阅读说明：本技术 防污性膜和聚合性组合物 (Antifouling film and polymerizable composition ) 是由 芝井康博 田口登喜生 于 2019-09-04 设计创作，主要内容包括：本发明提供即使长时间连续制造也能较高地维持防污性的防污性膜。本发明的防污性膜具备：基材；以及聚合物层,其配置于上述基材的表面上,在表面具有按可见光的波长以下的间距设置多个凸部的凹凸结构,在上述防污性膜中,上述聚合物层是聚合性组合物的固化物,上述聚合性组合物以有效成分换算含有2.5～12.5重量％的具有(甲基)丙烯酰基的氟系低聚物、1～10重量％的包括氟链段和非氟链段的嵌段共聚物,上述氟系低聚物是全氟聚醚系低聚物和全氟烷基系低聚物中的至少一方。(The invention provides an antifouling film which can maintain high antifouling property even if the film is continuously produced for a long time. The antifouling film of the present invention comprises: a substrate; and a polymer layer disposed on the surface of the substrate and having a concavo-convex structure in which a plurality of convex portions are provided at a pitch equal to or less than the wavelength of visible light, wherein the polymer layer is a cured product of a polymerizable composition containing, in terms of active ingredients, 2.5 to 12.5 wt% of a fluorine-based oligomer having a (meth) acryloyl group and 1 to 10 wt% of a block copolymer including a fluorine segment and a non-fluorine segment, and the fluorine-based oligomer is at least one of a perfluoropolyether-based oligomer and a perfluoroalkyl-based oligomer.)

1. An antifouling film comprising:

a substrate; and

a polymer layer disposed on the surface of the base material, the polymer layer having a concavo-convex structure in which a plurality of convex portions are provided at a pitch equal to or less than the wavelength of visible light on the surface, the antifouling film being characterized in that,

the polymer layer is a cured product of the polymerizable composition,

the polymerizable composition contains 2.5 to 12.5 wt% of a fluorine-based oligomer having a (meth) acryloyl group and 1 to 10 wt% of a block copolymer comprising a fluorine segment and a non-fluorine segment in terms of active ingredients,

the fluorine-based oligomer includes at least one of a perfluoropolyether-based oligomer and a perfluoroalkyl-based oligomer.

2. The antifouling film according to claim 1,

the polymerizable composition contains 5 to 10 wt% of the fluorine-based oligomer in terms of an active ingredient.

3. The antifouling film according to claim 1 or 2,

the polymerizable composition contains 3 to 8 wt% of the block copolymer in terms of active ingredient.

4. The antifouling film according to any one of claims 1 to 3,

the polymerizable composition further contains a monofunctional amide monomer.

5. The antifouling film according to any one of claims 1 to 4,

the polymer layer has a thickness of 5 to 20 μm.

6. The antifouling film according to any one of claims 1 to 5,

the average pitch of the plurality of projections is 100 to 400 nm.

7. The antifouling film according to any one of claims 1 to 6,

the average height of the plurality of projections is 50 to 600 nm.

8. The antifouling film according to any one of claims 1 to 7,

the average aspect ratio of the plurality of projections is 0.8 to 1.5.

9. A polymerizable composition characterized by containing, as a main component,

the fluorine-containing oligomer having a (meth) acryloyl group is contained in an amount of 2.5 to 12.5 wt% in terms of active ingredient, and the block copolymer includes a fluorine segment and a non-fluorine segment in an amount of 1 to 10 wt%,

the fluorine-based oligomer includes at least one of a perfluoropolyether-based oligomer and a perfluoroalkyl-based oligomer.

Technical Field

The present invention relates to a stain resistant film and a polymerizable composition.

Background

Various studies have been made on optical films having antireflection properties (for example, see patent documents 1 to 3). In particular, an optical film having a nano-sized uneven structure (nanostructure) is known to have excellent antireflection properties. According to such an uneven structure, since the refractive index changes continuously from the air layer to the base material, reflected light can be reduced significantly.

