JP2021143237A - Resin film, method of producing resin film, and display device - Google Patents

Abstract

To provide, e.g., a resin film on which, even if an extraneous material adheres, the adhering extraneous material is less likely to be visible and can be easily wiped out.SOLUTION: A resin film includes: a binder 171 including a resin; hollow silica particles 172 distributed in the binder 171; and an oil-repellent surface modifying agent and a lipophilic surface modifying agent that are mainly distributed on the surface side of the binder 171. In this case, the mass mixing ratio of the lipophilic surface modifying agent to the oil-repellent surface modifying agent is preferably from 0.05 to 20 inclusive.SELECTED DRAWING: Figure 2

Description

The present invention relates to a resin film or the like. More specifically, the present invention relates to a resin film or the like provided on the surface of the display means of the display device.

For example, in a display device provided with a liquid crystal panel, a polarizing film may be provided on the outermost surface thereof. It is desirable that the polarizing film has a function of suppressing reflection. Therefore, a resin film for making it difficult to reflect light emitted from the outside may be provided on the surface side as a low refractive index layer. Since the low refractive index layer is located on the outermost surface of the liquid crystal panel, deposits made of sebum Y or the like are likely to adhere to it. Therefore, it is desirable that the low refractive index layer can easily wipe off the deposits.

Patent Document 1 discloses an antireflection film. This antireflection film comprises a hard coat layer provided on a transparent substrate. The antireflection film is further provided with a low refractive index layer provided on the hard coat layer and having a lower refractive index than the hard coat layer. The low refractive index layer contains hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less, and the low refractive index layer further contains a binder resin and a surface modifier present on the surface. The surface modifier contains a silicon-containing compound and a fluorine-containing compound. The reflection Y value of the antireflection film measured from the low refractive index layer side is less than 0.3%. When the steel wool resistance test is performed on the surface of the low refractive index layer, the maximum load at which no scratches are confirmed is 200 g / cm ² or more.

Patent Document 2 discloses an antireflection optical film. This antireflection optical film has at least a hard coat layer and a low refractive index layer laminated on one surface of the hard coat layer. On the surface of the low refractive index layer opposite to the hard coat layer side, the root mean square roughness Rq, the ten-point average roughness Rz, and the maximum height roughness Ry are measured, respectively, with a cutoff wavelength of 2.5 mm. As a result, Rq is 0.010 μm or more and 0.050 μm or less. Further, Rz is 0.050 μm or more and 0.250 μm or less. Further, Ry is 0.050 μm or more and 0.350 μm or less.

Special Table 2019-148805 JP-A-2018-128541

In recent years, the low refractive index layer is required to have further low reflection. Therefore, the low refractive index layer may contain many hollow silica particles.
However, if a large amount of hollow silica particles are contained, it tends to be conspicuous when deposits are attached. Furthermore, it tends to be difficult to wipe off.
An object of the present invention is to provide a resin film or the like in which the deposits are inconspicuous even if the deposits adhere and the deposits can be easily wiped off.

The resin film of the present invention has a binder containing a resin, hollow silica particles distributed in the binder, an oil-repellent surface modifier, and a lipophilic surface modifier. Oil-repellent surface modifiers and lipophilic surface modifiers are mainly distributed on the surface side of the binder.
Here, the mass mixing ratio of the lipophilic surface modifier to the oil-repellent surface modifier can be 0.05 or more and 20 or less.
Further, the mass compounding ratio of the lipophilic surface modifier to the oil-repellent surface modifier can be 1 or more and 20 or less.
Further, at least one of the oil-repellent surface modifier and the oil-repellent surface modifier can have a reactive group that binds to the resin.
The oil-repellent surface modifier can be a fluorine-based compound having a photopolymerizable group.
In addition, at least a part of each of the oil-repellent surface modifier and the lipophilic surface modifier can be exposed on the surface side of the binder.
Further, the resin can be made to contain a fluororesin.
The hollow silica particles can have an average primary particle size of 35 nm or more and 100 nm or less.

Further, the resin film of the present invention has a binder containing a resin and hollow silica particles distributed in the binder. The surface of the binder is a mixture of oil-repellent parts and lipophilic parts.

The method for producing a resin film of the present invention includes a preparation step, a coating step, and a curing step. The preparatory step prepares a coating solution for preparing a resin film, and the coating step applies a coating solution to prepare a coating film. The curing step cures the applied coating film. The coating solution contains monomers and / or oligomers, hollow silica particles, an oil-repellent surface modifier, a lipophilic surface modifier, and a solvent. Monomers and / or oligomers are polymerized to form resins. The solvent disperses them.

Further, the display device of the present invention includes a display means for displaying an image and a low refractive index layer formed on the surface of the display means. The low refractive index layer has a binder containing a resin, hollow silica particles distributed in the binder, and an oil-repellent surface modifier and a lipophilic surface modifier. Oil-repellent surface modifiers and lipophilic surface modifiers are mainly distributed on the surface side of the binder.

The optical member of the present invention includes a base material and the above-mentioned resin film provided on the base material.

Further, the polarizing member of the present invention includes a polarizing means for polarizing light and the above-mentioned resin film provided on the polarizing means.

Further, the coating solution for forming a resin film of the present invention contains a monomer and / or an oligomer, hollow silica particles, an oil-repellent surface modifier, a lipophilic surface modifier, and a solvent. Monomers and / or oligomers are polymerized to form resins. The solvent disperses them.
Here, the mass mixing ratio of the lipophilic surface modifier to the oil-repellent surface modifier can be 1 or more and 20 or less.

According to the present invention, it is possible to provide a resin film or the like in which the deposits are easily wiped off even if the deposits are inconspicuous.

(A) is a figure explaining the display device to which this embodiment is applied. FIG. 1B is a cross-sectional view taken along the line Ib-Ib of FIG. 1A, showing an example of the configuration of the liquid crystal panel to which the present embodiment is applied. It is a figure which showed about the low refractive index layer. (A) to (c) are conceptual diagrams showing the state of the surface modifier on the surface of the low refractive index layer. It is a flowchart explaining the method of making the low refractive index layer of this embodiment. It is a figure which showed the component of the coating solution.

Hereinafter, embodiments for carrying out the present invention will be described in detail. The present invention is not limited to the following embodiments. In addition, it can be modified in various ways within the scope of the gist. Further, the drawings used are for explaining the present embodiment and do not represent the actual size.

<Explanation of display device>
FIG. 1A is a diagram illustrating a display device 1 to which the present embodiment is applied.
The illustrated display device 1 is, for example, a liquid crystal display for a PC (Personal Computer), a liquid crystal television, or the like. The display device 1 displays an image on the liquid crystal panel 1a.

