KR20140050538A - Resin film, polarizing plate comprising the same, method of producing the same and display apparatus comprising the same - Google Patents

Abstract

The present invention is to provide a novel and reformed resin film which has improved antifouling properties, sliding properties, and film strength and a manufacturing method of the resin. In order to solve the present object, according to one point of view of the present invention, a resin film which comprises a low refractive index layer which comprises a plurality of hollow silica particles and a coupling agent resin which couples the hollow silica particles each other, is formed with a concave portion and a convex portion having different thickness, and altitude difference of the concave and convex portions is 30-65 nm and a photo-polymeric fluoride polymer combined to the hollow silica particles distributed on the surface of the low refractive index layer and having lower surface tension than the coupling agent resin.

Description

Technical Field [0001] The present invention relates to a resin film, a polarizing plate including the resin film, a method of manufacturing the same, and a display device including the resin film.

The present invention relates to a resin film, a polarizing plate including the same, a method of manufacturing the same, and a display device including the same.

For example, as disclosed in Patent Literatures 1 and 2, antireflection films are often affixed on surfaces such as liquid crystal monitors and plasma displays. The antireflective film improves the visibility of the display by preventing reflection of light on the display surface. The conventional antireflection film includes a low refractive index layer having a low refractive index and a high refractive index layer having a higher refractive index than the low refractive index layer. The low refractive index layer contains hollow silica particles, an acrylic resin, a fluorinated acrylic resin, and an additive.

The hollow silica particles are hollow silica particles, and have a role of decreasing the refractive index of the low refractive index layer. Hollow silica particles have at least a photopolymerizable functional group. Here, as the photopolymerizable functional group, acryloyl group and methacryloyl group are known. Photopolymerizable functional groups are also referred to as ionizing radiation curable groups.

The acrylic resin has a role of a binder that binds the hollow silica particles to each other. The fluorinated acrylic resin bonds the hollow silica particles with each other, and has a role of lowering the refractive index of the low refractive index layer. The additive combines with the functional groups of the hollow silica particles distributed on the surface of the low refractive index layer to impart antifouling property and slipperiness to the low refractive index layer, that is, the antireflection film. Silicones and fluoropolymers are known as additives.

<Prior Art Literature>

<Patent Documents>

(Patent Document 1) JP2004-109966 A

(Patent Document 2) JP2006-336008 A

By the way, when an additive exists in the surface of a low refractive index layer, the function is exhibited. However, in the conventional low refractive index layer, additives were distributed not only on the surface but also on the inside. The reason why the additive is distributed inside the low refractive index layer is that the hollow silica particles and the fluorinated acrylic resin inhibit the bleed out of the additive (moving to the surface). That is, the additive cannot effectively move to the surface because the hollow silica particles become a barrier. Further, the additive is compatible with the fluorinated acrylic resin. For example, since both a fluoropolymer and a fluorinated acrylic resin contain fluorine, it is easy to be affinity. That is, the additive will remain in the vicinity of the fluorinated acrylic resin.

Therefore, the conventional low refractive index layer could not effectively distribute the additive to the surface of the low refractive index layer. For this reason, the conventional low-refractive-index layer improves to some extent an initial antifouling property and slipperiness | lubricacy, but there existed a problem that these characteristics fell remarkably by repeating surface wiping.

In addition, the conventional low refractive index layer also has a problem that the additive strength distributed inside the low refractive index layer lowers the crosslinking density of the binder resin (that is, the acrylic resin and the fluorinated acrylic resin), so that the film strength also drops. Specifically, additives (particularly fluoropolymers) repel acrylic resins. For this reason, an acrylic resin becomes difficult to distribute around the additive, and as a result, the crosslinking density of an acrylic resin falls.

On the other hand, patent document 1 discloses the technique which makes the surface of a low refractive index layer into an uneven shape by making the surface of a hard coating layer into an uneven | corrugated shape, and forming a low refractive index layer on the surface of a hard coating layer. According to this technique, the improvement of the antifouling property etc. of a low refractive index layer is anticipated by the uneven shape of a low refractive index layer. However, even with this technique, the additive could not be effectively localized on the surface of the low refractive index layer. Moreover, in this technique, since the surface of a hard-coat layer needs to be made into the uneven | corrugated shape as a premise to form a low refractive index layer, there existed another problem that it is very troublesome to make the surface of the low refractive index layer into the uneven | corrugated shape.

Patent document 2 discloses an antireflection film in which a sea island structure is formed as a phase having no silica particles and a phase having silica particles, but the additive could not be effectively localized on the surface of the low refractive index layer even by this technique. Moreover, this technique also had another problem that the durability of the antireflection film was very bad. Therefore, in the technique disclosed in patent documents 1 and 2, the said problem could not be solved at all.

Accordingly, the present invention has been made in view of the above problems, and an object of the present invention is to provide a novel and improved method for producing a resin film and a resin film which can improve antifouling property and slipperiness and also improve film strength. It is to offer.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, according to one viewpoint of this invention, the hollow resin particle and the binder resin which couple | bonds a hollow silica particle are included, The recessed part and convex part from which layer thickness differs are formed, and And a low refractive index layer having a high difference between the portions and the convex portions of 30 nm to 65 nm, and a photopolymerizable fluoropolymer bonded to the hollow silica particles distributed on the surface of the low refractive index layer and having a lower surface tension than the binder resin. A resin film is provided.

According to this aspect, the resin film is provided with a photopolymerizable fluoropolymer bonded to the hollow silica particles distributed on the surface of the low refractive index layer and repulsing with the binder resin. Therefore, since the photopolymerizable fluoropolymer is effectively bleed out by the repulsive force by the binder resin, the resin film can localize the photopolymerizable fluoropolymer on the surface of the low refractive index layer. Thereby, from this viewpoint, the antifouling property, slipperiness | lubricacy, scratch resistance, and film strength of a resin film can be improved.

In addition, according to this aspect, since an uneven shape, that is, a sea island structure is formed on the surface of the low refractive index layer, the frictional force between the surface of the resin film and another object can be reduced by this island structure, and further, the antifouling property of the resin film, Slip resistance and scratch resistance can be improved.

Here, at least a photopolymerizable fluoropolymer among the thermopolymerizable fluoropolymers and photopolymerizable fluoropolymers bonded to the hollow silica particles distributed on the surface of the low refractive index layer and having a lower surface tension than the binder resin, The content rate is larger than 5 mass% and less than 50 mass%, the sum total of the content rate of a photopolymerizable fluoropolymer and a thermopolymerizable fluoropolymer is 1.5 mass% or more and 7 mass% or less, and the content rate of a photopolymerizable fluoropolymer is 1.5 mass% or more. The ratio of the content of the thermally polymerizable fluoropolymer and the content of the photopolymerizable fluoropolymer may be smaller than 0.43.

According to this aspect, it is possible to more reliably form the concave portion and the convex portion in which the height difference becomes 30 nm to 65 nm in the low refractive index layer.

In addition, the binder resin may have a hydrogen bond former that can form hydrogen bonds with other functional groups.

According to this aspect, since the binder resin has a hydrogen bond former, it is possible to effectively bleed out the photopolymerizable fluoropolymer and the thermopolymerizable fluoropolymer.

