WO2015084097A1 - Film de résine et procédé de fabrication de film de résine - Google Patents

Film de résine et procédé de fabrication de film de résine Download PDF

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WO2015084097A1
WO2015084097A1 PCT/KR2014/011911 KR2014011911W WO2015084097A1 WO 2015084097 A1 WO2015084097 A1 WO 2015084097A1 KR 2014011911 W KR2014011911 W KR 2014011911W WO 2015084097 A1 WO2015084097 A1 WO 2015084097A1
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Prior art keywords
fluoropolymer
resin film
silica particles
photopolymerizable
less
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PCT/KR2014/011911
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English (en)
Korean (ko)
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코보리시게토
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삼성에스디아이 주식회사
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Priority claimed from JP2013251682A external-priority patent/JP2015108733A/ja
Application filed by 삼성에스디아이 주식회사 filed Critical 삼성에스디아이 주식회사
Priority to CN201480066313.5A priority Critical patent/CN105793741B/zh
Priority to JP2016557860A priority patent/JP6494654B2/ja
Priority to US15/101,405 priority patent/US10450465B2/en
Publication of WO2015084097A1 publication Critical patent/WO2015084097A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/0006—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 with means to keep optical surfaces clean, e.g. by preventing or removing dirt, stains, contamination, condensation

Definitions

  • the present invention relates to a resin film and a method for producing the resin film.
  • an antireflection film is often affixed on the surface of a liquid crystal display, a plasma display, or the like.
  • the antireflection film improves the visibility of the display by preventing light reflection 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 silica particles of a hollow structure and have a role of decreasing the refractive index of the low refractive index layer.
  • the acrylic resin has a role of a binder for bonding the hollow silica particles to each other.
  • the fluorinated acrylic resin has a role of bonding hollow silica particles to each other and reducing the refractive index of the low refractive index layer.
  • the additive combines with 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. When an additive exists in the surface of the low refractive index layer, the function is exhibited.
  • the additive in the conventional low refractive index layer, additives were distributed not only on the surface but also 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. That is, the additive cannot effectively move to the surface because the hollow silica particles serve as a barrier.
  • 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 mutually compatible. In such a case, the additive remains in the vicinity of the fluorinated acrylic resin.
  • the additive could not be effectively localized on the surface of the low refractive index layer.
  • lubricacy become somewhat favorable, there existed a problem that these characteristics fell remarkably by repeating surface wiping.
  • the additive distributed inside the low refractive index layer lowers the crosslinking density of binder resin (namely, acrylic resin and fluorinated acrylic resin), there also existed a problem that film strength fell. 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.
  • binder resin namely, acrylic resin and fluorinated acrylic resin
  • Patent Literature 1 discloses a technique in which the surface of the low refractive index layer is formed into the uneven shape by forming the surface of the hard coat layer into the uneven shape and forming the low refractive index layer on the surface of the hard coat layer. According to this technique, 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 the hard-coat layer needs to be formed in the uneven shape in order to form the low refractive index layer, there is another problem that it is very difficult to form the surface of the low refractive index layer in the uneven shape.
  • Patent document 2 discloses an antireflection film in which an island-in-sea structure is formed as a phase having no silica particles and a phase having silica particles.
  • the additive could not be effectively localized on the surface of the low refractive index layer.
  • 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.
  • Patent Document 1 JP2004-109966 A
  • Patent Document 2 JP2006-336008 A
  • One embodiment of the present invention relates to a resin film having a height difference of about 10 nm to about 65 nm of concave and convex portions of an outermost surface, and having a contact angle difference ⁇ CA represented by the following formula 1 below about 10 °:
  • CA1 is a droplet contact angle after 500 reciprocating wear tests with an eraser on a coated surface of the resin-coated substrate under a load of 500 g / cm 2
  • CA2 is an initial droplet contact angle before the reciprocating wear test.
  • the resin film may contain hollow silica particles having an average particle diameter of more than about 20 nm and about 100 nm or less and solid silica particles having an average particle diameter of about 20 nm or less.
  • the resin film may include more than about 5% by weight and less than about 50% by weight of the hollow silica particles, and more than about 0% by weight and less than about 10% by weight of the solid silica particles.
  • the resin film may contain a photopolymerizable fluoropolymer and a thermopolymerizable fluoropolymer.
  • the resin film may include the content of the photopolymerizable fluoropolymer and the thermopolymerizable fluoropolymer in a content of about 1.5% by mass or more and about 7% by mass or less in total.
  • thermopolymerizable fluoropolymer and the photopolymerizable fluoropolymer of the resin film may satisfy the following Equation 2.
  • P2 is the content of the thermopolymerizable fluoropolymer
  • P1 is the content of the photopolymerizable fluoropolymer
  • inventions include hollow silica particles having an average particle diameter of greater than about 20 nm and up to about 100 nm; Solid silica particles having an average particle diameter of about 20 nm or less; Additives including photopolymerizable fluoropolymers and thermopolymerizable fluoropolymers; And a resin film-forming composition comprising a binder monomer.
