester A-400" manufactured by Shin-Nakamura Chemical Co., Ltd.
Active ingredient: 100% by weight
・ "A-600"
"NK Ester A-600" manufactured by Shin-Nakamura Chemical Co., Ltd.
Active ingredient: 100% by weight
・ "U-10"
"U-10 HA" made by Shin-Nakamura Chemical Co., Ltd.
Active ingredient: 100% by weight

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

What converted the content rate of each component in 2nd resin into an active ingredient is shown to Tables 12-14.

<Base material>
The thickness was 80 micrometers using "TAC-TD80U" made from Fujifilm.

<Mold>
What was produced by the following method was used. First, aluminum, which is a material of a mold, was deposited by sputtering on a 10 cm square glass substrate. The thickness of the deposited layer of aluminum was 1.0 μm. Next, by alternately repeating anodic oxidation and etching on the deposited aluminum layer, a large number of minute holes (the distance between the bottom points of adjacent holes (concave portions (concave portions) is less than the wavelength of visible light) Anodized layer was formed. Specifically, a layer of aluminum is obtained by sequentially performing anodizing, etching, anodizing, etching, anodizing, etching, anodizing, etching, and anodizing (anodizing: 5 times, etching: 4 times) A large number of minute holes (concave portions) having a shape (tapered shape) which becomes thinner toward the inside of the mold is formed, and as a result, a mold having a concavo-convex structure is obtained. Anodization was performed using oxalic acid (concentration: 0.03% by weight) under the conditions of a liquid temperature of 5 ° C. and an applied voltage of 80 V. The time for one anodic oxidation was 25 seconds. Etching was performed under the conditions of a liquid temperature of 30 ° C. using phosphoric acid (concentration: 1 mol / l). The time for performing one etching was 25 minutes. When the mold was observed with a scanning electron microscope, the depth of the recesses was 290 nm. Thereafter, a mold release treatment was previously performed on the surface of the mold with "Optool AES4" manufactured by Daikin Industries, Ltd. Then, oxygen plasma cleaning (output: 100 W) is performed for 20 seconds on the surface of the mold subjected to the mold release treatment so that the contact angle of water (contact angle immediately after dripping) becomes 125 to 130 °. It was adjusted. Such adjustments were made with the purpose of intentionally degrading the mold and aligning the initial mold releasability among the examples.

Example 1
The antifouling film of Example 1 was manufactured by the manufacturing method of the embodiment described above.

(A) Application of first resin (process (1))
The first resin A1 was applied in a band shape on the surface of the mold (on the surface subjected to release treatment). Thereafter, the mold coated with the first resin A1 was placed in an oven and heat treated at a temperature of 80 ° C. for 1 minute. The thickness of the first resin A1 was 1 μm.

(B) Application of second resin (process (2))
The second resin B1 was applied in a band on the surface of the substrate. Then, the base material with which 2nd resin B1 was apply | coated was put into oven, and it heat-processed at the temperature of 80 degreeC for 1 minute. The thickness of the second resin B1 was 9 μm.

(C) Formation of resin layer (process (3))
With the first resin A1 and the second resin B1 sandwiched therebetween, the base was pressed against the mold by a hand roller. As a result, a resin layer having a concavo-convex structure on the surface (surface opposite to the substrate) was formed.

(D) Formation of polymer layer (process (4))
The resin layer was cured by irradiation with ultraviolet light (irradiation dose: 1 J / cm ² ) from the substrate side. As a result, a polymer layer was formed.

(E) Release of mold The mold of the mold was peeled off 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.
Shape of convex part: Average pitch of bell-shaped convex part: 200 nm
Average height of projections: 200 nm
Average aspect ratio of projections: 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, an osmium coater “Neoc-ST” manufactured by Meiwa Pfosis Co., Ltd. was used to form osmium oxide VIII (thickness: manufactured by Wako Pure Chemical Industries, Ltd.) on the surface (surface opposite to the substrate) of the polymer layer. : 5 nm) was applied.

Thereafter, the above (a) to (e) (transfer of 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 time is referred to as “specification 2”. That is, the antifouling film obtained by the first transfer of the mold is referred to as "the antifouling film of specification 1", and the antifouling film obtained by the transfer of the 20th mold is referred to as "the antifouling of specification 2 Called “sex film”. In addition, the mold after the first transfer is referred to as "the mold of specification 1", and the mold after the twentieth transfer is referred to as "the mold of specification 2".