<Explanation of liquid crystal panel 1a>
FIG. 1B is a cross-sectional view taken along the line Ib-Ib of FIG. 1A, showing an example of the configuration of the liquid crystal panel 1a to which the present embodiment is applied.
The liquid crystal panel 1a is an example of a display means for displaying an image. The liquid crystal panel 1a of the present embodiment is, for example, a VA type liquid crystal panel. The illustrated liquid crystal panel 1a has a backlight 11 and a polarizing film 12a. Further, the liquid crystal panel 1a includes a retardation film 13a, a liquid crystal 14, a retardation film 13b, and a polarizing film 12b. Further, the liquid crystal panel 1a has a hard coat layer 15, a high refractive index layer 16, and a low refractive index layer 17. Then, these have a structure in which they are laminated in this order. Hereinafter, when the polarizing film 12a and the polarizing film 12b are not distinguished, they may be simply referred to as the polarizing film 12. Further, when the retardation film 13a and the retardation film 13b are not distinguished, it may be simply referred to as the retardation film 13.

The backlight 11 irradiates the liquid crystal 14 with light. The backlight 11 is, for example, a cold cathode fluorescent lamp or a white LED (Light Emitting Diode).
The polarizing film 12a and the polarizing film 12b are examples of polarizing means for polarizing light. The polarization directions of the polarizing film 12a and the polarizing film 12b are orthogonal to each other. The polarizing film 12a and the polarizing film 12b include, for example, a resin film in which an iodine compound molecule is contained in polyvinyl alcohol (PVA). Then, this is sandwiched and bonded with a resin film made of triacetylcellulose (TAC). Light is polarized by including iodine compound molecules.

The retardation film 13 compensates for the viewing angle dependence of the liquid crystal panel 1a. The light transmitted through the liquid crystal 14 changes its polarization state from linearly polarized light to elliptically polarized light. For example, when the liquid crystal panel 1a is displayed in black, the liquid crystal panel 1a looks black when viewed from the vertical direction. On the other hand, when the liquid crystal panel 1a is viewed from an oblique direction, the retardation of the liquid crystal 14 occurs. Also, the axis of the polarizing film 12 is no longer 90 °. Therefore, there arises a problem that light is lost, the image becomes white, and the contrast is lowered. That is, the liquid crystal panel 1a is dependent on the viewing angle. The retardation films 13a and 13b have a function of returning the elliptically polarized light to linearly polarized light. As a result, the retardation films 13a and 13b can compensate for the viewing angle dependence of the liquid crystal panel 1a.

A power supply (not shown) is connected to the liquid crystal 14, and when a voltage is applied by this power supply, the arrangement direction of the liquid crystal 14 changes. Then, the liquid crystal 14 controls the light transmission state by this.
In the case of the VA type liquid crystal panel, when no voltage is applied to the liquid crystal 14 (voltage OFF), the liquid crystal molecules are arranged in the vertical direction in the figure. Then, when the light is irradiated from the backlight 11, the light first passes through the polarizing film 12a and becomes polarized light. Then, the polarized light passes through the liquid crystal 14 as it is. Further, since the polarizing film 12b has different polarization directions, this polarization is blocked. In this case, the user who sees the liquid crystal panel 1a cannot visually recognize this light. That is, when no voltage is applied to the liquid crystal 14, the color of the liquid crystal is "black".

On the other hand, when the maximum voltage is applied to the liquid crystal 14, the liquid crystal molecules are arranged in the horizontal direction in the figure. Then, the polarized light that has passed through the polarizing film 12a is rotated by 90 degrees in the direction of polarization due to the action of the liquid crystal display 14. Therefore, the polarizing film 12b does not block this polarized light but allows it to pass through. In this case, the user who sees the liquid crystal panel 1a can visually recognize this light. That is, when the maximum voltage is applied to the liquid crystal 14, the color of the liquid crystal is "white". The voltage can also be between the voltage OFF and the maximum voltage. In this case, the liquid crystal 14 is in a state between the vertical direction in the figure and the vertical direction with respect to the vertical direction in the figure. That is, the liquid crystals 14 are arranged in the oblique direction, which is a direction that intersects both the vertical direction and the vertical direction. In this state, the color of the liquid crystal is "gray". Therefore, by adjusting the voltage applied to the liquid crystal 14 between OFF and the maximum voltage, it is possible to express intermediate gradations in addition to black and white. Then, the image is displayed by this.
Although not shown, a color image can be displayed by using a color filter.

The hard coat layer 15 is a functional layer for making it difficult for the liquid crystal panel 1a to be scratched. The hard coat layer 15 is made of, for example, a binder as a base material containing a resin as a main component. As the binder, the same binder as those exemplified in the low refractive index layer 17 described later can be used.
Further, in addition to the binder, metal oxide particles can be included. As the metal oxide particles, for example, zirconium oxide, tin oxide, titanium oxide, cerium oxide and the like can be used. As a result, the hard coat property of the hard coat layer 15 is improved.
Further, a conductive substance may be added. The conductive substance is, for example, metal fine particles or a conductive polymer. More specifically, the conductive substance is, for example, an antimony (Sb), phosphorus (P), indium (In) -doped tin oxide, an ionic liquid containing a fluorine-based anion or an ammonium salt, PEDOT / PSS, or the like. Conductive polymers, carbon nanotubes, etc. Further, the conductive substance is not limited to one type, and two or more types may be added. As a result, the surface resistance value of the hard coat layer 15 is lowered, and the hard coat layer 15 can be provided with an antistatic function.

The high refractive index layer 16 is provided under the low refractive index layer 17, and is a functional layer for further reducing the reflectance.
The high refractive index layer 16 includes a binder and high refractive index particles. The high refractive index layer 16 can be formed from, for example, a coating solution containing a binder and high refractive index particles. The high refractive index layer 16 may be formed as a single layer or as a plurality of layers, but it is preferable to form the high refractive index layer 16 with as few layers as possible from the viewpoint of manufacturing cost.

In order to reduce the reflection of the liquid crystal panel 1a, it is preferable to increase the refractive index of the high refractive index layer 16. The specific refractive index is preferably 1.55 or more and 1.80 or less, and more preferably 1.60 or more and 1.75 or less.
The upper limit of the thickness of the high refractive index layer 16 is preferably 500 nm or less. Further, 350 nm or less is more preferable, and 200 nm or less is further preferable. The lower limit of the thickness of the high refractive index layer 16 is preferably 50 nm or more. Further, 80 nm or more is more preferable, and 100 nm or more is further preferable.