  • the composition comprises greater than about 5% and less than about 50% by weight of the hollow silica particles; Greater than about 0 weight percent less than about 10 weight percent of the solid silica particles; About 1.5 wt% or more and about 7 wt% or less of the photopolymerizable fluoropolymer and the thermopolymerizable fluoropolymer; And a monomer for the binder.
  • the binder monomer may have a hydrogen bond forming group capable of forming hydrogen bonds with other functional groups.
  • the hydrogen bond former may include a hydroxyl group.
  • the surface tension of the binder monomer may be about 36 dyne / cm to about 45 dyne / cm.
  • the hollow silica particles and the solid silica particles each include a photopolymerizable functional group, and the photopolymerizable functional group may be at least one of acryloyl group and methacryloyl group.
  • the hollow silica particles and the solid silica particles may each further comprise a thermopolymerizable functional group.
  • the weight average molecular weight of the thermally polymerizable fluoropolymer may be greater than the weight average molecular weight of the photopolymerizable fluoropolymer.
  • the weight average molecular weight of the thermally polymerizable fluoropolymer may be about 10,000 or more, and the weight average molecular weight of the photopolymerizable fluoropolymer may be less than about 10,000.
  • Still another embodiment of the present invention provides a monomer for a binder, hollow silica particles having an average particle diameter of more than about 20 nm and about 100 nm or less, solid silica particles having an average particle diameter of about 20 nm or less, a photopolymerizable fluoropolymer and a thermopolymerizable fluoropolymer.
  • Preparing a coating solution for forming a resin film comprising a; Coating the resin film forming coating liquid onto a substrate to form a coating layer; Forming a protective layer made of the photopolymerizable fluoropolymer and the thermopolymerizable fluoropolymer bleed out to the surface of the coating layer; And initiating a polymerization reaction; It relates to a method for producing a resin film comprising a.
  • the content of the hollow silica particles may be greater than about 5% by mass and less than about 50% by mass, and the content of the solid silica particles may be greater than about 0% by mass and less than about 10% by mass.
  • the total content of the photopolymerizable fluoropolymer and the thermopolymerizable fluoropolymer may be about 1.5% by mass or more and about 7% by mass or less.
  • thermopolymerizable fluoropolymer and the photopolymerizable fluoropolymer may satisfy the following Equation 2.
  • P2 is the content of the thermopolymerizable fluoropolymer
  • P1 is the content of the photopolymerizable fluoropolymer
  • the hollow silica particles and the solid silica particles each include a photopolymerizable functional group
  • the photopolymerizable functional group may be at least one or more of acryloyl group and methacryloyl group.
  • the hollow silica particles and the solid silica particles may each further include a thermopolymerizable functional group.
  • the binder monomer may include a hydrogen bond former, and the hydrogen bond former may include a hydroxyl group.
  • the weight average molecular weight of the thermally polymerizable fluoropolymer may be greater than the weight average molecular weight of the photopolymerizable fluoropolymer.
  • the weight average molecular weight of the thermopolymerizable fluoropolymer may be about 10,000 or more, and the weight average molecular weight of the photopolymerizable fluoropolymer may be less than about 10,000.
  • the photopolymerizable fluoropolymer and the thermopolymerizable fluoropolymer are effectively bleed out and localized by the repulsive force by the binder resin, and an island-in-sea structure is formed on the surface of the low refractive index layer. Therefore, according to embodiments of the present invention, it is possible to improve the antifouling property, slipperiness, scratch resistance, and film strength of the resin film.
  • the height difference of the islands structure can also be controlled.
  • hollow silica particles used in the present specification means silica particles in a form in which pores are intentionally included in the particles.
  • Such hollow silica particles may mean, for example, silica particles having a porosity of about 10% or more, about 15% or more, or about 20% or more.
  • solid silica particles used in the present specification means silica particles in a form in which pores are not intentionally included in the particles.
  • the solid silica particles may have a higher effect when the porosity is closer to 0%, but the porosity of about 5% or less, about 3% or less, about 1% or less, or about 0% to about 1% in the manufacturing process. It may be included.
  • the porosity may be measured by transmission electron microscopy (TEM).
  • TEM transmission electron microscopy
  • TEM can clearly image the contrast of hollow and solid parts. Therefore, a hollow part and a solid part are specified using the TEM picked-up image, and the volume of a particle and the volume of a hollow part are computed based on this result.
  • the resin film has an elevation difference of about 10 nm to about 65 nm, and a contact angle difference ⁇ CA represented by the following Equation 1 is less than about 10 °:
  • CA1 is the droplet contact angle after 500 reciprocating wear tests with an eraser while applying a load of 500 g / cm 2 to the coated surface of the resin-coated substrate
  • CA2 is the initial droplet contact angle before the reciprocating wear test.
  • the water droplet contact angle difference ⁇ CA may be specifically 5.4 ° or less, more specifically 5 ° or less.