In addition, the binder resin may have a hydroxyl group as a hydrogen bond former.

According to this aspect, since the binder resin has a hydroxyl group as a hydrogen bond former, it is possible to effectively bleed out the photopolymerizable fluoropolymer and the thermopolymerizable fluoropolymer.

The weight average molecular weight of the thermopolymerizable fluoropolymer may be larger than the weight average molecular weight of the photopolymerizable fluoropolymer.

According to this aspect, the weight average molecular weight of the thermopolymerizable fluoropolymer is larger than the weight average molecular weight of the photopolymerizable fluoropolymer. Thus, the photopolymerizable fluoropolymer and the thermopolymerizable fluoropolymer can be effectively bleed out. In addition, since the photopolymerizable fluoropolymer functions as a compatibilizer, the solubility of the photopolymerizable fluoropolymer and the thermopolymerizable fluoropolymer in the solvent is improved.

The weight average molecular weight of the thermopolymerizable fluoropolymer may be 10000 g / mol or more, and the weight average molecular weight of the photopolymerizable fluoropolymer may be less than 10000 g / mol.

According to this aspect, since the weight average molecular weight of the thermopolymerizable fluoropolymer is 10000 g / mol or more, and the weight average molecular weight of the photopolymerizable fluoropolymer is less than 10000 g / mol, the photopolymerizable fluoropolymer and the thermopolymerizable fluoropolymer can be effectively bleed out. have. In addition, since the photopolymerizable fluoropolymer functions as a compatibilizer, the solubility of the photopolymerizable fluoropolymer and the thermopolymerizable fluoropolymer in the solvent is improved.

According to another aspect of the present invention, a binder monomer capable of bonding hollow silica particles and hollow silica particles, a photopolymerizable fluoropolymer and a thermopolymerizable fluorine capable of bonding to hollow silica particles and having a lower surface tension than the binder monomer Producing a coating liquid comprising at least a photopolymerizable fluoropolymer in the polymer, applying the coating liquid to a substrate, and initiating a polymerization reaction, wherein the content of the hollow silica particles is greater than 5% by mass and 50% by mass It is smaller, and the sum total of the content rate of a photopolymerizable fluoropolymer and a thermopolymerizable fluoropolymer is 1.5 mass% or more and 7 mass% or less, the content rate of a photopolymerizable fluoropolymer is 1.5 mass% or more, and the content rate and photopolymerizability of a thermopolymerizable fluoropolymer. The ratio of the content rate of the fluoropolymer is smaller than 0.43. It is a ball.

According to this viewpoint, a resin film can be created simply by apply | coating the coating liquid in which each material melt | dissolved, and starting a polymerization reaction, and therefore it is easily created.

As described above, according to the present invention, the photopolymerizable fluoropolymer is effectively bleeded out by the repulsive force by the binder resin, and a sea island structure is formed on the surface of the low refractive index layer. Therefore, according to the present invention, the antifouling property, slipperiness, scratch resistance and film strength of the resin film can be improved.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a side cross-sectional view schematically showing the structure of a resin film according to an embodiment of the present invention. FIG.
2 is a photograph of the surface of a resin film by a shape measurement laser microscope.
3 is a cross-sectional view of a polarizing plate according to an embodiment of the present invention.

EMBODIMENT OF THE INVENTION Preferred embodiment of this invention is described in detail, referring an accompanying drawing below. In addition, in this specification and drawing, duplication description is abbreviate | omitted by attaching | subjecting the same code | symbol about the component which has a substantially same functional structure. The terms "upper" and "lower" in this specification are based on the drawings, and "upper" may be changed to "lower" and "lower" may be changed to "upper" depending on the point of view. It will be understood that where a layer or structure is referred to herein as "on" or "on ", it encompasses not only just another layer or structure but also intervening layers or structures in between. On the other hand, a layer being referred to as "directly on" or "directly above" In the drawings, the thickness, length, width, and the like of the constituent elements are slightly enlarged in size and can be sufficiently changed by those skilled in the art.

<1. Structure of Resin Film>

First, the structure of the resin film 10 which concerns on this embodiment is demonstrated based on FIG. The resin film 10 includes a low refractive index layer 10a and an additive 40. The low refractive index layer 10a contains hollow silica particles (hollow silica fine particles) 20, binder resin 30, and a photoinitiator. The resin film 10 of the present embodiment is used for, for example, an antireflection film, but is suitably applied to other fields, for example, a field using a low refractive index film. The low refractive index layer 10a may have a refractive index of 1.10 to 1.45. In the above range, it may be effective to lower the surface reflectivity.

The hollow silica particles 20 may be uniformly distributed in the low refractive index layer 10a. As shown in FIG. 1, the “uniformly dispersed” is a low refractive index layer without distinction between a phase including hollow silica particles 20 and a phase not including hollow silica particles 20. (10a) It can distribute uniformly to the whole surface. For example, all hollow silica particles 20 may be in contact with adjacent hollow silica particles 20.

The hollow silica particles 20 are nanoscale particles dispersed in the low refractive index layer 10a and having at least a photopolymerizable functional group. Specifically, the hollow silica particles 20 have an outer layer, and the inside of the outer layer is hollow or porous. The outer layer and the porous body mainly consist of silicon oxide. In addition, many photopolymerizable functional groups are couple | bonded with the outer layer. The photopolymerizable functional group and the outer layer are bonded via at least one of Si—O—Si bonds and hydrogen bonds. As a photopolymerizable functional group, acryloyl group and methacryloyl group are mentioned. That is, the hollow silica particles 20 include at least one of acryloyl group and methacryloyl group as the photopolymerizable functional group. Photopolymerizable functional groups are also referred to as ionizing radiation curable groups. The hollow silica particles 20 may have at least a photopolymerizable functional group, and the number and kind of these functional groups are not particularly limited. In addition, the hollow silica particles 20 may have other functional groups, for example, thermopolymerizable functional groups. As a thermopolymerizable functional group, a hydroxyl group, a silanol group, an alkoxy group, a halogen, hydrogen, an isocyanate group, etc. are mentioned, for example. The thermopolymerizable functional group is bonded to the hollow silica particles 20 in the same manner as the photopolymerizable functional group.

Although the average particle diameter of the hollow silica particle 20 is not specifically limited, It is preferable that it is 10-100 nm, and it is more preferable that it is 40-60 nm. When the average particle diameter is less than 10 nm, the hollow silica particles 20 tend to aggregate, so that uniform dispersion of the hollow silica particles 20 may not be easy. In addition, when the average particle diameter exceeds 100 nm, the transparency of the low refractive index layer 10a may be inferior.

Here, an average particle diameter is an arithmetic mean value of the particle diameter of the hollow silica particle 20 (diameter when the hollow silica particle 20 is assumed to be a sphere). The particle diameter of the hollow silica particles 20 is measured by, for example, a laser diffraction scattering particle size distribution meter (specifically, HORIBA LA-920). On the other hand, the laser diffraction scattering particle size distribution meter is not limited to HORIBA LA-920. The refractive index of the hollow silica particles 20 varies depending on the refractive index required for the low refractive index layer 10a, but is, for example, 1.10 to 1.40, preferably 1.15 to 1.25. The refractive index of the hollow silica particles 20 is measured by simulation software (Lambda Research, Inc. TracePro), for example.