High refractive index particles include zirconium oxide, hafnium oxide, tantalum oxide, titanium oxide, zinc oxide, aluminum oxide, magnesium oxide, tin oxide, yttrium oxide, barium titanate, antimony-doped tin oxide (ATO), and phosphorus-doped tin oxide (ATO). PTO), indium-doped tin oxide (ITO), zinc sulfide and the like. From the viewpoint of durability stability, zirconium oxide, barium titanate, antimony-doped tin oxide (ATO), phosphorus-doped tin oxide (PTO), and indium-doped tin oxide (ITO) are particularly preferable.

The average particle size (average primary particle size) of the primary particles of the high refractive index particles is preferably 1 nm or more and 200 nm or less. Further, it is more preferably 3 nm or more and 100 nm or less, and further preferably 5 nm or more and 50 nm or less.
The average primary particle size of high refractive index particles can be measured by observation images using SEM (Scanning Electron Microscope), TEM (Transmission Electron Microscope) and STEM (Scanning Transmission Electron Microscope) of the dry film of the particle dispersion. Is.

The high-refractive index particles are preferably subjected to a dispersion stabilization treatment from the viewpoint of suppressing aggregation. Examples of the means for stabilizing the dispersion include those using surface-treated particles and means for adding a dispersant. Further, there is also a means for adding another particle having a smaller amount of surface charge than the high refractive index particle.

The content of the high refractive index particles is preferably 20 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the binder. Further, it is more preferably 50 parts by mass or more and 400 parts by mass or less, and further preferably 100 parts by mass or more and 300 parts by mass or less.

As the binder, the same binder as those exemplified in the low refractive index layer 17 described later can be used. However, in order to reduce the content of high refractive index particles, the refractive index of the binder is preferably about 1.50 or more and 1.70 or less.
The high refractive index layer 16 may contain other components in addition to the binder and the high refractive index particles, if necessary. For example, it may contain additives such as a polymerization initiator, an ultraviolet absorber, a leveling agent, a surfactant, and a diluting solvent. The surface state of the high refractive index layer 16 can be controlled by adding a leveling agent, a surfactant, or the like, and as a result, the performance of the upper layer can be improved. In this case, the upper layer is, for example, a low refractive index layer 17.

FIG. 2 is a diagram showing the low refractive index layer 17.
Here, in the figure, the upper side is the surface side of the liquid crystal panel 1a, and the lower side is the inner side of the liquid crystal panel 1a.
The low refractive index layer 17 is an example of a resin film, and is a functional layer for reducing the reflectance of the liquid crystal panel 1a.
The low refractive index layer 17 has a lower refractive index than the high refractive index layer 16. Specifically, the low refractive index layer 17 preferably has a refractive index of 1.20 or more and 1.32 or less. In this case, the SCI (Specular Component Include) reflectance Y, which will be described later, is 0.3 or less. As a result, a liquid crystal panel 1a having a low reflectance can be realized. The low refractive index layer 17 may be formed as a single layer or as a plurality of layers, but it is preferable to form the low refractive index layer 17 with as few layers as possible from the viewpoint of manufacturing cost. The low refractive index layer 17 preferably has a thickness of 50 nm or more and 500 nm or less.

The low refractive index layer 17 includes a binder 171 and hollow silica particles 172 distributed in the binder 171. Further, the low refractive index layer 17 further contains a surface modifier 173 that is mainly distributed on the surface side of the binder 171.

The binder 171 has a network structure and connects the hollow silica particles 172 to each other. The binder 171 contains a resin as a main component. The resin preferably contains a fluororesin. In this case, all the resins may be fluororesins, and some of them may be fluororesins. The fluororesin is a resin containing fluorine, for example, polytetrafluoroethylene (PTFE). Also, for example, perfluoroalkoxy alkane (PFA). Further, for example, perfluoroethylene propene copolymer (FEP) and ethylene tetrafluoroethylene copolymer (ETFE). Fluororesin has a low refractive index. Therefore, by using the fluororesin, the low refractive index layer 17 tends to have a lower refractive index, and the reflectance can be further reduced.

Further, the fluororesin is more preferably a photocurable fluororesin. The photocurable fluororesin is a photopolymerizable fluoropolymer represented by the following general formulas (1) and (2). Then, the structural unit M is contained in an amount of 0.1 mol% or more and 100 mol% or less. Further, the structural unit A is contained in an amount of more than 0 mol% and 99.9 mol% or less. Further, the number average molecular weight is 30,000 or more and 1,000,000 or less.

In the general formula (1), the structural unit M is a structural unit derived from the fluorine-containing ethylenic monomer represented by the general formula (2). The structural unit A is a structural unit derived from a monomer copolymerizable with the fluorine-containing ethylenic monomer represented by the general formula (2).
In the general formula (2), X ¹ and X ² are H or F. Also, X ³ is H, F, CH ₃ or CF ₃ . X ⁴ and X ⁵ are H, F or CF ₃ . Rf is an organic group in the fluorine-containing alkyl group having ether bond having 1 or more and 40 or less of the fluorine-containing alkyl group or 100 having two or more carbon atoms or less carbon atoms, Y ¹ is bonded to one or more 3 or less. Y ¹ is a monovalent organic group having an ethylenic carbon-carbon double bond at the terminal and having 2 to 10 carbon atoms. Further, a is 0, 1, 2 or 3, and b and c are 0 or 1.
As the photopolymerizable fluororesin, for example, OPTOOL AR-100 manufactured by Daikin Industries, Ltd. can be exemplified.

The hollow silica particles 172 have an outer shell layer, and the inside of the outer shell layer is a hollow or porous body. The outer shell layer and the porous body are mainly composed of silicon oxide (SiO ₂ ). In addition, a large number of photopolymerizable groups and hydroxyl groups are bonded to the surface side of the outer shell layer. The photopolymerizable group and the outer shell layer are bonded via at least one of the Si—O—Si bond and the hydrogen bond. Examples of the photopolymerizable group include an acryloyl group and a methacryloyl group. That is, the hollow silica particles 172 contain at least one of an acryloyl group and a methacryloyl group as a photopolymerizable group. The photopolymerizable group is also referred to as an ionizing radiation curable group. The hollow silica particles 172 may have at least photopolymerizable groups, and the number and types of these functional groups are not particularly limited.

The average primary particle size of the hollow silica particles 172 is preferably 35 nm or more and 100 nm or less. Further, it is more preferable that the average primary particle diameter of the hollow silica particles 172 is 50 nm or more and 85 nm or less. When the average primary particle size is less than 35 nm, the porosity of the hollow silica particles 172 tends to be small. Therefore, the effect of lowering the refractive index of the low refractive index layer 17 is less likely to occur. Further, when the central particle size exceeds 100 nm, the unevenness of the surface of the low refractive index layer 17 tends to be remarkable. Therefore, the antifouling property and the scratch resistance are likely to decrease.