  • the contact angle before and after the said abrasion test can be measured using a fully automatic contact goniometer. For example, 2 microliters of pure water can be dripped on the board
  • the resin film 10 may include the low refractive index layer 10a and the additive 40.
  • the additive 40 may be bleed out and localized on the surface of the low refractive index layer 10a to form the protective layer 50.
  • the low refractive index layer 10a may include hollow silica particles (hollow silica fine particles) 20a, solid silica particles (solid silica fine particles) 20b, and a binder resin 30.
  • the hollow silica particles 20a may have an average particle diameter of more than about 20 nm and about 100 nm or less, and the solid silica particles 20b may have an average particle diameter of about 20 nm or less.
  • the additive 40 may include a photopolymerizable fluoropolymer and a thermopolymerizable fluoropolymer.
  • the resin film includes more than about 5% by weight and less than about 50% by weight of the hollow silica particles, more than about 0% by weight and less than about 10% by weight of the solid silica particles, and the sum of the photopolymerizable fluoropolymer and the thermopolymerizable fluoropolymer. To about 1.5% by mass or more and about 7% by mass or less. In this case, the value (P2 / P1) obtained by dividing the content of the thermopolymerizable fluoropolymer by the content of the photopolymerizable fluoropolymer may be less than about 0.43.
  • the height difference between the concave and convex portions of the outermost surface is about 10 nm to about 65 nm, and the contact angle difference ⁇ CA before and after the eraser reciprocating wear test is less than about 10 °. It may also be particularly advantageous to form a contact angle difference ⁇ CA of less than or equal to about 5.4 degrees or less than or equal to about 5 degrees.
  • the resin film 10 of the present embodiment can be used, for example, for the outermost layer of the optical film, the antireflection film, or coated over the protective layer of the polarizer. Moreover, it can apply suitably to the field etc. which use a film
  • inventions include hollow silica particles 20a having an average particle diameter of greater than about 20 nm and about 100 nm or less; Solid silica particles 20b having an average particle diameter of about 20 nm or less; Photopolymerizable fluoropolymers and thermopolymerizable fluoropolymers; And a resin film-forming composition comprising a binder monomer.
  • the hollow silica particles 20a may be dispersed in the low refractive index layer 10a.
  • the hollow silica particles 20a have an outer layer, and the inside of the outer layer is hollow or porous.
  • the outer layer and the porous body are mainly composed of silicon oxide.
  • many photopolymerizable functional groups mentioned later may couple
  • the hollow silica particles 20a may be nanoscale particles (particulates) having a photopolymerizable functional group.
  • the photopolymerizable functional group may be bonded to the outer layer through at least one of Si-O-Si bond and hydrogen bond.
  • the hollow silica particles 20a may include at least one of acryloyl group and methacryloyl group as a photopolymerizable functional group.
  • Photopolymerizable functional groups are also referred to as ionizing radiation curable groups.
  • the hollow silica particles 20a may have at least one photopolymerizable functional group, and the number and type of these functional groups are not particularly limited.
  • the hollow silica particles 20a may further have other functional groups, such as thermopolymerizable functional groups. Examples of the thermopolymerizable functional group include hydroxyl group, silanol group, alkoxy group, halogen, hydrogen, isocyanate group and the like.
  • the thermopolymerizable functional group may be bonded to the outer layer of the hollow silica particles 20a via at least one of Si—O—Si bonds and hydrogen bonds.
  • the average particle diameter of the hollow silica particles 20a is not particularly limited as long as it is larger than the average particle diameter of the solid silica particles 20b.
  • the average particle diameter of the hollow silica particles 20a may be greater than about 20 nm and up to about 100 nm or from about 40 nm to about 60 nm. Within this range, the hollow silica particles 20a can be prevented from excessively agglomerated. In addition, the uniformity, dispersibility, and transparency of the low refractive index layer 10a can be improved within the above range.
  • the average particle diameter of the hollow silica particles 20a is an arithmetic mean value of the particle diameter of the hollow silica particles 20a (the diameter when the hollow silica particles 20a are assumed to be spherical).
  • the particle diameter of the hollow silica particles 20a is measured by, for example, a laser diffraction scattering particle size distribution meter (for example, HORIBA LA-920).
  • the laser diffraction scattering particle size distribution system is not limited to HORIBA LA-920.
  • the refractive index of the hollow silica particles 20a varies depending on the refractive index required for the low refractive index layer 10a, but may be, for example, 1.10 to 1.40 or 1.15 to 1.25.
  • the refractive index of the hollow silica particles 20a is measured, for example, by simulation software (Lambda Research Corporation, TracePro).
  • the content of the hollow silica particles 20a is greater than about 5 mass%. Less than about 50 mass%. In the above range, it may be advantageous to form an island-in-the-sea structure having a height difference (h) of about 10 nm to about 65 nm. In addition, in the above range, the hollow silica particles 20a sufficiently lower the refractive index of the low refractive index layer 10a, so that the characteristics of the resin film 10 may be improved.
  • the content of the hollow silica particles 20a may be, for example, about 6% by mass to about 49% by mass or about 20% by mass to about 40% by mass.