The content rate of the hollow silica particles 20 (mass% with respect to the total mass of the hollow silica particles 20, the binder resin 30, the additive 40, and the photoinitiator) is greater than 5% by mass and less than 50% by mass. . As will be described later, when the content rate of the hollow silica particles 20 falls within this range, an island-in-the-sea structure having a height difference (h) of 30 nm to 65 nm is formed, and further, the properties of the resin film 10 become good. In addition, since the hollow silica particles 20 have a role of lowering the refractive index of the low refractive index layer 10a, when the content rate is too low (5 mass% or less), the refractive index of the low refractive index layer 10a is sufficiently lowered. I never do that. A more preferable content rate is 10 mass% or more and 45 mass% or less and 20 mass% or more and 40 mass% or less. When the content rate of the hollow silica particles falls within this range, the properties of the resin film 10 become further better. On the other hand, as the content rate of the hollow silica particles 20 increases, the height difference h tends to increase.

The binder resin 30 has a network structure and connects the hollow silica particles 20 to each other. The monomer constituting the binder resin 30, that is, the monomer for the binder, has a hydrogen bond former and two or more photopolymerizable functional groups. The hydrogen bond former is a functional group capable of forming a hydrogen bond with another functional group, for example, a hydroxyl group. On the other hand, the hydrogen bond former is not limited to this example, and hydrogen bonds (that is, hydrogen atoms connected with other atoms in covalent bonds are formed with lone pairs of electrons such as nitrogen, oxygen, sulfur, fluorine, and π electrons located near the hydrogen atoms). Any functional group may be used as long as it forms a noncovalent attraction force interaction. The photopolymerizable functional group is, for example, acryloyl group and methacryloyl group as described above. Therefore, the binder monomer is a polyfunctional acrylate monomer.

Here, since the binder resin 30 polymerizes the monomer for a binder which has a hydrogen bond formation group, the additive 40 mentioned later can be effectively bleeded out. That is, since the binder resin 30 has a hydrogen bond former, the surface tension is increased. On the other hand, since the additive 40 is a fluoropolymer, the surface tension is low. Accordingly, the additive 40 is effectively bleeded out by repelling the binder resin 30. In addition, the surface tension of the binder monomer is preferably 36 dyne / cm or more and 45 dyne / cm or less. When the surface tension is within this range, the additive 40 bleeds out effectively. Surface tension is measured by an automatic surface tension meter (specifically, DY-300 of Kyowa Interface Science Co., Ltd.). In addition, the automatic surface tension meter is not limited to DY-300 from Kyowa Interface Science. And the present inventor further examined binder resin 30, and it turned out that a structure is not formed even in the low refractive index layer 10a, when the binder monomer does not have a hydrogen bond forming group. Therefore, the hydrogen bond former is also an important structure in that it forms a structure also in the low refractive index layer 10a. Surface tension herein is a value at 25 ℃.

As a monomer for a binder, diacrylates, such as glycerine di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, and isocyanurate acrylate, and pentaerythritol (meth) Penta (meth) acrylates, such as a tri (meth) acrylate, such as an acrylate, a pentaerythritol (meth) acrylate derivative, and a dipentaerythritol (meth) acrylate, etc. are mentioned. Of course, the binder monomer may be other than these. That is, the binder monomer may be any one as long as it has a hydrogen bond former and two or more photopolymerizable functional groups.

Since the binder monomer has three or more functional groups in total, it superposes | polymerizes and forms the binder resin 30 of a complicated three-dimensional structure (network structure). That is, the hydrogen bond former of the binder monomer is thermally polymerized (condensation polymerization) with the thermopolymerizable functional group of the hollow silica particles 20 or with the hydrogen bond former of the other binder monomer. In addition, the photopolymerizable functional group of the binder monomer photopolymerizes with the photopolymerizable functional group of the hollow silica particles 20 or the photopolymerizable functional group of the other binder monomer. Thereby, binder resin 30 of a complicated three-dimensional structure (network structure) is formed. In addition, since the binder monomer bleeds out the additive 40, the additive 40 remaining in the low refractive index layer 10a can be reduced. Therefore, the crosslinking density of binder resin 30 improves, and also the mechanical strength of the low refractive index layer 10a improves.

The content rate of the binder resin 30 (mass% with respect to the total mass of the hollow silica particle 20, the binder resin 30, the additive 40, and a photoinitiator) can be 50-85 mass%. In the above range, there may be an effect of bleeding out the additive to the surface.

On the other hand, the hollow silica particles 20 may be directly bonded to each other. That is, the thermopolymerizable functional group of the hollow silica particles 20 is bonded to the thermopolymerizable functional group of the other hollow silica particles 20, and the photopolymerizable functional group of the hollow silica particles 20 is a photopolymerizable functional group of the other hollow silica particles 20. Combine with This bonding is possible because the hollow silica particles 20 are not modified beforehand in the production of the resin film 10.

The additive 40 is added to impart antifouling, slip and scratch resistance to the low refractive index layer 10a. The additive 40 consists of at least the photopolymerizable fluoropolymer 41. The additive 40 may contain the thermopolymerizable fluoropolymer 42.

At least one of the additive, ie, the photopolymerizable fluoropolymer and the thermopolymerizable fluoropolymer, can be easily bleed out to the surface of the low refractive index layer only when the surface tension is lower than that of the binder resin. To this end, at least one of the photopolymerizable fluoropolymer and the thermopolymerizable fluoropolymer may have a surface tension of 6 to 20 dyne / cm.

The photopolymerizable fluoropolymer is a fluoropolymer having a photopolymerizable functional group, and is represented by the following general formula (1).

[Chemical Formula 1]

In formula (1), Rf1 represents a (per) fluoroalkyl group or a (per) fluoropolyether group, W1 represents a linking group, and RA1 represents a functional group having a polymerizable unsaturated group, that is, a photopolymerizable functional group. n is an integer of 1 to 3, m represents an integer of 1 to 3)

The structure of the (per) fluoroalkyl group is not particularly limited. That is, the (per) fluoroalkyl group is linear (e.g., -CF ₂ CF ₃ , -CH ₂ (CF ₂ ) ₄ H, -CH ₂ (CF ₂ ) ₈ CF ₃ , -CH ₂ CH ₂ (CF ₂ ) may be either ₄ H, etc.), a branch structure (e. _{g., CH (CF 3) 2,} CH 2 CF (CF 3) 2, CH (CH 3) CF 2 CF 3, CH (CH 3) (CF 2) ₅ CF ₂ H or the like) or an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, or an alkyl group substituted therewith).

The (per) fluoropolyether group is a (per) fluoroalkyl group having an ether bond, and the structure thereof is not particularly limited. That is, as the (per) fluoropolyether group, for example, -CH ₂ OCH ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, -CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , —CH ₂ CH ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, and a fluorocycloalkyl group having 4 to 20 carbon atoms having 5 or more fluorine atoms. As the perfluoropolyether group, for example,-(CF ₂ ) _x O (CF ₂ CF ₂ O) _y ,-[CF (CF ₃ ) CF ₂ O] _x- [CF ₂ (CF ₃ )] , (CF ₂ CF ₂ CF ₂ O) _x , (CF ₂ CF ₂ O) _x and the like. Here, x and y are arbitrary natural numbers.