Disclosure of Invention

Problems to be solved by the invention

However, although such an optical film has excellent antireflection properties, on the other hand, due to the uneven structure of the surface thereof, when dirt such as fingerprints (sebum) adheres, the adhered dirt tends to spread, and it may be difficult to wipe off dirt that has entered between the convex portions. In addition, the attached dirt is easily visible because its reflectance is greatly different from that of the optical film. Therefore, a functional film (antifouling film) having a nano-sized uneven structure on the surface and excellent in dirt-wiping properties (e.g., fingerprint-wiping properties), i.e., antifouling properties, has been required.

In view of the above, the present inventors have studied and found that when a fluorine-based compound is added as a constituent component to a polymer layer constituting an uneven structure of an optical film, the antifouling property is improved.

However, the inventors of the present invention have further studied and found that when a mold is used for forming the uneven structure of the polymer layer, the mold releasability of the mold tends to decrease with an increase in the number of times of transfer of the mold, and as a result, the stain-proofing property of the resulting stain-proofing film tends to decrease.

As described above, conventionally, there has been a problem of realizing an antifouling film which can maintain a high antifouling property even when continuously produced for a long time. However, a solution to the above problem has not yet been found. For example, patent documents 1 to 3 do not describe reduction in the stain-proofing property of a stain-proofing film due to long-term continuous production, and do not solve the above-mentioned problems.

The present invention has been made in view of the above-mentioned situation, and an object thereof is to provide a stain-resistant film capable of maintaining high stain resistance even in continuous production for a long period of time, and a polymeric composition capable of forming a polymer layer of the stain-resistant film.

Means for solving the problems

One aspect of the present invention may be an antifouling film comprising: a substrate; and a polymer layer disposed on the surface of the substrate and having a concavo-convex structure in which a plurality of convex portions are provided at a pitch equal to or less than the wavelength of visible light, wherein the polymer layer is a cured product of a polymerizable composition containing, in terms of active ingredients, 2.5 to 12.5 wt% of a fluorine-based oligomer having a (meth) acryloyl group and 1 to 10 wt% of a block copolymer including a fluorine segment and a non-fluorine segment, the fluorine-based oligomer including at least one of a perfluoropolyether-based oligomer and a perfluoroalkyl-based oligomer.

Another aspect of the present invention may be a polymerizable composition containing, in terms of active ingredients, 2.5 to 12.5 wt% of a fluorine-based oligomer having a (meth) acryloyl group, the fluorine-based oligomer including at least one of a perfluoropolyether-based oligomer and a perfluoroalkyl-based oligomer, and 1 to 10 wt% of a block copolymer including a fluorine segment and a non-fluorine segment.

Effects of the invention

The present invention provides a stain-resistant film which can maintain a high stain resistance even when continuously produced for a long period of time, and a polymerizable composition which can form a polymer layer of the stain-resistant film.

Drawings

Fig. 1 is a schematic cross-sectional view showing an antifouling film according to an embodiment.

Fig. 2 is a schematic perspective view illustrating the polymer layer of fig. 1.

Fig. 3 is a schematic view showing the form of the fluorine-based compound present on the surface of the polymer layer in fig. 1.

Fig. 4A is a schematic cross-sectional view for explaining an example of the method for producing the antifouling film according to the embodiment.

Fig. 4B is a schematic cross-sectional view for explaining an example of the method for producing the antifouling film according to the embodiment.

Fig. 4C is a schematic cross-sectional view for explaining an example of the method for producing the antifouling film according to the embodiment.

Fig. 4D is a schematic cross-sectional view for explaining an example of the method for producing the antifouling film according to the embodiment.

Fig. 4E is a schematic cross-sectional view for explaining an example of the method for producing the antifouling film according to the embodiment.

Description of the reference numerals

1: antifouling film

2: base material

3: polymer layer

4: convex part

5: die set

6: polymerizable composition

7: mold release agent

10: fluorine-based oligomer (R)

20: block copolymer (S)

21: fluorine segment

22: non-fluorine segments

P: pitch of the convex part

H: height of the convex part

T: the thickness of the polymer layer.

Detailed Description

The present invention will be described in more detail below with reference to the accompanying drawings by way of examples, but the present invention is not limited to these examples. The configurations of the embodiments may be appropriately combined or modified within a range not departing from the gist of the present invention.

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