  • the properties of the resin film 10 can be further improved.
  • the larger the content of the hollow silica particles 20a the higher the height difference h tends to be.
  • the solid silica particles 20b may be dispersed in the low refractive index layer 10a.
  • the solid silica particles 20b may be configured in the same manner as the hollow silica particles 20a, except that the solid silica particles 20b are solid particles and have a smaller particle diameter than the hollow silica particles 20a.
  • the solid silica particles 20b are made of solid solid particles.
  • the porosity ratio of hollow portion to total volume of solid silica particles
  • the solid silica particles 20b have a smaller average particle diameter than the hollow silica particles 20a.
  • the solid silica particles 20b may be about 20 nm or less. More specifically, the average particle diameter of the solid silica particles 20b may be greater than about 0 nm and about 20 nm or less, greater than about 0 nm and about 15 nm or less or about 0.1 nm and about 15 nm or less. Within this range, formation of a sea-island structure to be described later is advantageous, and the low refractive index layer 10a can be prevented from breaking due to the size of the solid silica particles.
  • the average particle diameter of the solid silica particle 20b is an arithmetic mean value of the particle diameter of the solid silica particle 20b (the diameter when the solid silica particle 20b is assumed to be spherical).
  • the particle diameter of the solid silica particles 20b is measured by, for example, a laser diffraction scattering particle size distribution meter (for example, HORIBA LA-920).
  • the laser diffraction scattering particle size distribution system is not limited to HORIBA LA-920.
  • the solid silica particles 20b may be nanoscale particles (particulates) having a photopolymerizable functional group.
  • a plurality of photopolymerizable functional groups may be bonded to the surface of the solid silica particles 20b.
  • the surface of the photopolymerizable functional group and the solid silica particles 20b may be bonded via at least one of the Si—O—Si bonds and the hydrogen bonds.
  • the photopolymerizable functional group on the surface of the solid silica particles 20b may be mutatis mutandis to the description of the photopolymerizable functional group on the surface of the hollow silica particles 20a.
  • the solid silica particles 20b include at least one of an acryloyl group and a methacryloyl group as a photopolymerizable functional group. More specifically, the solid silica particles 20b may have at least one photopolymerizable functional group, and the number and type of these functional groups are not particularly limited. In other embodiments, the solid silica particles 20b may further have other functional groups, such as thermopolymerizable functional groups. Examples of the thermopolymerizable functional group include hydroxyl group, silanol group, alkoxy group, halogen, hydrogen, isocyanate group and the like. The thermopolymerizable functional group may be bonded through at least one of hollow silica particles 20a, Si—O—Si bonds, and hydrogen bonds in the same manner as the photopolymerizable functional groups.
  • the content of the solid silica particles 20b exceeds about 0% by mass. Less than about 10 mass%. Specifically, about 1% by mass to about 10% by mass. In the above range, it may be advantageous to form an island-in-the-sea structure having a height difference (h) of about 10 nm to about 65 nm. In addition, the properties of the resin film 10 in the above content range can be improved.
  • the height difference of the unevenness of the island-in-the-sea structure is hollow silica particles 20a and solid silica particles 20b.
  • the low refractive index layer 10a includes hollow silica particles 20a and solid silica particles 20b, thereby forming an island-in-the-sea structure in which a high and low difference h in the form of irregularities exists on the surface.
  • the hollow silica particles 20a contained in the resin film may be directly bonded to each other.
  • the thermopolymerizable functional group of the hollow silica particles 20a is combined with the thermopolymerizable functional group of the other hollow silica particles 20a, and the photopolymerizable functional group of the hollow silica particles 20a is in the light of the other hollow silica particles 20a. It can be combined with synthetic functional groups. This coupling is possible because the hollow silica particles 20a are not subjected to network modification in advance in the production of the resin film 10.
  • the solid silica particles 20b may be directly bonded to each other, and the hollow silica particles 20a and the solid silica particles 20b may be directly bonded to each other.
  • the binder resin 30 has a network structure (network structure), and serves to connect the hollow silica particles 20a and the solid silica particles 20b with each other.
  • the binder resin 30 may include at least one monomer for a binder in a polymerized state.
  • the monomer for the binder may include, for example, 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, and may be, for example, a hydroxyl group.
  • the hydrogen bond former is not limited to this example, and hydrogen bonds (that is, hydrogen atoms connected to other atoms by covalent bonds) are isolated from pairs of lone electrons such as nitrogen, oxygen, sulfur, fluorine, and ⁇ electron systems located near hydrogen atoms. As long as it creates a noncovalent, attractive interaction that can be used without limitation.
  • the photopolymerizable functional group include at least one of acryloyl group and methacryloyl group.
  • the binder monomer may be a polyfunctional (meth) acrylate monomer containing a hydroxyl group.
  • the multifunctional (meth) acrylate monomer containing a hydroxyl group may be glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, isocyanurate acrylate.