The average primary particle size of the hollow silica particles 172 can be measured in the same manner as in the case of the high refractive index layer 16. That is, it is possible to measure by the observation image using SEM, TEM and STEM of the dry film of the particle dispersion liquid.

The blending amount of the hollow silica particles 172 is preferably 30% by mass or more and 65% by mass or less in the low refractive index layer 17. When the blending amount of the hollow silica particles 172 is less than 30% by mass, the reflectance of the low refractive index layer 17 tends to be high. Further, when the blending amount of the hollow silica particles 172 exceeds 65% by mass, the film strength tends to decrease. Further, the deposits are easily noticeable and difficult to wipe off.

Further, the hollow silica particles 172 can have a plurality of maximum values in the frequency curve (particle size distribution curve) with respect to the particle size of the hollow silica particles 172. That is, in this case, the hollow silica particles 172 are composed of a plurality of particles having different particle size distributions. For example, a plurality of hollow silica particles 172 having an average primary particle diameter of 30 nm, 60 nm, and 75 nm are selected and mixed for use.

The surface modifier 173 is mainly distributed on the surface side of the binder 171 to modify the surface of the low refractive index layer 17. That is, the surface modifier 173 is segregated on the surface side of the low refractive index layer 17. Even if it exists inside the binder 171, it does not impair the function of the low refractive index layer 17.
In this embodiment, the surface modifier 173 includes an oil-repellent surface modifier and a lipophilic surface modifier.

The oil-repellent surface modifier plays a role of improving the oil-repellent property of the film surface by blending it with binder 171 or the like and segregating it on the surface. The effect of the oil-repellent surface modifier can be confirmed by measuring the contact angle of oleic acid or the like. In this case, the effect can be confirmed by the difference in the contact angle of the film surface between when the oil-repellent surface modifier is added and when it is not added (contact angle when added-contact angle when not added). In this case, the contact angle becomes larger when an oil-repellent surface modifier is added. The difference in contact angles is preferably 10 ° or more. Further, the difference in contact angle is more preferably 20 ° or more, and further preferably 30 ° or more.

The oil-repellent surface modifier is preferably a fluorine-based compound having a photopolymerizable group.
Specific examples of the oil-repellent surface modifier include KY-1203 and KY-1207 manufactured by Shin-Etsu Chemical Co., Ltd. Further, for example, Optool DAC-HP manufactured by Daikin Industries, Ltd. can be mentioned. Further, for example, Megafvck F-477, F-554, F-556, F-570, RS-56, RS-75, RS-78, RS-90 manufactured by DIC Corporation can be mentioned. Further, for example, FS-7024, FS-7025, FS-7026, FS-7031, and FS-7032 manufactured by Fluorotechnology Co., Ltd. can be mentioned. Further, for example, H-3595 and H-3594 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. can be mentioned. Further, for example, SURECO AF Series manufactured by AGC Inc. can be mentioned. Then, for example, Futergent F-222F, M-250, 601AD, 601ADH2 manufactured by Neos Co., Ltd. can be mentioned.

The lipophilic surface modifier plays a role of improving the lipophilicity of the film surface by blending it with binder 171 or the like and segregating it on the surface. The effect of the lipophilic surface modifier can be confirmed by measuring the contact angle of oleic acid or the like. In this case, the effect can be confirmed by the difference in the contact angle of the film surface between when the lipophilic surface modifier is not added and when it is added (contact angle when not added-contact angle when added). In this case, the contact angle becomes smaller when a lipophilic surface modifier is added. The difference in contact angles is preferably 3 ° or more. Further, the one having a contact angle difference of 5 ° or more is more preferable, and the one having a contact angle difference of 7 ° or more is further preferable.

Specific examples of the lipophilic surface modifier include Mercuria 350L manufactured by Sanyo Chemical Industries, Ltd. Further, for example, Futergent 730LM, 602A, 650A, 650AC manufactured by Neos Co., Ltd. can be mentioned.

3A to 3C are conceptual diagrams showing the state of the surface modifier 173 on the surface of the low refractive index layer 17. Here, in the figure, the upper side is the surface side of the liquid crystal panel 1a, and the lower side is the inner side of the liquid crystal panel 1a.

FIG. 3A is a diagram showing a case where the oil-repellent surface modifier 173a is used and the lipophilic surface modifier 173b is not used. Further, FIG. 3B is a diagram showing a case where the lipophilic surface modifier 173b is used and the oil-repellent surface modifier 173a is not used. Further, FIG. 3C is a diagram showing a case where both the oil-repellent surface modifier 173a and the lipophilic surface modifier 173b are used. That is, FIG. 3C is a conceptual diagram showing the state of the surface of the low refractive index layer 17 of the present embodiment.

In the case of FIG. 3A, the surface of the low refractive index layer 17 is mainly covered with the oil-repellent surface modifier 173a. Then, for example, when sebum Y adheres here, since sebum Y is an oil component, the wettability with respect to the oil-repellent surface modifier 173a is poor. That is, the sebum Y is repelled by the oil-repellent surface modifier 173a. As a result, the sebum Y tends to be beaded on the surface of the low refractive index layer 17. In this case, when the sebum Y is wiped off, the amount of the sebum Y adhered after wiping off is small. On the other hand, when the sebum Y adheres, the ball-shaped sebum Y can be visually confirmed, and the dirt is easily conspicuous.

In the case of FIG. 3B, the surface of the low refractive index layer 17 is mainly covered with the lipophilic surface modifier 173b. Then, for example, when sebum Y adheres here, since sebum Y is an oil component, it has good wettability with respect to the lipophilic surface modifier 173b. That is, the sebum Y tends to spread on the surface of the low refractive index layer 17. In this case, when the sebum Y is wiped off, it is difficult to wipe it off, and the amount of the sebum Y after wiping off tends to increase. On the other hand, when the sebum Y adheres, it is difficult to visually confirm the spread sebum Y, and the dirt is not conspicuous.

In the case of FIG. 3C, at least a part of each of the oil-repellent surface modifier 173a and the lipophilic surface modifier 173b is exposed on the surface side of the binder 171. That is, both the oil-repellent surface modifier 173a and the lipophilic surface modifier 173b are exposed on the surface. In the illustrated example, the oil-repellent surface modifier 173a and the lipophilic surface modifier 173b are alternately distributed to cover the surface of the low refractive index layer 17. As a result, the oil-repellent surface modifier 173a and the lipophilic surface modifier 173b are alternately exposed on the surface of the low refractive index layer 17. It can also be said that the surface of the binder 171 has a mixture of oil-repellent parts and lipophilic parts. In this case, when the low refractive index layer 17 is viewed from the surface side, for example, one of the oil-repellent surface modifier 173a and the lipophilic surface modifier 173b is distributed in a sea shape. The other is distributed in an island shape. However, it is not limited to this. For example, the oil-repellent surface modifier 173a and the lipophilic surface modifier 173b may be alternately distributed in a band shape.