(Examples 2 to 9 and Comparative Examples 1 to 8)
The soil resistant film of each example was manufactured in the same manner as in Example 1 except that the conditions were changed to those shown in Tables 15-19.

[Evaluation]
The following evaluation was performed about the antifouling film and die of each example. The results are shown in Tables 15-19.

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

(Water repellant)
Water was dropped onto the surface of the polymer layer (surface opposite to the substrate) for each of the antifouling films of Specifications 1 and 2, and the contact angle immediately after the dropping was measured.

(Oil-repellent)
For each of the stain resistant films of Specifications 1 and 2, hexadecane was dropped onto the surface of the polymer layer (the surface opposite to the substrate), and the contact angle immediately after the drop was measured.

As the contact angle, using a portable contact angle meter “PCA-1” manufactured by Kyowa Interface Science Co., Ltd., the θ / 2 method (θ / 2 = arctan (h / r), θ: contact angle, r: droplet) The average value of the contact angles at three points measured by radius, h: height of droplet) is shown. Here, as the first measurement point, the central portion of the antifouling film is selected, and as the second and third measurement points, it is separated by 20 mm or more from the first measurement point, and 1 Two points which were point-symmetrical to each other with respect to the measurement point of the point were selected.

(Fingerprint wiping ability)
First, with respect to the antifouling film of specification 2, a black acrylic plate was attached to the surface of the base opposite to the polymer layer through the optical adhesive layer. And after making a fingerprint adhere to the surface (surface on the opposite side to a substrate) of the polymer layer of the antifouling film of specification 2, 10 by "Bencott (registered trademark) S-2" made by Asahi Kasei Corp. It was visually observed under an environment of an illumination intensity of 100 lx (fluorescent light) whether or not the fingerprints could be wiped off by reciprocal rubbing. The judgment criteria were as follows.
○: The fingerprints were completely wiped off and no wipes were visible.
Δ: The fingerprints are not noticeable, but when the fluorescent light is reflected, the wiping residue is slightly visible.
X: The fingerprint could not be wiped out at all.
Here, it was judged that the fingerprint wiping property is excellent when the judgment is ○ or △.

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

(Steel wool resistant)
First, the surface (surface on the opposite side to the substrate) of the polymer layer of the antifouling film of specification 2 was rubbed in a state where a load of 400 g was applied to steel wool "# 0000" manufactured by Nippon Steel Wool Corporation. And the number “N” of scratches attached to the surface (surface opposite to the substrate) of the polymer layer of the antifouling film of specification 2 while visually observing under the environment of illuminance 100 lx (fluorescent light) Unit: Counted books. When rubbing with steel wool, the surface width measurement machine “HEIDON (registered trademark) -14FW” manufactured by Shinto Scientific Co., Ltd. is used as a testing machine, the stroke width is 30 mm, the speed is 100 mm / s, and the number of rubbing times is 10 reciprocations. did. The judgment criteria were as follows.
:: N = 0
○: N = 1 to 3
Δ: N = 4 to 10
X: N = 11 to 20
Xx: N 21 21
Here, when the determination is ◎, 、, or Δ, it was determined that the steel wool resistance is excellent.

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

(Water repellant)
First, water was dropped onto the surface (the surface subjected to the release treatment) for each of the molds of specifications 1 and 2, and the contact angle immediately after the drop was measured. And based on the following formula (X), 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 the specifications 1 and 2.
“Change rate of water contact angle” = 100 × (“water contact angle in mold of specification 1” − “contact angle of water in mold of specification 2”) / “water contact in mold of specification 1” Corner "(X)
The judgment criteria were as follows.
○: The rate of change of the contact angle of water was less than 5%.
Δ: The change rate of the contact angle of water was 5% or more and less than 10%.
X: The change rate of the contact angle of water was 10% or more.
Here, it was judged that the mold releasability (water repellency) was maintained high even when the judgment was ○ or し て も, even if the number of times of transfer of the mold increased.

As shown in Tables 15 to 17, in Examples 1 to 9, even when the number of times of transfer of the mold increased, the stain resistance was excellent while the decrease in the releasability of the polymer layer and the mold was suppressed. An antifouling film was realized. Moreover, in Examples 1 to 9, even when the number of times of transfer of the mold increased, an antifouling film excellent in abrasion resistance was realized.