  • Penta (meth) acrylates such as diacrylates such as diacrylate, tri (meth) acrylates such as pentaerythritol (meth) acrylate, pentaerythritol (meth) acrylate derivatives, and dipentaerythritol (meth) acrylate Etc.
  • the binder monomer may be other than the above examples. 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.
  • the binder resin 30 effectively bleeds out the additive 40 described later by including a multifunctional (meth) acrylate monomer containing a hydrogen bond former, specifically, a (meth) acrylate monomer having a hydrogen bond former. You can. Specifically, 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. Therefore, the additive 40 can be effectively bleeded out by repelling the binder resin 30. Specifically, the surface tension of the monomer for the binder may be, for example, about 36 dyne / cm or more and about 45 dyne / cm or less. In this range, the additive 40 bleeds out more effectively.
  • the surface tension is measured by, for example, an automatic surface tension meter.
  • the automatic surface tension meter is not limited to DY-300, a product of Kyowa Interface Science Corporation. Specifically, the surface tension may be a value measured at a temperature of 25 ° C.
  • the binder resin 30 can further advantageously form the structure even in the low refractive index layer 10a by including a hydrogen bond former. Therefore, the hydrogen bond former is also an important constitution in that a structure is formed even in the low refractive index layer 10a.
  • the binder monomer has at least three or more functional groups (a hydrogen bond former and two or more photopolymerizable functional groups), so that the binder resin 30 having a complicated three-dimensional structure (net nose structure) can be formed by polymerization with each other.
  • the hydrogen bond former of the monomer for a binder can be thermally polymerized (condensation polymerization) with the thermopolymerizable functional group of the hollow silica particle 20a, or the hydrogen bond former of another binder monomer.
  • the photopolymerizable functional group of the monomer for binder can photopolymerize with the photopolymerizable functional group of the solid silica particle 20a and the solid silica particle 20b, or the photopolymerizable functional group of another monomer for binder.
  • the binder resin 30 of a complicated three-dimensional structure can be formed.
  • the binder monomer bleeds out the additive 40, the amount of the additive 40 remaining in the low refractive index layer 10a is reduced, so that the additive 40 is localized on the surface of the low refractive index layer 10a. can do. Therefore, the crosslinking density of the binder resin 30 can be improved, and furthermore, the mechanical strength of the low refractive index layer 10a can be improved.
  • Content of the binder resin 30 (mass% with respect to the total mass of the hollow silica particle 20a, the solid silica particle 20b, the binder resin 30, the additive 40, and a photoinitiator) is hollow silica, for example.
  • the remaining amount may be other than the particles 20a, the solid silica particles 20b, the binder resin 30, the additive 40, and the photoinitiator. Specifically, about 45% by mass to about 85% by mass, about 48% by mass to about 85% by mass, about 50% by mass to about 85% by mass, or about 50% by mass to about 80% by mass. In the above range, the effect of bleeding out the additive to the surface may be excellent.
  • the additive 40 is added to impart antifouling property, slipperiness, 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 further include a thermopolymerizable fluoropolymer 42.
  • the photopolymerizable fluoropolymer 41 is a fluoropolymer having a photopolymerizable functional group, and specifically, may be represented by Formula 1 below:
  • Rf1 represents a (per) fluoroalkyl group or a (per) fluoropolyether group
  • W1 represents a linking group
  • RA1 represents a functional group having a polymerizable unsaturated group, that is, a photopolymerizable functional group.
  • n is 1-3
  • m represents the integer of 1-3.
  • the structure of the (per) fluoroalkyl group is not particularly limited. That is, the (per) fluoroalkyl group has a straight chain structure (eg, -CF 2 CF 3 , -CH 2 (CF 2 ) 4 H, -CH 2 (CF 2 ) 8 CF 3 , -CH 2 CH 2 ( CF 2 ) 4 H, etc.), branched 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, etc.), and an alicyclic structure (specifically, a 5- or 6-membered ring structure, more specifically, a perfluorocyclohexyl group, a perfluorocyclopentyl group, or an alkyl group substituted therewith).
  • a straight chain structure eg, -CF 2 CF 3 , -CH 2 (CF 2
  • 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, a fluorocycloalkyl group having 4 to 20 carbon atoms having 5 or more fluorine atoms, and the like.
  • 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, a fluorocycloalkyl group having
  • 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.
  • x and y are each arbitrary natural numbers.
  • the linking group is not particularly limited, but examples thereof include a methylene group, a phenylene group, an alkylene group, an arylene group, a heteroalkylene group, or a combination of these. These linking groups may have a carbonyl group, a carbonyloxy group, a carbonylimino group, a sulfonamide group, or the like, or a combination thereof. Acryloyl group, methacryloyl group, etc. are mentioned as a photopolymerizable functional group.
  • the additive 40 has a lower surface tension than the binder resin 30 so that the additive 40 can be easily bleed out to the surface of the low refractive index layer.
  • the photopolymerizable fluoropolymer and / or the thermopolymerizable fluoropolymer may have a surface tension of, for example, about 6 dyne / cm to about 20 dyne / cm. Within this range, it can be bleed out more easily to the surface of the low refractive index layer.