Then, for example, when sebum Y adheres here, since sebum Y is an oil component, the wettability with respect to the oil-repellent surface modifier 173a is poor. On the other hand, it has good wettability with respect to the lipophilic surface modifier 173b. As a result, sebum Y is likely to spread and be distributed on the lipophilic surface modifier 173b. On the other hand, it is difficult to be placed on the oil-repellent surface modifier 173a. In this case, when the sebum Y is wiped off, it is easy to wipe off, and the amount of sebum Y adhered after wiping off tends to be small. Further, when the sebum Y adheres, it is difficult to visually confirm the spread sebum Y, and the dirt is not conspicuous.

Further, when a fluororesin is used as the resin of the binder 171, the lipophilic surface modifier 173b tends to segregate on the surface of the low refractive index layer 17. On the other hand, the oil-repellent surface modifier 173a is generally less likely to segregate on the surface of the low refractive index layer 17. However, when both the oil-repellent surface modifier 173a and the lipophilic surface modifier 173b are used, both tend to segregate on the surface of the low refractive index layer 17. Therefore, the amount of the oil-repellent surface modifier 173a added can be reduced.

The mass content ratio of the lipophilic surface modifier 173b to the oil-repellent surface modifier 173a is preferably 0.05 or more and 20 or less. That is, these are preferably in the range of 1: 0.05 to 1:20. If the oil-repellent surface modifier 173a is out of this range and is too much, it repels sebum Y and the like too much, and the attached sebum Y and the like become conspicuous. Further, these surface modifiers are less likely to segregate on the surface side of the low refractive index layer 17. That is, these surface modifiers are less likely to be distributed on the surface side. On the other hand, if the lipophilic surface modifier 173b is out of this range and is too much, it becomes difficult to wipe off the sebum Y and the like. Then, the amount of sebum Y or the like adhered after wiping is likely to increase.
It is more preferable that the oil-repellent surface modifier 173a is larger than the lipophilic surface modifier 173b in terms of mass ratio. Alternatively, the mass ratio may be the same. That is, the mass compounding ratio of the lipophilic surface modifier 173b to the oil-repellent surface modifier 173a is more preferably 1 or more and 20 or less. In this case, when the sebum Y is wiped off, it is easy to wipe off, and the amount of sebum Y adhered after wiping is likely to be further reduced. Further, when the sebum Y adheres, it is difficult to visually confirm the spread sebum Y, and the dirt is less noticeable.

It is preferable that at least one of the oil-repellent surface modifier 173a and the lipophilic surface modifier 173b has a reactive group that binds to the resin contained in the binder 171. Specifically, this reactive group is a photopolymerizable group, for example, an acryloyl group and a methacryloyl group. As a result, a covalent bond is formed between the binder 171 and these surface modifiers, and the bond is stronger. As a result, the low refractive index layer 17 is less likely to change with time, and its performance can be maintained for a long period of time.

Further, the low refractive index layer 17 may contain an additive used in forming the low refractive index layer 17.
In the present embodiment, a photopolymerization initiator for initiating photopolymerization is required when forming the low refractive index layer 17. Therefore, the low refractive index layer 17 contains a photopolymerization initiator as an additive. The photopolymerization initiator is not particularly limited. However, those that are less susceptible to oxygen inhibition and have good surface curability are preferable. Specifically, for example, IGM Resins B.I. V. Omnirad 127 manufactured by the manufacturer can be mentioned. In addition, IRGACURE127, IRGACURE819, and OXE-01 manufactured by BASF Japan Ltd. can be mentioned.
Further, in the present embodiment, an additive is used in the coating solution used when forming the low refractive index layer 17. Therefore, the low refractive index layer 17 also contains these additives. This additive is, for example, a dispersant, an antifoaming agent, an ultraviolet absorber, a leveling agent and the like.

<Explanation of Method for Creating Low Refractive Index Layer 17>
Next, a method for producing the low refractive index layer 17 will be described.
FIG. 4 is a flowchart illustrating a method for producing the low refractive index layer 17 according to the present embodiment.
First, a coating solution for forming the low refractive index layer 17 is prepared (step 101: preparation step). This coating solution is an example of a coating solution for forming a resin film. Further, here, "preparation" includes not only the case of preparing by preparing a coating solution but also the case of purchasing and preparing a coating solution.

FIG. 5 is a diagram showing the components of the coating solution.
The coating solution consists of a solid content and a solvent. The solid content then contains hollow silica particles 172, monomers and / or oligomers, and surface modifier 173. That is, the coating solution contains a monomer and / or an oligomer, hollow silica particles 172, a surface modifier 173, and a solvent. Then, a coating solution can be prepared by adding a monomer and / or an oligomer, hollow silica particles 172, and a surface modifier 173 into a solvent and stirring the mixture. At this time, the concentration of the solid content is preferably 0.5% by mass or more and 20% by mass or less. Further, it is preferable that the hollow silica particles 172 are 30% by mass or more and 65% by mass or less in the solid content. Further, the concentration of the surface modifier 173 is preferably 3% by mass or more and 20% by mass or less.

The monomer and / or oligomer is polymerized to become the resin contained in the binder 171. In this embodiment, the polymerization is photopolymerization. Hereafter, this monomer and / or oligomer may be referred to as a "binder component". The binder component preferably becomes the above-mentioned fluororesin when polymerized. Specifically, Optool AR-100 manufactured by Daikin Industries, Ltd., Opstar JN35 manufactured by JSR Corporation, LINK-162A, UA-306H manufactured by Kyoeisha Chemical Co., Ltd., KAYARAD PET-30 manufactured by Nippon Kayaku Co., Ltd., etc. Can be used.

Further, as described above, the surface modifier 173 contains both an oil-repellent surface modifier 173a and a lipophilic surface modifier 173b. In addition, the coating solution contains a photopolymerization initiator. Furthermore, the coating solution may contain the above-mentioned dispersant, antifoaming agent, ultraviolet absorber, leveling agent and the like.