The linking group is not particularly limited, and examples thereof include a methylene group, a phenylene group, an alkylene group, an arylene group, a heteroalkylene group, or a combination thereof. These linking groups may further have a carbonyl group, a carbonyloxy group, a carbonylimino group, a sulfonamide group or the like or a combination of these functional groups. Acryloyl group, methacryloyl group, etc. are mentioned as a photopolymerizable functional group.

The weight average molecular weight (Mw) of the photopolymerizable fluoropolymer 41 is smaller than the weight average molecular weight (Mw) of the thermally polymerizable fluoropolymer 42 described later, preferably less than 10000 g / mol. The lower limit of the weight average molecular weight (Mw) of the photopolymerizable fluoropolymer is not particularly limited, but is, for example, 3000 g / mol or more. For example, Mw of a photopolymerizable fluoropolymer is 3000-8000 g / mol. In addition, although the sliding angle of oleic acid of the photopolymerizable fluoropolymer 41 is selected according to the antifouling property and slipperiness | lubricacy requested | required of the resin film 10, it becomes 10 degrees or less, for example. The oleic acid drop angle is measured by, for example, a fully automatic contact angle meter DM700 (manufactured by Kyowa Interface Science Co., Ltd.).

The thermally polymerizable fluoropolymer 42 is a fluoropolymer having a thermally polymerizable functional group, and is represented by the following general formula (2).

(2)

In formula (2), Rf2 is a (per) fluoroalkyl group or a (per) fluoropolyether group, W2 is a linking group, X is a thermopolymerizable functional group, for example, an alkoxy group having 1 to 4 carbon atoms, silanol group, halogen or hydrogen to be. n represents the integer of 1-3. The thermopolymerizable functional group is a concept including the above-mentioned hydrogen bond former.

The structures of the (per) fluoroalkyl group, the (per) fluoropolyether group and the linking group are the same as those of the photopolymerizable fluoropolymer. The weight average molecular weight (Mw) of the thermopolymerizable fluoropolymer is larger than the weight average molecular weight (Mw) of the photopolymerizable fluoropolymer, preferably 10000 g / mol or more. On the other hand, the upper limit of the weight average molecular weight (Mw) of the thermopolymerizable fluoropolymer is not particularly limited, but is, for example, 50000 g / mol or less. In addition, although the oleic acid fall angle of the thermopolymerizable fluoropolymer 41 is selected according to the antifouling property and slipperiness | lubricacy requested | required of the resin film 10, it becomes 10 degrees or less, for example.

Thus, since the photopolymerizable fluoropolymer 41 and the thermally polymerizable fluoropolymer 42 have a fluoropolymer portion as a basic skeleton, the fluoropolymer portion and the hydrogen bond formers of the binder resin 30 repel each other. Thereby, the photopolymerizable fluoropolymer 41 and the thermopolymerizable fluoropolymer 42 are effectively bleeded out (that is, unevenly distributed on the surface of the low refractive index layer 10a).

The photopolymerizable fluoropolymer 41 is bonded to the photopolymerizable functional groups of the hollow silica particles 20 and the binder resin 30 distributed on the surface of the low refractive index layer 10a, and the thermally polymerizable fluoropolymer 42 is It combines with the thermopolymerizable functional groups of the hollow silica particles 20 and the binder resin 30 distributed on the surface of the low refractive index layer 10a. As described above, in the present embodiment, the hollow silica particles 20 and the binder resin 30 disposed on the surface of the low refractive index layer 10a are protected by the photopolymerizable fluoropolymer 41 and the thermopolymerizable fluoropolymer 42. .

In addition, conventionally, only a photopolymerizable polymer was used as an additive. Therefore, in the conventional low refractive index layer, the hydroxyl part of the hollow silica particle arrange | positioned at the surface was exposed. For this reason, there existed a problem that the antifouling property and slipperiness | lubricacy of a low refractive index layer fell remarkably.

In contrast, in the present embodiment, the hollow silica particles 20 disposed on the surface of the low refractive index layer 10a are protected by the photopolymerizable fluoropolymer 41 and the thermopolymerizable fluoropolymer 42. That is, the hydroxyl groups of the hollow silica particles 20 are also protected by the thermopolymerizable fluoropolymer 42. Therefore, in this embodiment, since the surface of the low refractive index layer 10a can be uniformly protected by the photopolymerizable fluoropolymer 41 and the thermopolymerizable fluoropolymer 42, antifouling property and slipperiness | lubricacy improve.

In addition, the weight average molecular weight (Mw) of the thermopolymerizable fluoropolymer 42 is larger than the weight average molecular weight (Mw) of the photopolymerizable fluoropolymer 41. The weight average molecular weight (Mw) of the photopolymerizable fluoropolymer 41 and the thermally polymerizable fluoropolymer 42 is set in this manner for the following reasons. That is, the photopolymerizable fluoropolymer 41 and the thermopolymerizable fluoropolymer 42 are preferable because the surface tension decreases as the weight average molecular weight Mw increases (that is, the antifouling property, slipperiness, and bleed-out property are improved).

However, since the acryloyl group and the methacryloyl group are large in polarity, when the weight average molecular weight (Mw) of the fluoropolymer is too large, it is difficult to introduce these functional groups into the fluoropolymer. That is, the photopolymerizable fluoropolymer 41 becomes difficult to manufacture. In addition, when the weight average molecular weight (Mw) of the photopolymerizable fluoropolymer 41 and the thermally polymerizable fluoropolymer 42 is too large, it becomes difficult to dissolve in the solvent during the production of the resin film 10 (details for the binder Compatibility with monomers is reduced).

Thus, the weight average molecular weight (Mw) of the photopolymerizable fluoropolymer 41 was set as described above. Thereby, since the weight average molecular weight (Mw) of the fluoropolymer into which an acryloyl group and a methacryloyl group are introduce | transduced can be made small, acryloyl group and a methacryloyl group can be introduce | transduced easily into a fluoropolymer.

In addition, the photopolymerizable fluoropolymer 41 serves as a compatibilizer for the thermally polymerizable fluoropolymer 42. That is, the thermally polymerizable fluoropolymer 42 is easily dissolved in the solvent by being added to the solvent together with the photopolymerizable fluoropolymer 41 having a small weight average molecular weight Mw. That is, in the present embodiment, the weight average molecular weight (Mw) of the entire additive 40 is increased by increasing the weight average molecular weight (Mw) of the thermally polymerizable fluoropolymer 42, while the weight of the photopolymerizable fluoropolymer 41 is increased. By making average molecular weight Mw small, the additive 40 is made easy to melt | dissolve in a solvent.

Moreover, the content rate (mass% with respect to the gross mass of the hollow silica particle 20, the binder resin 30, the additive 40, and a photoinitiator) of the additive 40 becomes 1.5 mass% or more and 7 mass% or less. Preferably they are 2.0 mass% or more and 7.0 mass% or less. Here, the content rate of the additive 40 becomes a total value of the content rate of the photopolymerizable fluoropolymer 41 and the thermopolymerizable fluoropolymer 42.