On the other hand, as shown in Tables 18 and 19, in Comparative Examples 1 to 8, when the number of times of transfer of the mold increased, the decrease in the releasability of the polymer layer and the mold was not suppressed, and the stain resistance was excellent. An antifouling film was not realized.

Comparative Example 1 was obtained by changing 2- (2-vinyloxyethoxy) ethyl acrylate in the first resin to the monofunctional amide monomer (N-acryloyl morpholine) in the first resin. Therefore, in Comparative Example 1, 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 property of the antifouling film decreased. Moreover, in the comparative example 1, the abrasion resistance of the antifouling film was also low.

Comparative Example 2 was the same as Example 4 except that 2- (2-vinyloxyethoxy) ethyl acrylate in the first resin was changed to a monofunctional amide monomer (N, N-diethylacrylamide). . Therefore, in Comparative Example 2, 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 property of the antifouling film decreased.

Comparative Example 3 was the same as Example 5 except that 2- (2-vinyloxyethoxy) ethyl acrylate in the first resin was changed to a monofunctional amide monomer (N-acryloyl morpholine). Therefore, in Comparative Example 3, 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 property of the antifouling film decreased. Moreover, in the comparative example 3, the abrasion resistance of the antifouling film was also low.

Comparative Example 4 was the same as Example 6 except that 2- (2-vinyloxyethoxy) ethyl acrylate in the first resin was changed to a monofunctional amide monomer (N-acryloyl morpholine). Therefore, in Comparative Example 4, 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 property of the antifouling film decreased. Moreover, in the comparative example 4, the abrasion resistance of the antifouling film was also low.

In Comparative Example 5, since the first resin does not contain 2- (2-vinyloxyethoxy) ethyl acrylate and the other has multifunctional acrylate (dipropylene glycol diacrylate), the number of times of transfer of the mold increases. Then, the releasability of the polymer layer and the mold was reduced, and as a result, the antifouling property of the antifouling film was reduced. Moreover, in the comparative example 5, the abrasion resistance of the antifouling film was also low.

Comparative Example 6 was the same as Example 9 except that 2- (2-vinyloxyethoxy) ethyl acrylate in the first resin was changed to a monofunctional amide monomer (N, N-diethylacrylamide). . Therefore, in Comparative Example 6, 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 property of the antifouling film decreased. Moreover, in the comparative example 6, the abrasion resistance of the antifouling film was also low.

In the comparative example 7, since the content rate of 2- (2-vinyloxy ethoxy) ethyl acrylate in 1st resin was lower than 40 weight% in conversion of an active ingredient, abrasion resistance was low.

In Comparative Example 8, since the content of 2- (2-vinyloxyethoxy) ethyl acrylate in the first resin was higher than 95% by weight in terms of the active ingredient, the antifouling property (in particular, the fingerprint wiping property) It was low.

[Supplementary note]
One aspect of the present invention is an anti-soil comprising a base material and a polymer layer disposed on the surface of the base material and having a concavo-convex structure provided with a plurality of convex portions at a pitch equal to or less than a wavelength of visible light. A process of applying a first resin on the surface of a mold, a process of applying a second resin on the surface of the substrate, and A process (3) of pressing the base material against the mold with the first resin and the second resin interposed therebetween to form a resin layer having the uneven structure on the surface; Curing (4) to form the polymer layer, wherein the first resin contains at least one fluorine-based release agent and 2- (2-vinyloxyethoxy) ethyl acrylate And, in terms of active ingredient, the above acrylic acid 2- (2-vinyloxyetoki ) Ethyl or a process for the preparation of the antifouling film containing 40 to 95 wt%. According to this aspect, even if the number of times of transfer of the mold is increased, the stain resistance excellent in the stain resistance and the abrasion resistance while suppressing the decrease in the releasability of the polymer layer and the mold. Films can be produced.

The at least one fluorine-based release agent may be a plurality of fluorine-based release agents. Thereby, the antifouling property is further enhanced.

The at least one fluorine-based release agent may contain at least one of a fluorine-based release agent having a perfluoropolyether group and a fluorine-based release agent having a perfluoroalkyl group. Thereby, the antifouling property and the abrasion resistance are further enhanced as compared with other types of mold release agents (for example, silicone type mold release agent, phosphate ester type mold release agent, etc.).