The solvent disperses the binder component, hollow silica particles 172 and surface modifier 173. As the solvent, for example, methylene chloride, toluene, xylene, ethyl acetate, butyl acetate, and acetone can be used. In addition, MEK (methyl ethyl ketone), ethanol, methanol, and normal propyl alcohol can be used. In addition, isopropyl alcohol, tert-butyl alcohol, mineral spirit, oleic acid, cyclohexanone can be used. Furthermore, NMP (N-methyl-2-pyrrolidone) and DMP (dimethyl phthalate) can be used.

Returning to FIG. 4, next, the coating solution is applied to prepare a coating film (step 102: coating step). The method of coating is not particularly limited, but the coating solution can be dropped onto the high refractive index layer 16 and coated with a bar coater. Further, it is also possible to adopt a method in which the coating solution is dropped onto the high refractive index layer 16 and rotated to form a film-like body having a uniform thickness by centrifugal force.
At this time, the oil-repellent surface modifier 173a and the lipophilic surface modifier 173b segregate on the surface side of the coating film.

Further, the applied coating film is dried (step 103: drying step). Drying can be carried out by a method of volatilizing the solvent by leaving it at room temperature, or a method of forcibly removing the solvent by heating or evacuation.

Then, it irradiates light such as ultraviolet rays to photopolymerize the binder component in the coating film. As a result, the binder component in the coating film is cured to become the binder 171 (step 104: polymerization step). By the above steps, the low refractive index layer 17 can be formed. The drying step and the polymerization step can be regarded as a curing step of curing the applied coating solution.

The hard coat layer 15 and the high refractive index layer 16 can also be produced in the same steps as in steps 101 to 104. That is, in step 101, a coating solution for forming the hard coat layer 15 and the high refractive index layer 16 is prepared. In this case, the coating solution contains a binder component, a solvent and the like. In addition, the coating solution may contain predetermined particles. Then, the coating step of step 102, the drying step of step 103, and the curing step of step 104 are performed.

In the low refractive index layer 17 described in detail above, even if deposits such as sebum Y adhere, the deposits are inconspicuous. In addition, it is easy to wipe off the deposits. This is the same even if a large amount of hollow silica particles 172 is contained.

In the above-mentioned example, the display device 1 shows a case where the hard coat layer 15, the high refractive index layer 16 and the low refractive index layer 17 are formed on the liquid crystal panel. However, the present invention is not limited to this, and for example, it may be formed in an organic EL or a cathode ray tube.
Further, these layers may be formed on the surface of a lens or the like made of a material such as glass or plastic. In this case, the lens or the like is an example of the base material. Further, a lens or the like on which the hard coat layer 15, the high refractive index layer 16 and the low refractive index layer 17 are formed is an example of an optical member. Further, as a base material, a film made of TAC or the like is used. Then, these layers may be formed on this film. It can be used as a low index film or antireflection film. This is also an example of an optical member.
Further, the hard coat layer 15, the high refractive index layer 16 and the low refractive index layer 17 can be formed on the polarizing film 12. This is an example of a polarizing member and can be used as a polarizing film.

Further, in the above-mentioned example, the hard coat layer 15 and the high refractive index layer 16 are provided, but if these are not required, they do not need to be provided. That is, it may not be necessary to provide either the hard coat layer 15 or the high refractive index layer 16. Further, it may not be necessary to provide both the hard coat layer 15 and the high refractive index layer 16.
Further, in the above-mentioned example, the case where the binder component is polymerized by photopolymerization is shown, but the binder component may be polymerized by thermal polymerization.

Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to these examples as long as the gist of the present invention is not exceeded.

[Formation of high refractive index layer 16]
First, a method for producing the high refractive index layer 16 will be described. Here, a coating solution of the high refractive index layer 16 was prepared with the composition shown in Table 1.

(Example A-1)
The coating solution of Example A-1 contains a binder component, a monomer and / or an oligomer, high refractive index particles, a photopolymerization initiator, and a solvent. As the binder component, KAYARAD DPMA manufactured by Nippon Kayaku Co., Ltd. was used. Further, as the high refractive index particles, zirconium oxide having an average primary particle diameter of 10 nm was used. Further, as the photopolymerization initiator, IRGACURE184 manufactured by BASF Japan Ltd. was used. These are solid contents, and the compounding ratio is as shown in Table 1.
Then, these solid contents were added to methyl isobutyl ketone as a solvent so as to be 7% by mass, and the mixture was stirred. As a result, a coating solution for the high refractive index layer 16 was prepared.

The coating solution was applied onto the hard coat layer 15 with a wire bar to prepare a coating film. Further, the coating film was left at room temperature for 1 minute and then heated at 100 ° C. for 1 minute to dry. Then, an ultraviolet lamp (metal halide lamp, light intensity 1000 mJ / cm ² ) was irradiated for 5 seconds. As a result, the coating film can be cured. By the above steps, the high refractive index layer 16 could be formed.

(Example A-2)
The coating solution of Example A-2 is different from the coating solution of Example A-1 in the following points, and the others are the same. That is, as the high refractive index particles, zirconium oxide having an average primary particle diameter of 30 nm was used. In addition, a fluorine-based additive was added as a solid content. As the fluorine-based additive, Megafvck F-568 manufactured by DIC Corporation was used. The compounding ratio of Example A-2 is as shown in Table 1.

(Example A-3)
The coating solution of Example A-3 is different from the coating solution of Example A-2 in the following points, and the others are the same. That is, as the high refractive index particles, antimony-doped tin oxide having an average primary particle size of 20 nm was used. The compounding ratio of Example A-3 is as shown in Table 1.

[Formation of hard coat layer 15]
Next, a method of creating the hard coat layer 15 will be described. Here, a coating solution of the hard coat layer 15 was prepared with the composition shown in Table 2.

(Example B-1)
The coating solution of Example B-1 contains a binder component, a monomer and / or oligomer, a photopolymerization initiator, an antistatic agent, an antifoaming agent, and a solvent. As the binder component, UA-306T manufactured by Kyoeisha Chemical Co., Ltd. was used. Further, as the binder component, Viscoat # 300 manufactured by Osaka Organic Chemical Industry Co., Ltd. and KAYARAD PET-30 manufactured by Nippon Kayaku Co., Ltd. were used. As the photopolymerization initiator, IRGACURE184 manufactured by BASF Japan Ltd. was used. Further, as the antistatic agent, NR-121X-9IPA manufactured by Corcote Co., Ltd. was used. Then, as the defoaming agent, BYK-066N manufactured by ALTANA was used. These are solid contents, and the compounding ratio is as shown in Table 2.
Then, these solids were put into methyl ethyl ketone as a solvent so as to be 30% by mass, and the mixture was stirred. As a result, a coating solution for the hard coat layer 15 was prepared.