Moreover, the content rate (mass% with respect to the gross mass of the hollow silica particle 20, the binder resin 30, the additive 40, and a photoinitiator) of the photopolymerizable fluoropolymer 41 will be 1.5 mass% or more. Preferably they are 1.8 mass% or more and 6.0 mass% or less, More preferably, they are 1.8 mass% or more and 4.0 mass% or less. The thermopolymerizable fluoropolymer 42 is an optional component, and the additive 40 does not need to include the thermopolymerizable fluoropolymer 42. On the other hand, the photopolymerizable fluoropolymer 41 becomes an essential structure of the additive 40. When the present inventor examined the additive 40, when the photopolymerizable fluoropolymer 41 was not contained in the additive 40, it turned out that the structure is not formed even if it has a high difference of 30 nm-65 nm. Therefore, the photopolymerizable fluoropolymer 41 becomes an essential structure of the additive 40.

In addition, the ratio of the content rate of the thermopolymerizable fluoropolymer 42 and the content rate of the photopolymerizable fluoropolymer 41 is less than 0.43. For example, it may be less than 0.25, for example, 0.11 to 0.33. As described later, when these conditions are satisfied, an island-in-the-sea structure having a height difference of 30 nm to 65 nm is formed, and further, the characteristics of the resin film 10 become good. On the other hand, when the present inventor examined the additive 40, when the additive 40 is not a fluoropolymer (for example, it becomes a silicone type polymer), even if it does not form a structure even in the low refractive index layer 10a, It turned out. Therefore, the additive 40 being a fluoropolymer is also an important structure from the point of forming a structure also in the low refractive index layer 10a.

The photoinitiator is a material for initiating photopolymerization, and any kind thereof. That is, in the present embodiment, all the photoinitiators can be used. However, it is preferable that photoinitiator is less likely to receive oxygen inhibition and has good surface hardenability.

The content rate of the photoinitiator (mass% with respect to the total mass of the hollow silica particles 20, the binder resin 30, the additive 40, and the photoinitiator) is 2 to 5 mass%. In the above range, there may be an effect of improving the film strength.

In this embodiment, the material of the resin film 10 becomes each material mentioned above, and since the content ratio of each material becomes the range mentioned above, the island-in-water structure is formed in the surface of the low refractive index layer 10a. Specifically, in the low refractive index layer 10a, convex portions 10b and concave portions 10c having different layer thicknesses are formed. The layer thickness of the convex part 10b is larger than the layer thickness of the concave part 10c. Here, the layer thickness of the convex part 10b is the distance from the surface (surface in which the island-in-sea structure is formed) of the convex part 10b to the back surface (surface in contact with the substrate etc. to which the resin film 10 is coated). Similarly, the layer thickness of the recessed part 10c is the distance from the surface (surface in which the island-in-sea structure is formed) from the recessed part 10c to the back side (surface in contact with the substrate etc. to which the resin film 10 is coated).

For example, the convex part 10b becomes an island part, and the recessed part 10c becomes a sea part. Of course, the convex part 10b may be a sea part, and the recessed part 10c may be an island part. Therefore, in the present embodiment, even when the substrate on which the low refractive index layer 10a is coated is horizontal, a sea island structure is formed on the surface of the low refractive index layer 10a. This is because unevenness, that is, an island-in-sea structure, is formed on the surface of the low refractive index layer 10a by the difference in the layer thicknesses of the convex portions 10b and the concave portions 10c.

The height difference h between the convex portion 10b and the concave portion 10c, that is, the distance from the upper end portion 10b 'of the convex portion 10b to the lower end portion 10c' of the concave portion 10c is 30 nm to 65 nm. . In addition, the angle of the inclination of each point on the surface of the low refractive index layer 10a and the plane direction (direction perpendicular to the thickness direction of the low refractive index layer 10a) is within a predetermined range (for example, within ± 30 degrees). Becomes the value of. Here, the direction from the surface direction toward the surface of the low refractive index layer 10a is made into the positive direction. Therefore, the uneven | corrugated shape of the low refractive index layer 10a becomes a smooth shape. Moreover, the additive 40 is arrange | positioned at the surface of the convex part 10b and the recessed part 10c.

Here, when the height difference h is smaller than 30 nm, the surface of the low refractive index layer 10a is close to the plane, so that the effect described later becomes difficult to be exhibited. On the other hand, when the height difference h is larger than 65 nm, the uneven shape becomes steep, and therefore, other objects (for example, fingerprints) attached to the surface of the resin film 10 become difficult to wipe off. The correlation between the steepness of the uneven shape and the ease of wiping off other objects will be described later.

In addition, the formation of the island-in-the-sea structure on the surface of the low refractive index layer 10a can be confirmed, for example, by observation with a scanning electron microscope (SEM) or a shape measurement laser microscope. 2 is a photograph of the surface of the resin film 10 according to the present embodiment by a shape measurement laser microscope (magnification x 50). Here, the shape measuring laser microscope acquires three-dimensional data of the entire observation field by performing non-contact three-dimensional measurement of the object using a laser. The shape measuring laser microscope is VK-9500 manufactured by KEYENCE JAPAN. Of course, the shape measurement laser microscope is not limited to this example.

In addition, the height difference h can be measured by a shape-measuring laser microscope. Specifically, a predetermined number (for example, 5) of three-dimensional data is obtained by acquiring the roughness (measurement point) of the convex part 10b and the recessed part 10c which adjoin each other, and calculate these height differences. And the calculated arithmetic mean of the height difference is made into the height difference h of the low refractive index layer 10a. On the other hand, since the photopolymerizable fluoropolymer 41 and the thermopolymerizable fluoropolymer 42 which are the additives 40 are bleed out on the surface of the low refractive index layer 10a, the shape measurement laser microscope is substantially an additive 40. ), The concave-convex shape of the layer 50 (hereinafter also referred to as a protective layer) 50 is measured. That is, the shape measurement laser microscope measures the height difference between the convex part 51 and the concave part 52 of the protective layer 50. Here, the convex portion 51 of the protective layer 50 is formed on the convex portion 10b of the low refractive index layer 10a, and the concave portion 52 of the protective layer 50 is formed of the low refractive index layer 10a. It is formed on the recessed part 10c.

However, since the protective layer 50 is formed along the uneven shape of the low refractive index layer 10a, the uneven shape of the protective layer 50 is substantially the same as the uneven shape of the low refractive index layer 10a. That is, the height difference of the protective layer 50 becomes substantially the same as the height difference h of the low refractive index layer 10a. Therefore, the shape measurement microscope can measure the height difference h of the low refractive index layer 10a.

In addition, the inclination of each point on the surface of the low refractive index layer 10a and the angle which the surface direction makes can also be measured by a shape measurement microscope. Specifically, the angle can be measured with the above-mentioned three-dimensional data.

The resin film 10 has the following structure, especially the sea island structure, and has the following characteristics. First, since other objects (for example, oils such as fingerprints, cloth, sharp objects, etc.) may contact only the convex portions 51 of the protective layer 50, the contact area between the other objects and the protective layer 50 may be reduced. Degrades. The protective layer 50 is made of fluoropolymer. Thus, the frictional force between the other object and the protective layer 50 is significantly lowered. This makes it difficult to attach other objects to the resin film 10. Moreover, even if another object adheres to the resin film 10, another object can be wiped off easily. In addition, since other objects tend to slip on the surface of the protective layer 50, other objects are less likely to be scratched on the protective layer 50. Therefore, slipperiness | lubricacy, antifouling property, and scratch resistance of the resin film 10 are improved. On the other hand, when the frictional force decreases, the contact angle increases, so that the frictional force can be substantially measured by measuring the contact angle.