  • the weight average molecular weight Mw of the photopolymerizable fluoropolymer 41 may be smaller than the weight average molecular weight Mw of the thermally polymerizable fluoropolymer 42 described later. Specifically, less than about 10,000.
  • the lower limit of the weight average molecular weight (Mw) of the photopolymerizable fluoropolymer may be about 3000 or more, for example.
  • the oleic acid fall angle of the photopolymerizable fluoropolymer 41 is selected according to the antifouling property and slipperiness
  • the oleic acid fall angle is measured by, for example, a fully automatic contact angle meter DM700 (manufactured by Kyowa Interface Science Co., Ltd.).
  • thermopolymerizable fluoropolymer 42 is a fluoropolymer having a thermopolymerizable functional group, and specifically, may be represented by the following Chemical 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, a silanol group, Halogen or hydrogen.
  • n represents 1-3.
  • the thermopolymerizable functional group is a concept including the aforementioned 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 may be larger than the weight average molecular weight (Mw) of the photopolymerizable fluoropolymer. Specifically, it may be 10,000 or more.
  • the upper limit of the weight average molecular weight (Mw) of the thermally polymerizable fluoropolymer is not particularly limited, but may be, for example, about 50,000 or less.
  • the oleic acid fall angle of the photopolymerizable fluoropolymer 41 is chosen according to the antifouling property and slipperiness
  • the photopolymerizable fluoropolymer 41 and the thermopolymerizable fluoropolymer 42 have a fluoropolymer portion as a basic skeleton, the fluoropolymer portion and the hydrogen bond formers of the binder resin 30 can repel each other. .
  • the photopolymerizable fluoropolymer 41 and the thermopolymerizable fluoropolymer 42 can be effectively bleeded out.
  • the additive may be bleeded out and localized on the surface of the low refractive index layer 10a.
  • the protective layer 50 made of a fluorine polymer bleed out on the surface of the low refractive index layer 10a can be formed.
  • the photopolymerizable fluoropolymer 41 is bonded to the photopolymerizable functional groups of the hollow silica particles 20a, the solid silica particles 20b, and / or the binder resin 30 distributed on the surface of the low refractive index layer 10a, and thermally polymerizable.
  • the fluoropolymer 42 may combine with the thermopolymerizable functional groups of the hollow silica particles 20a, the solid silica particles 20b, and / or the binder resin 30 distributed on the surface of the low refractive index layer 10a.
  • the hollow silica particles 20a, the solid silica particles 20b, and / or the binder resin 30 disposed on the surface of the low refractive index layer 10a may be protected by a ubiquitous fluoropolymer. .
  • positioned at the surface of the low refractive index layer 10a are made into the photopolymerizable fluoropolymer 41 and the thermopolymerizable fluoropolymer 42.
  • 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.
  • the weight average molecular weight (Mw) of the thermally polymerizable fluoropolymer 42 may be 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 thermopolymerizable fluoropolymer 42 is set in this manner for the following reasons. That is, the surface tension of the photopolymerizable fluoropolymer 41 and the thermally polymerizable fluoropolymer 42 may be smaller as the weight average molecular weight Mw is larger. In this case, bleed out is easy, and antifouling property, slipperiness, and bleed out property can be improved.
  • 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 may be difficult to manufacture. Therefore, when the weight average molecular weight (Mw) of the photopolymerizable fluoropolymer 41 and the thermally polymerizable fluoropolymer 42 is adjusted within the above-described range, it may be advantageous to be dissolved in a solvent during the production of the resin film 10 ( Specifically, the compatibility of the binder monomer and the additive may be improved).
  • the weight average molecular weight (Mw) of the photopolymerizable fluoropolymer 41 in the said range by this, the weight average molecular weight (Mw) of the fluoropolymer into which acryloyl group and a methacryloyl group are introduce
  • 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.
  • 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). By reducing the weight average molecular weight (Mw), the additive 40 can be easily dissolved in a solvent.
  • the content of the additive 40 (mass% with respect to the total mass of the hollow silica particles 20a, the solid silica particles 20b, the binder resin 30, the additive 40, and the photopolymerization initiator) is about 1.5% by mass or more. It may be about 7 mass% or less, specifically about 2.0 mass% or more and about 5.0 mass% or less.
  • the content of the additive 40 may be a total value of the content of the photopolymerizable fluoropolymer 41 and the thermopolymerizable fluoropolymer 42.
  • the content of the photopolymerizable fluoropolymer 41 (mass% relative to the total mass of the hollow silica particles 20a, the solid silica particles 20b, the binder resin 30, the additive 40, and the photopolymerization initiator) is about 1.5. It may be about 1.8 mass% or more, specifically about 1.8 mass% or more.
  • the photopolymerizable fluoropolymer 41 becomes an essential structure of the additive 40.