The second resin may contain at least one of the at least one fluorine-based release agent. Thereby, since the same fluorine-based release agent is blended in the first resin and the second resin, when the two resins are integrated, the fluorine-based release agent in the second resin is It becomes easy to be attracted to the said fluorine-type mold release agent in said 1st resin. As a result, since the active ingredient in the fluorine-based release agent is oriented at a high concentration on the surface of the polymer layer (the surface opposite to the substrate), the antifouling property is further enhanced.

The second resin may contain a monofunctional amide monomer. Thereby, the cure shrinkage of the resin layer is suppressed, and the cohesion with the base material is enhanced, so the adhesion between the polymer layer and the base material is enhanced. Further, since the compatibility between the first resin and the second resin is enhanced, the adhesion between both resins is enhanced.

The surface of the mold may be subjected to a release treatment with a release treatment agent. Thereby, the mold releasability (for example, water repellency) of the mold is enhanced, and the mold can be easily peeled off from the polymer layer. Further, since the surface free energy of the mold becomes low, when pressing the base material against the mold (the process (3)), the active ingredient in the fluorine-based release agent is the surface of the resin layer. It can be uniformly oriented (surface opposite to the substrate). Furthermore, before curing the resin layer, it is possible to prevent the active ingredient in the fluorine-based release agent from separating from the surface of the resin layer (the surface on the opposite side to the base material). As a result, in the antifouling film, the active ingredient in the fluorine-based release agent can be uniformly oriented on the surface of the polymer layer (the surface opposite to the substrate).

The thickness of the polymer layer may be 5.0 to 20.0 μm. As a result, the active component in the fluorine-based release agent is oriented at a higher concentration on the surface of the polymer layer (the surface 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 moiré and rainbow unevenness.

The average height of the plurality of convex portions may be 50 to 600 nm. Thereby, it can be made compatible with the desirable average aspect ratio of the above-mentioned a plurality of convex parts.

The average aspect ratio of the plurality of convex portions may be 0.8 to 1.5. As a result, the occurrence of optical phenomena such as moiré and rainbow unevenness can be sufficiently prevented, and excellent antireflection performance can be realized. Furthermore, the occurrence of sticking and the deterioration of the transfer condition at the time of forming the uneven structure due to the decrease in the processability of the uneven structure are sufficiently prevented.

1: Antifouling film 2: base material 3: polymer layer 4: convex portion 5: mold 6: first resin 7: second resin 8: resin layer P: convex portion pitch H: convex portion Height T: thickness of polymer layer T1: thickness of first resin T2: thickness of second resin

Claims (10)

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 on the surface of which a plurality of convex portions are provided at a pitch smaller than the wavelength of visible light. ,
Applying a first resin onto the surface of the mold (1);
Applying a second resin onto the surface of the substrate (2);
A process (3) of pressing the base material against the mold while sandwiching the first resin and the second resin to form a resin layer having the uneven structure on the surface;
Curing the resin layer to form the polymer layer (4).
The first resin contains at least one fluorine-based release agent and 2- (2-vinyloxyethoxy) ethyl acrylate, and, in terms of active ingredient, the acrylic acid 2- (2-vinyl) A method for producing an antifouling film comprising 40 to 95% by weight of (oxyethoxy) ethyl. The method for producing an antifouling film according to claim 1, wherein the at least one fluorine-based release agent is a plurality of types of fluorine-based release agents. The at least one fluorine-based release agent includes at least one of a fluorine-based release agent having a perfluoropolyether group and a fluorine-based release agent having a perfluoroalkyl group. The manufacturing method of the antifouling film as described in claim 1 or 2. The method for producing an antifouling film according to any one of claims 1 to 3, wherein the second resin contains at least one of the at least one fluorine-based release agent. The method for producing an antifouling film according to any one of claims 1 to 4, wherein the second resin contains a monofunctional amide monomer. The method for producing an antifouling film according to any one of claims 1 to 5, wherein the surface of the mold is subjected to a release treatment with a release treatment agent. The thickness of the said polymer layer is 5.0-20.0 micrometers, The manufacturing method of the antifouling film in any one of the Claims 1-6 characterized by the above-mentioned. The method for producing an 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 method for producing an antifouling film according to any one of claims 1 to 8, 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 9, wherein an average aspect ratio of the plurality of convex portions is 0.8 to 1.5.

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