Second, since the surface area of the low refractive index layer 10a increases, the amount of the additive 40 to bleed out also increases. As a result, since the frictional force of the resin film 10 falls, the antifouling property, slipperiness, and scratch resistance of the resin film 10 improve.

Third, a gap is formed between the other object and the recess 52 of the protective layer 50. That is, another object is in the state which floated on the recessed part 52. FIG. And air exists in this space | gap, and the surface tension of air becomes theoretically zero. Therefore, also in this point, the friction force between another object and the resin film 10 falls.

Moreover, since the uneven | corrugated shape of the protective layer 50 is made into a gentle shape, it can wipe off other objects easily and reliably. That is, when wiping off the other object (for example, fingerprint) attached to the convex part 51 of the protective layer 50, there exists a possibility that another object may enter the recessed part 52. FIG. However, since the concave-convex shape of the protective layer 50 is gentle, cilia of the cloth for wiping can easily enter the recess 52, and further, other objects in the recess 52 can be easily wiped off.

On the other hand, in the field of a photoresist etc., the film in which the uneven | corrugated shape is steep like a moth-eye type film is known, for example. In the moth-eye type film, in order to improve a contact angle, a convex part rises substantially perpendicularly to a plane direction, and the height difference of a convex part and a concave part becomes large (for example, several hundred nm). For this reason, once another object enters a recessed part, since the cilia of the cloth for wiping are hard to enter a recessed part, other objects in a recessed part cannot be wiped off.

The resin film may have a thickness of 60 to 150 nm. In the above range, it can be used for the antireflection film.

The resin film may have a water contact angle with respect to distilled water at 25 ° C of 105 to 120 °. In the above range, there may be an antifouling effect.

The resin film can be used for an antireflection film application. Specifically, in the polarizing plate comprising a polarizer, a first optical film formed on the polarizer, a second optical film formed on the lower part of the polarizer, the resin film is coated on the upper part of the first optical film, that is, the top of the polarizing plate, to prevent reflection Can act as a film. The first optical film and the second optical film may be a protective film or a retardation film. Specific examples of the transparent film include polyester-based, cyclic polyolefin-based (COP), triacetyl Cellulose, acrylic, polycarbonate, polyether sulfone, polysulfone, polyamide, polyimide, polyarylate, and polyvinyl alcohol films, including cellulose (TAC) It does not.

<2. Method of Manufacturing Resin Film (10)

Next, a method of manufacturing the resin film 10 will be described. First, the hollow silica particle 20, the photoinitiator, the binder monomer, and the additive 40 are thrown into a solvent, and a coating liquid is produced. Although the kind of solvent is not specifically limited, Boiling point 110? The above ketone solvent is suitably used. This solvent can stably dissolve each material and easily bleed out the photopolymerizable fluoropolymer 41 and the thermopolymerizable fluoropolymer 42. Next, a coating layer is formed by apply | coating (coating) and drying a coating liquid to arbitrary board | substrates. The substrate may be a substrate of a plastic material such as glass or silicon, or may be an optical film. In the case where the substrate is an optical film, an optical film on which a resin film is formed can be obtained, and a polarizing plate including a resin film can be produced when the polarizing plate is adhered to a polarizer. The optical film on which the resin film is formed can serve as a protective film or a retardation film for the polarizer used in the polarizing plate described above and also can provide an antireflection effect. Moreover, a coating method does not have a problem in particular, A well-known method is arbitrarily applied. At this time, the photopolymerizable fluoropolymer 41 and the thermopolymerizable fluoropolymer 42 are bleed out by the repulsive force from the binder monomer, and are localized on the surface of the coating layer. Next, each polymerization reaction is started. As a result, the binder resin 30 is formed, while the photopolymerizable fluoropolymer 41 and the thermopolymerizable fluoropolymer 42 are hollow silica particles 20 and binder resin 30 disposed on the surface of the coating layer. To combine. As a result, the resin film 10 is formed.

In this way, the binder monomer can effectively bleed out the photopolymerizable fluoropolymer 41 and the thermally polymerizable fluoropolymer 42, so that the resin film 10 according to the present embodiment is manufactured by a very simple process. In addition, since the additive 40 is unevenly distributed on the surface of the low refractive index layer 10a, there is no need to attach an antifouling sheet or the like separately to the surface of the low refractive index layer 10a.

<3. Polarizer>

Next, the polarizing plate will be described. The polarizing plate may include a resin film. As a result, the antireflection effect, the slipperiness, the scratch resistance, and the film strength improvement effect can be provided to the polarizing plate. 3, a polarizer 100 according to an exemplary embodiment of the present invention includes a polarizer 110, a first optical film 120 formed on an upper portion of the polarizer 110, a second optical film 120 formed on a lower portion of the polarizer 110, A film 130 and a resin film 140 formed on the first optical film 120. The resin film 140 may include a resin film according to one embodiment of the present invention.

The polarizer 110 may be manufactured from a film made of a polyvinyl alcohol-based resin. As the polyvinyl alcohol-based resin, polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, or a saponified product of an ethylene-vinyl acetate copolymer can be used. The degree of saponification of the film made of the polyvinyl alcohol-based resin may be 99 mol% or more, preferably 99-99.5 mol%, the degree of polymerization may be 2000 or more, preferably 2000-2500, and the thickness may be 10 탆 to 200 탆. The polarizer 110 can be produced by dying and stretching iodine onto a film made of a polyvinyl alcohol-based resin. The stretching ratio may be 2.0-6.0. After stretching, the color correction step may be performed by immersing the boric acid solution and the aqueous potassium iodide solution. The thickness of the polarizer 110 may be 10 占 퐉 to 200 占 퐉 and may be used in a display device in the above range.

The first optical film 120 and the second optical film 130 may be formed of the above-mentioned transparent film as a protective film or a retardation film. Specifically, the first optical film may be a polyethylene terephthalate (PET) film, and the second optical film may be a cyclic polyolefin (COP) film. The first optical film 120 and the second optical film 130 may have a thickness of 10 to 200 탆 and may be used in a display device in the above range. Although the first optical film 120 and the second optical film 130 are formed directly on the polarizer 110 in FIG. 3, although not shown in FIG. 3, the first optical film 120 and the second optical film 130 2 optical film 130 may be formed on the upper and lower sides of the polarizer 110 respectively by an adhesive composition for a polarizing plate. Further, although not shown in Fig. 3, the second optical film may be formed on the display panel and the organic light emitting element by the pressure sensitive adhesive for the polarizing plate.

The resin film 140 may be formed of a resin film according to embodiments of the present invention, and may be formed at the uppermost portion of the polarizing plate to realize an antireflection effect. Although the resin film 140 is formed directly on the first optical film 120 in FIG. 3, a functional layer or an optional optical film (not shown in FIG. 3) may be interposed between the resin film and the first optical film. May be further intervened.