  • the inventors have examined the additive 40 and found that when the photopolymerizable fluoropolymer 41 is not included in the additive 40, it has a height difference of about 10 nm to about 65 nm or about 30 nm to about 65 nm. It has been found that no seam structure is formed. Therefore, the photopolymerizable fluoropolymer 41 becomes an essential structure of the additive 40.
  • thermopolymerizable fluoropolymer 42 the value obtained by dividing the content of the thermopolymerizable fluoropolymer 42 by the content of the photopolymerizable fluoropolymer 41 may be less than about 0.43, more specifically, less than about 0.25. That is, the thermopolymerizable fluoropolymer and the photopolymerizable fluoropolymer may satisfy the following Equation 2.
  • P2 is the content of the thermopolymerizable fluoropolymer
  • P1 is the content of the photopolymerizable fluoropolymer
  • P2 / P1 may be less than about 0.43 or less than about 0.25.
  • an island-in-the-sea structure having a height difference of about 10 nm to about 65 nm or about 30 nm to about 65 nm is formed, and further, the characteristics of the resin film 10 are good. Become.
  • the additive 40 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 is the low refractive index layer 10a, a structure will not be formed. It turned out. Therefore, the additive 40 being a fluoropolymer is also an important structure in that a structure is formed also in the low refractive index layer 10a.
  • a fluoropolymer for example, it becomes a silicone type polymer
  • the photoinitiator is a material for initiating photopolymerization, and any kind thereof. That is, in this embodiment, all the photoinitiators can be used. However, photopolymerization initiators are hardly susceptible to oxygen inhibition, and those having good surface hardenability can be used. Specifically, the photopolymerization initiator may use, for example, a radical polymerization initiator including at least one of Azobisisobutyronitrile, Potassium persulfate, tert-butylhydroperoxide, and diisopropylbenzene hydroperoxide, but is not limited thereto.
  • the content of the photopolymerization initiator (mass% relative to the total mass of the hollow silica particles 20a, the solid silica particles 20b, the binder resin 30, the additive 40 and the photopolymerization initiator) is about 0.5% by mass to about 5% by mass Can be. Specifically, it may be about 2% by mass to about 4% by mass. Within this range, the physical properties of the resin film can be improved.
  • the material of the resin film 10 becomes each material mentioned above, and also the content ratio of each material becomes the range mentioned above, and also an island-in-water structure is formed in the surface of the low refractive index layer 10a.
  • 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.
  • the layer thickness of the convex part 10b is the distance from the surface (surface in which the island-in-sea structure is formed) from the convex part 10b to the back surface (surface in contact with the substrate etc. to which the resin film 10 is coated).
  • 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).
  • the convex part 10b becomes an island part
  • the recessed part 10c becomes a sea part
  • the convex part 10b may be a sea part
  • the recessed part 10c may be an island part. Therefore, in the present embodiment, even if 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 is about 10 nm to about.
  • the angle between the inclination of each point on the surface of the low refractive index layer 10a and the plane direction is within a predetermined range (for example, ⁇ about 30 degrees). Value).
  • a predetermined range for example, ⁇ about 30 degrees. Value.
  • 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 shape of the low refractive index layer 10a has a gentle shape.
  • the additive 40 is unevenly distributed on the surfaces of the convex portion 10b and the concave portion 10c.
  • the height difference h between the convex portion 10b and the concave portion 10c may improve the antireflection performance by adjusting the scattering rate of light in the case where the resin film of one embodiment is used as the antireflection film of the display. Can be.
  • 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 measuring laser microscope.
  • 2 is a surface photograph by a shape measurement laser microscope of the resin film 10 according to the present embodiment (magnification x 50).
  • the shape measurement laser microscope acquires three-dimensional data of the whole field of view by performing non-contact three-dimensional measurement of the object using a laser.
  • Examples of the shape measurement laser microscope include VK-9500 manufactured by KEYENCE JAPAN.
  • the shape measuring laser microscope is not limited to this example.
  • the height difference h can be measured with a shape measuring laser microscope. Specifically, the convex part 10b and the concave part 10c which adjoin each other are determined as a unit (measurement point), are acquired by predetermined number (for example, 5 unit) from three-dimensional data, and these height differences are computed.
  • the calculated arithmetic mean of the height difference is referred to as the height difference h of the low refractive index layer 10a.
  • the shape measuring laser microscope is substantially an additive (The uneven shape of the layer 50 (hereinafter also referred to as "protective layer") 50 made of 40) 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.
  • the convex part 51 of the protective layer 50 is formed on the convex part 10b of the low refractive index layer 10a
  • the recessed part 52 of the protective layer 50 is the low refractive index layer 10a. It is formed on the recessed part 10c.
  • the protective layer 50 is formed according to the uneven shape of the low refractive index layer 10a, the uneven shape of the protective layer 50 becomes almost 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.
  • corner of the inclination of each point on the surface of the low refractive index layer 10a, and the surface direction can be measured similarly by a shape measurement microscope. Specifically, the angle can be measured from the above-mentioned three-dimensional data.