The coating solution was applied onto the substrate with a wire bar to prepare a coating film. A TAC film was used as the substrate. Further, the coating film was left at room temperature for 1 minute and then heated at 100 ° C. for 1 minute to dry. Then, an ultraviolet lamp (metal halide lamp, light intensity 1000 mJ / cm ² ) was irradiated for 5 seconds. As a result, the coating film can be cured. By the above steps, the hard coat layer 15 could be formed.

[Formation of low refractive index layer 17]
Next, a method for producing the low refractive index layer 17 will be described. Here, a coating solution of the low refractive index layer 17 was prepared with the compositions shown in Tables 3 to 5.

(Example 1)
The coating solution of Example 1 contains a monomer and / or oligomer which is a binder component, and hollow silica particles 172. The coating solution also contains an oil-repellent surface modifier 173a and a lipophilic surface modifier 173b. Further, the coating solution contains a photopolymerization initiator and a solvent. As the binder component, Optool AR-100 manufactured by Daikin Industries, Ltd. was used. Further, as the hollow silica particles 172, those having an average primary particle diameter of 75 nm were used. Further, KY-1203 manufactured by Shin-Etsu Chemical Co., Ltd. was used as the oil-repellent surface modifier 173a. Furthermore, as the lipophilic surface modifier 173b, Futergent 650A manufactured by Neos Co., Ltd. was used. Then, as the photopolymerization initiator, IRGACURE 127 manufactured by BASF Japan Ltd. was used. These are solid contents, and the mass compounding ratio is as shown in Table 3.
Then, these solids were put into a mixed solution of methyl isobutyl ketone and tert-butyl alcohol as a solvent, and the mixture was stirred. At this time, the solid content was adjusted to 3.5% by mass. As a result, a coating solution for the low refractive index layer 17 was prepared. The mass mixing ratio of the solvent is as shown in Table 3.

The coating solution was applied onto the high refractive index layer 16 with a wire bar to prepare a coating film. At this time, as the high refractive index layer 16, the one prepared in Example A-1 was used. Further, as the hard coat layer 15, the one prepared in Example B-1 was used.
Then, the coating film was left at room temperature for 1 minute and then heated at 100 ° C. for 1 minute to dry it. Then, an ultraviolet lamp (metal halide lamp, light intensity 1000 mJ / cm ² ) was irradiated for 5 seconds. As a result, the coating film can be cured. By the above steps, the low refractive index layer 17 could be formed.

(Example 2)
In Example 2, the mass compounding ratio of the lipophilic surface modifier 173b to the oil-repellent surface modifier 173a was changed from that of Example 1. That is, as shown in Table 3, the mass compounding ratio was set to 14.5 / 0.5 = 29. Other than that, the low refractive index layer 17 was formed in the same manner as in Example 1.

(Example 3)
In Example 3, the mass compounding ratio of the lipophilic surface modifier 173b to the oil-repellent surface modifier 173a was changed from that of Example 1. That is, as shown in Table 3, the mass compounding ratio was set to 7/8 = 0.875. In this case, the oil-repellent surface modifier 173a is less in mass ratio than the lipophilic surface modifier 173b. Other than that, the low refractive index layer 17 was formed in the same manner as in Example 1.

(Example 4)
In Example 4, the oil-repellent surface modifier 173a was changed from that of Example 1. That is, it was changed from KY-1203 manufactured by Shin-Etsu Chemical Co., Ltd. to Mega Fuck F-477 manufactured by DIC Corporation. In this case, the former has a photopolymerizable group, but the latter does not have a photopolymerizable group. In Tables 3 to 5, the case of having a photopolymerizable group is indicated as "with a reactive group". Other than that, the low refractive index layer 17 was formed in the same manner as in Example 1.

(Example 5)
In Example 5, the lipophilic surface modifier 173b was changed from that of Example 1. That is, the foot gent 650A manufactured by Neos Co., Ltd. was changed to the foot gent 730LM manufactured by Neos Co., Ltd. In this case, the former has a photopolymerizable group, but the latter does not have a photopolymerizable group. Other than that, the low refractive index layer 17 was formed in the same manner as in Example 1.

(Example 6)
In Example 6, the oil-repellent surface modifier 173a was changed from that of Example 1. That is, it was changed from KY-1203 manufactured by Shin-Etsu Chemical Co., Ltd. to Mega Fuck RS-90 manufactured by DIC Corporation. In this case, the former is a fluorine-based compound having a photopolymerizable group, but the latter is different in that it has a photopolymerizable group but is not a fluorine-based compound. Other than that, the low refractive index layer 17 was formed in the same manner as in Example 1.

(Example 7)
In Example 7, the binder component was changed with respect to Example 1. That is, the optool AR-100 manufactured by Daikin Industries, Ltd. was changed to KAYARAD PET-30 manufactured by Nippon Kayaku Co., Ltd. In this case, the former becomes a fluororesin after photopolymerization. That is, fluorine is contained in the monomer and oligomer which are binder components. In Tables 3 to 5, this case is indicated by "including F". On the other hand, the latter differs in that the resin after photopolymerization is not a fluororesin. Other than that, the low refractive index layer 17 was formed in the same manner as in Example 1.

(Example 8)
In Example 8, the hollow silica particles 172 were changed from those in Example 1. That is, the average primary particle size was changed from 75 nm to 30 nm. Other than that, the low refractive index layer 17 was formed in the same manner as in Example 1.

(Examples 9 to 13)
In Examples 9 to 13, the binder component, hollow silica particles 172, surface modifier 173, photopolymerization initiator, and solvent were changed as shown in Table 4 with respect to Example 1. Other than that, the low refractive index layer 17 was formed in the same manner as in Example 1.

(Examples 14 to 16)
In Examples 14 to 16, the high refractive index layer 16 and the hard coat layer 15 were changed from those in Example 1. Of these, in Example 14, the high refractive index layer 16 prepared in Example A-2 was used. Further, in Example 15, the high refractive index layer 16 prepared in Example A-3 was used. In Example 16, the high refractive index layer 16 was not formed.

(Comparative Example 1)
Comparative Example 1 did not use the lipophilic surface modifier 173b as compared with Example 1. That is, only the oil-repellent surface modifier 173a was used as the surface modifier.

(Comparative Examples 2 to 4)
In Comparative Examples 2 to 4, the binder component, the hollow silica particles 172, the surface modifier 173, and the solvent were changed as shown in Table 5 with respect to Comparative Example 1. Other than that, the low refractive index layer 17 was formed in the same manner as in Comparative Example 1. That is, the lipophilic surface modifier 173b was not used as the surface modifier.