The polarizing plate can be produced by a conventional method. Specifically, a polarizer is manufactured by the above-described method, a resin film is coated on one surface of the first optical film, a first optical film is bonded to the upper surface of the polarizer with a surface facing the resin film, And then adhering the film.

<4. Display device>

Next, the display device will be described. The display device according to an embodiment of the present invention may include a resin film, or a polarizing plate including a resin film. The display device may be a liquid crystal display device, an organic light emitting diode display device, or the like.

Example

(Example 1)

Next, an embodiment of the present embodiment will be described. In Example 1, the resin film 10 was produced by the following production method.

55 mass% (mass part) pentaerythritol triacrylate (Shin Nakamura Chemical Co., Ltd.) A-TMM-3LMN) as a monomer for a binder, 40 mass% hollow silica particles (Nikki catalyst property) Thru 4320), 1.8% by mass of photopolymerizable perfluoropolyether (PFPE) (Shin-Etsu Chemical Co., Ltd. KY-1203) and 0.2% by mass of thermopolymerizable PFPE (Shin-Etsu) Chemical industry KY-108) and 3 mass% photoinitiator (BASF JAPAN Irgacure 184) were prepared. And these materials were put into 8000 mass% methyl isobutyl ketone (MIBK), and it stirred, and created the coating liquid.

Here, the particle size of the hollow silica particles was a value within the range of 50 nm to 60 nm. Therefore, the average particle diameter also becomes a value within the corresponding range. The refractive index of the hollow silica particles was 1.25. In addition, the surface tension of pentaerythritol triacrylate was 39.8 dyne / cm. The weight average molecular weight (Mw) of the photopolymerizable PFPE was 8000 g / mol and the surface tension was 16.7 dyne / cm. In addition, the weight average molecular weight (Mw) of the thermopolymerizable PFPE was 17000 g / mol, and the surface tension was 16.5 dyne / cm. In addition, the measurement was performed by the apparatus or simulation software mentioned above.

Next, the coating liquid was applied onto a substrate made of PMMA, and dried at 90 ° C. for about 1 minute to form a coating layer. Subsequently, the coating layer was cured by irradiating ultraviolet light (metal halide lamp: light quantity 1000mJ / cm ² ) for 5 seconds with nitrogen atmosphere (oxygen concentration of 1000 ppm or less). Thus, a resin film was formed. The average thickness of the resin film was about 110 nm. As a film thickness measuring method, the visible spectroscopic ellipsometer SMART SE etc. of HORIBA Corporation are mentioned, for example. Here, average thickness was made into the arithmetic mean of the maximum value and minimum value of a measured value.

(Examples 2 to 12, Comparative Examples 1 to 13)

Except having changed the content rate of each material, the kind of additive, and the kind of binder monomer, the resin film which concerns on Examples 2-12 and Comparative Examples 1-13 was created by performing the process similar to Example 1. Here, the content rate of each material, the kind of additive, and the kind of binder monomer are put together in Table 1, and are shown.

<Table 1>

In Table 1, * 1 shows the monomer for a binder which does not have a hydrogen bond former (specifically, a hydroxyl group), ie, pentaerythritol tetraacrylate (surface tension 38.9 dyne / cm). * 2 represents the monomer for a binder which does not have a hydroxyl group, ie isocyanurate triacrylate (surface tension 38.8 dyne / cm). * 3 represents the monomer for a binder which does not have a hydroxyl group, ie, dipentaerythritol hexaacrylate (surface tension 40.1 dyne / cm). * 4 represents the monomer for a binder which has a hydroxyl group, ie, isocyanurate diacrylate (surface tension 40.2 dyne / cm).

* 5 represents a photopolymerizable silicone polymer (Shin-Etsu Chemical Co., Ltd. X-22-164E. Surface tension 19.1 dyne / cm. MW is about 12000 g / mol). * 6 represents a photopolymerizable fluoropolymer (Daikin Industries Co., Ltd. Otsuru DAC. Surface tension of 16.9 dyne / cm. MW is about 8000 g / mol). * 7 is a thermopolymerizable fluoropolymer (Shin-Etsu Chemical Co., Ltd. KY-164. Surface tension of 16.1 dyne / cm. MW is about 18000 g / mol).

※ 8 shows ethoxylated (n = 6) trimethylolpropane triacrylate (surface tension 38.9 dyne / cm), ※ 9 is propoxylated (n = 6) trimethylolpropane triacrylate (surface tension) 34.1 dyne / cm). In addition, unattended shows the same material as Example 1.

(exam)

Next, the following tests were done about the resin film which concerns on each Example and a comparative example.

(Rubber eraser rub test)

The surface of the substrate coated with the resin film was subjected to abrasion 100 times with a rubber eraser while applying a load of 500 g / cm ^{2 in} the vertical direction (up and down direction). The rubber eraser used MONOPE-04A manufactured by TOMBOW PENCIL CO., LTD.

(evaluation)

The following evaluation was performed about each resin film.

(Evaluation of island structure)

Whether the islands-in-the-sea structure was formed in the resin film of the initial stage (before performing the rubber rub rub test) was determined using the shape measurement microscope mentioned above. In addition, in this evaluation, when the height difference h was measured with the number of measurement points as 5, and it was determined that the height difference h became 20 nm or more, it was determined that the island-in-sea structure was formed.

(High and low evaluation)

The elevation difference (h) was measured about the resin film in which the sea-island structure was confirmed. The shape measurement microscope mentioned above was used for the measurement. In addition, the number of measurement points was made into five.

(Slow evaluation)

The angle between the inclination of each point on the surface of the resin film and the surface direction was measured. The shape measurement microscope mentioned above was used for the measurement. That is, arbitrary regions were selected as the observation field from the surface of the resin film, and three-dimensional data of the entire observation field was obtained. And based on the three-dimensional data, the angle | corner of the inclination of each point on the surface of a resin film, and surface direction was measured.

(Evaluation of contact angle (CA, unit: °))

The contact angle was measured by dropping 2 µl of pure water onto a substrate coated with a resin film using a fully automatic contact angle meter DM700 (manufactured by Kyowa Interface Science Co., Ltd.). In addition, this evaluation was performed with respect to both the resin film of an initial stage (before performing a rubber eraser rub test), and the resin film after a rubber eraser rub test.

(Magic wipe evaluation)

About 3 cm line was drawn with the magic pen on the surface (namely, the surface of the resin film) of the board | substrate which coated the resin film, and left to stand for 1 minute. After that, it was wiped off as a circle with Kimwipe. The Magic Pen uses Mckee black fine powder manufactured by ZEBRA, and the Kim Wipe used Kim Wiper S-200 manufactured by Japan Paper Cresia. Then, the presence or absence of what remained after wiping with the naked eye was confirmed. Nothing left after wiping was called OK, and what remained after wiping was called NG.

(Fingerprint adhesion and wiping evaluation)

Fingerprints at the fingertips were pressed to the surface of the substrate coated with the resin film (that is, the surface of the resin film) so as to have a load of about 200 g. After that, I wiped the circle with Kimwipe 20 times. Kimwipe used Kimwiper Wiper S-200 manufactured by Nippon Paper Cresia. Then, the presence or absence of the fingerprint was visually confirmed. Then, the presence or absence of what remained after wiping with the naked eye was confirmed. Nothing left after wiping was made OK, and what remained after wiping was made into NG. The evaluation results are shown in Table 2.

<Table 2>

On the other hand, in the resin film which concerns on an Example, it was confirmed that uneven | corrugated shape is smooth. That is, the angle mentioned above was ± 30 degrees or less over the entire field of view of the shape measurement microscope.

When comparing an Example and a comparative example, except for the comparative example 6, the comparative example did not identify the original seam structure. Moreover, the Example obtained the favorable result not only the initial characteristic but also the characteristic after a rubber eraser rub test. On the other hand, in the comparative example, although the initial characteristic of a contact angle was favorable, the result after a rubber eraser rub test was not good. Therefore, good properties can be obtained by forming a binder resin using at least a photopolymerizable fluoropolymer as an additive and using a binder monomer that repels the photopolymerizable fluoropolymer and the like, and the content of each material is in the above-described range. It can be seen. Moreover, according to Example 9 and the comparative example 7, it turns out that a photopolymerizable fluoropolymer becomes an essential structure of this embodiment, but a thermopolymerizable fluoropolymer is arbitrary structures.

By the above, according to this embodiment, the resin film 10 couple | bonds with the hollow silica particle distributed on the surface of the low refractive index layer 10a, and also the additive 40 which repels with the binder resin 30 is carried out. Equipped. Therefore, since the additive 40 bleeds out effectively by the repulsive force by the binder resin 30, the resin film 10 can localize the additive 40 on the surface of the low refractive index layer 10a. As a result, in the present embodiment, the antifouling property, slipperiness, scratch resistance, and film strength of the resin film 10 can be improved.

In addition, in this embodiment, since the island-in-the-sea structure is formed in the surface of the low refractive index layer 10a, the frictional force between the surface of the resin film 10 and another object can be reduced by this island-in-water structure, and furthermore, the resin film The antifouling property, slipperiness, and scratch resistance of (10) can be improved.

Moreover, in this embodiment, since the content rate of each material is made into the value within a predetermined range, the recessed part and convex part whose height difference becomes 30 nm-65 nm can be formed more reliably in a low refractive index layer.

In addition, since the binder resin 30 has a hydrogen bond former, the additive 40 can be effectively bleeded out.

And since the binder resin 30 has a hydroxyl group as a hydrogen bond former, the additive 40 can be effectively bleeded out.

The weight average molecular weight of the thermopolymerizable fluoropolymer 42 is greater than the weight average molecular weight of the photopolymerizable fluoropolymer 41. Thus, the additive 40 can be effectively bleed out. In addition, since the photopolymerizable fluoropolymer 41 functions as a compatibilizer, the solubility of the additive 40 in the solvent is improved.

In addition, since the weight average molecular weight of the thermopolymerizable fluoropolymer is 10000 g / mol or more, and the weight average molecular weight of the photopolymerizable fluoropolymer is less than 10000 g / mol, the additive 40 can be effectively bleeded out. In addition, since the photopolymerizable fluoropolymer 41 functions as a compatibilizer, the solubility of the additive 40 in the solvent is improved.

And since the resin film 10 can be created only by apply | coating the coating liquid in which each material melt | dissolved, and starting a polymerization reaction, it is created easily.

As mentioned above, although preferred embodiment of this invention was described in detail, referring an accompanying drawing, this invention is not limited to this example. It will be understood by those skilled in the art that various changes and modifications may be made without departing from the scope of the invention as defined in the appended claims. But is to be understood as falling within the technical scope of the invention.

10: resin film, 10a: low refractive index layer
10b: convex portion, 10c: concave portion
20: hollow silica particles, 30: binder resin
40: additive, 41: photopolymerizable fluoropolymer
42: thermopolymerizable fluoropolymer
100: polarizer, 110: polarizer, 120: first optical film, 130: second optical film, 140:

Claims (15)

A plurality of hollow silica particles and a binder resin for bonding the hollow silica particles to each other, wherein recesses and protrusions having different layer thicknesses are formed, and the height difference between the recesses and the protrusions is 30 nm to 65 nm. A refractive index layer,
A resin film comprising a photopolymerizable fluoropolymer bonded to hollow silica particles distributed on the surface of the low refractive index layer and having a lower surface tension than the binder resin. 2. The photopolymerizable fluorine polymer according to claim 1, wherein the photopolymerizable fluorine polymer is bonded to the hollow silica particles distributed on the surface of the low refractive index layer and has a lower surface tension than the binder resin. Polymers,
The content rate of the said hollow silica particle is larger than 5 mass%, and smaller than 50 mass%,
The sum total of the content rate of the said photopolymerizable fluoropolymer and the said thermopolymerizable fluoropolymer is 1.5 mass% or more and 7 mass% or less,
The content rate of the said photopolymerizable fluoropolymer is 1.5 mass% or more,
The ratio of the content rate of the thermally polymerizable fluoropolymer to the content rate of the photopolymerizable fluoropolymer is less than 0.43. The resin film according to claim 1, wherein the binder resin has a hydrogen bond forming group capable of forming a hydrogen bond with another functional group. The resin film according to claim 3, wherein the binder resin has a hydroxyl group as the hydrogen bond former. The resin film of Claim 2 whose weight average molecular weight of the said thermopolymerizable fluoropolymer is larger than the weight average molecular weight of the said photopolymerizable fluoropolymer. 6. The resin film according to claim 5, wherein a weight average molecular weight of the thermopolymerizable fluoropolymer is 10000 g / mol or more, and a weight average molecular weight of the photopolymerizable fluoropolymer is less than 10000 g / mol. The resin film of claim 1, wherein the low refractive index layer has a refractive index of 1.10 to 1.45. The resin film of claim 1, wherein the low refractive index layer has a sea island structure. The resin film according to claim 2, wherein the photopolymerizable fluoropolymer and the thermopolymerizable fluoropolymer are localized on the surface of the low refractive index layer. The resin film according to claim 1, wherein the hollow silica particles are uniformly dispersed on the surface of the low refractive index layer. The resin film according to claim 1, wherein the resin film has a water contact angle of 100 to 120 ° with respect to distilled water at 25 ° C. The polarizing plate containing the resin film of any one of Claims 1-11. At least photopolymerizable fluorine among the photopolymerizable fluoropolymer and thermally polymerizable fluoropolymer which can bind the hollow silica particles, the binder monomer which can couple the said hollow silica particles, and the said hollow silica particle, and repels the said binder monomer. Generating a coating liquid comprising a polymer;
Applying the coating liquid to a substrate; And
Initiating a polymerization reaction,
The content rate of the said hollow silica particle is larger than 5 mass%, and smaller than 50 mass%,
The sum total of the content rate of the said photopolymerizable fluoropolymer and the said thermopolymerizable fluoropolymer is 1.5 mass% or more and 7 mass% or less,
The content rate of the said photopolymerizable fluoropolymer is 1.5 mass% or more,
The ratio of the content rate of the said thermopolymerizable fluoropolymer and the content rate of the said photopolymerizable fluoropolymer is less than 0.43, The manufacturing method of the resin film characterized by the above-mentioned. The method of claim 13, wherein the substrate is a polarizer protective film. A display device comprising the polarizing plate of claim 12.

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