〔evaluation〕
The SCI (Specular Component Include) reflectance Y was measured for Examples 1 to 16 and Comparative Examples 1 to 4. In addition, a fingerprint wiping property test, an oil-based pen test, and a scratch resistance test were performed.

The SCI reflectance Y was measured using CM-2600d manufactured by Konica Minolta. The measurement was performed after attaching a black PET film to the back surface of the measurement film. The smaller the SCI reflectance Y, the better the result. Then, if the SCI reflectance Y is 0.3 or less, it is determined to pass. Further, it is more preferably less than 0.2.

In the fingerprint wiping property test, a fingerprint was adhered to the surface of the low refractive index layer 17, and the wiping property when the fingerprint was wiped off was evaluated in four stages of A to D. In this test, the easier it is to wipe off the fingerprints, the better the results. Then, as it goes from A to D, the wiping property becomes worse, which means that it becomes difficult to wipe the fingerprint. Then, when the evaluation was A or B, it was determined to be acceptable, and when the evaluation was C or D, it was determined to be unacceptable.

In the oil-based pen test, whether or not the ink of the oil-based pen was repelled when drawn on the surface of the low refractive index layer 17 with the oil-based pen was evaluated on a four-point scale from A to D. In this test, repelling the ink gives a better evaluation. Then, from A to D, it means that the ink is less likely to be repelled and the ink is more likely to adhere. Then, when the evaluation was A or B, it was determined to be acceptable, and when the evaluation was C or D, it was determined to be unacceptable.

In the scratch resistance test, the surface of the low refractive index layer 17 was rubbed with steel wool, and whether or not scratches were generated was evaluated in four stages of A to D. In this test, the less scratches are, the better the result. And, as it goes from A to D, it means that scratches are likely to occur. Then, when the evaluation was A or B, it was determined to be acceptable, and when the evaluation was C or D, it was determined to be unacceptable.

Comparing Examples 1 to 16 and Comparative Examples 1 to 4, respectively, the evaluations shown in Tables 3 to 5 were obtained.
First, the SCI reflectance Y was all passed.
Further, in the fingerprint wiping property test and the oil-based pen test, all of Examples 1 to 16 passed, but all of Comparative Examples 1 to 4 failed.
Further, the scratch resistance test was passed in Examples 1 to 16 and Comparative Example 1, but failed in Comparative Examples 2 to 4.
That is, Examples 1 to 16 passed all the tests. This is a case where both the oil-repellent surface modifier 173a and the lipophilic surface modifier 173b are used. On the other hand, Comparative Examples 1 to 4 failed in at least one test. This is the case when the lipophilic surface modifier 173b was not used.

Further, among Examples 1 to 16, Examples 1 and 9 to 16 gave particularly good results. These are cases where all of the following conditions (1) to (6) are satisfied.
(1) The weight-mass compounding ratio of the lipophilic surface modifier 173b to the oil-repellent surface modifier 173a is 0.05 or more and 20 or less.
(2) The oil-repellent surface modifier 173a has a larger mass ratio than the lipophilic surface modifier 173b.
(3) At least one of the oil-repellent surface modifier 173a and the lipophilic surface modifier 173b has a reactive group that binds to the resin in the binder 171.
(4) The oil-repellent surface modifier 173a is a fluorine-based compound having a photopolymerizable group.
(5) The resin in the binder 171 contains a fluororesin.
(6) The hollow silica particles 172 have an average primary particle size of 35 nm or more and 100 nm or less.

1 ... Display device, 1a ... Liquid crystal panel, 11 ... Backlight, 12, 12a, 12b ... Polarizing film, 13, 13a, 13b ... Phase difference film, 14 ... Liquid crystal, 15 ... Hard coat layer, 16 ... High refractive index layer , 17 ... Low refractive index layer, 171 ... Binder, 172 ... Hollow silica particles, 173 ... Surface modifier, 173a ... Oil repellent surface modifier, 173b ... Oil-based surface modifier

Claims (15)

Binder containing resin and
Hollow silica particles distributed in the binder and
Oil-repellent surface modifiers and lipophilic surface modifiers that are mainly distributed on the surface side of the binder,
Resin film having. The resin film according to claim 1, wherein the mass compounding ratio of the lipophilic surface modifier to the oil-repellent surface modifier is 0.05 or more and 20 or less. The resin film according to claim 2, wherein the mass content ratio of the lipophilic surface modifier to the oil-repellent surface modifier is 1 or more and 20 or less. The resin film according to claim 1, wherein at least one of the oil-repellent surface modifier and the oil-repellent surface modifier has a reactive group that binds to the resin. The resin film according to claim 4, wherein the oil-repellent surface modifier is a fluorine-based compound having a photopolymerizable group. The resin film according to claim 1, wherein at least a part of each of the oil-repellent surface modifier and the lipophilic surface modifier is exposed on the surface side of the binder. The resin film according to claim 1, wherein the resin contains a fluororesin. The resin film according to claim 1, wherein the hollow silica particles have an average primary particle size of 35 nm or more and 100 nm or less. Binder containing resin and
Hollow silica particles distributed in the binder and
Have,
The surface of the binder is a resin film in which oil-repellent parts and lipophilic parts are mixed. The preparatory process for preparing the coating solution for creating the resin film, and
The coating process of applying the coating solution to prepare a coating film, and
A curing step of curing the applied coating film and
Have,
The coating solution contains a monomer and / or oligomer that becomes a resin by polymerization, hollow silica particles, an oil-repellent surface modifier, a lipophilic surface modifier, and the monomer and / or oligomer. Hollow silica particles, a solvent that disperses the oil-repellent surface modifier and the lipophilic surface modifier, and
How to make a resin film containing. Display means for displaying images and
A low refractive index layer formed on the surface of the display means,
With
The low refractive index layer is
Binder containing resin and
Hollow silica particles distributed in the binder and
Oil-repellent surface modifiers and lipophilic surface modifiers that are mainly distributed on the surface side of the binder,
Display device with. With the base material
The resin film provided on the substrate and according to any one of claims 1 to 9.
Optical member having. Polarizing means to polarize light and
The resin film according to any one of claims 1 to 9, which is provided on the polarizing means.
Polarizing member having. Monomers and / or oligomers that become resins by polymerization,
Hollow silica particles and
Oil-repellent surface modifier and
Lipophilic surface modifiers and
A solvent that disperses the monomer and / or oligomer, the hollow silica particles, the oil-repellent surface modifier, and the lipophilic surface modifier.
A coating solution for forming a resin film containing. The coating solution for forming a resin film according to claim 14, wherein the mass content ratio of the lipophilic surface modifier to the oil-repellent surface modifier is 1 or more and 20 or less.

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