  • the resin film 10 has the following features, in particular, having the above-described structure, in particular, an island-in-sea structure.
  • the protective layer 50 is made of fluoropolymer.
  • 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.
  • another object can be wiped off easily.
  • 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
  • the frictional force decreases, the contact angle increases, so that the frictional force can be substantially measured by measuring the contact angle.
  • the amount of the additive 40 bleed out also increases.
  • the frictional force of the resin film 10 falls, the antifouling property, slipperiness, and scratch resistance of the resin film 10 improve.
  • corrugated shape of the protective layer 50 is a gentle shape, other objects can be wiped easily and surely. 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. As shown in 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. have.
  • the film which becomes a shape with a steep uneven shape like a moth-eye film is known, for example.
  • the MOS 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 off cannot enter a recessed part, other objects in a recessed part cannot be wiped off.
  • the hollow silica particles 20a having a particle diameter of more than about 20 nm and about 100 nm or less, the solid silica particles 20b having an average particle diameter of about 20 nm or less, a photoinitiator, a binder monomer and an additive 40 for a solvent are added to the solvent.
  • Injecting and stirring may comprise the step of producing a coating solution.
  • the additive 40 includes a photopolymerizable fluoropolymer and a thermally polymerizable fluoropolymer.
  • the composition of the coating solution is as described above.
  • the kind of solvent is not specifically limited,
  • the ketone solvent of boiling point about 110 degreeC or more can be used suitably.
  • This solvent can stably dissolve each material and easily bleed out the photopolymerizable fluoropolymer 41 and the thermopolymerizable fluoropolymer 42.
  • the coating liquid may be applied to any substrate and dried to form a coating layer.
  • a coating method is not specifically limited, A well-known method is arbitrarily applied. At this time, the photopolymerizable fluoropolymer 41 and the thermally polymerizable fluoropolymer 42 are bleed out by the repulsive force to the binder monomer, and are localized on the surface of the coating layer.
  • the protective layer 50 may be formed by the photopolymerizable fluoropolymer and the thermopolymerizable fluoropolymer bleed out to the surface of the coating layer.
  • each polymerization reaction is started.
  • the binder resin 30 is formed, while the photopolymerizable fluoropolymer 41 and the thermopolymerizable fluoropolymer 42 are hollow silica particles 20a and solid silica particles 20b disposed on the surface of the coating layer. And binder resin 30.
  • the resin film 10 is formed.
  • the binder monomer can bleed out the photopolymerizable fluoropolymer 41 and the thermopolymerizable fluoropolymer 42 effectively, the resin film 10 which concerns on this embodiment is manufactured by a very simple process.
  • the additive 40 is unevenly distributed on the surface of the low refractive index layer 10a, it is not necessary to attach an antifouling sheet or the like to the surface of the low refractive index layer 10a.
  • the resin film may be formed to have a thickness of about 60 nm to about 150 nm. In the above range, it may be advantageous to be used for the anti-reflection film applications.
  • the resin film prepared as described above can be used, for example, for an antireflection film.
  • 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 substrate on which the coating solution for forming a resin film is applied may be, for example, a first optical film or a second optical film, which may be a protective film or a retardation film.
  • the substrate may be a transparent film, the transparent film, for example, polyester-based, cyclic polyolefin-based (COP), triacetyl cellulose (TAC) and the like, including polyethylene terephthalate (PET) and the like Cellulose-based, acryl-based, polycarbonate-based, polyether sulfone-based, polysulfone-based, polyamide-based, polyimide-based, polyarylate-based, polyvinyl alcohol-based film and the like, but is not limited thereto.
  • polyester-based polyester-based, cyclic polyolefin-based (COP), triacetyl cellulose (TAC) and the like, including polyethylene terephthalate (PET) and the like
  • PET polyethylene terephthalate
  • the resin film may be coated on the polarizer except for the first optical film.
  • Example 1 the resin film 10 was manufactured by the following manufacturing method.
  • a monomer for a binder 50 mass% pentaerythritol triacrylate (made by Shin-Nakamura Kagaku Co., A-TMM-3LMN), 40 mass% hollow silica particle (Nikki Shokyu Chemical Co., Ltd., thru 4320), 5 mass % Solid silica particles (V8802 manufactured by Nikki Shokyubaikasei Co., Ltd.), 1.8% by mass of photopolymerizable perfluoropolyether (PFPE) (Shin-Etsu Chemical Co., Ltd. KY-1203) and 0.2% by mass of thermal polymerization Perfluoropolyether (PFPE) (Shin-Etsu Chemical Co., Ltd.
  • PFPE photopolymerizable perfluoropolyether
  • PFPE thermal polymerization Perfluoropolyether
  • the particle diameter of the hollow silica particles was a value within the range of 50 nm to 60 nm. Therefore, an average particle diameter also becomes a value within the said range.
  • the refractive index of the hollow silica particle was 1.25.
  • the particle diameter of the solid silica particle was more than 0 nm and 15 nm or less. Therefore, an average particle diameter also becomes a value within the said range.
  • the porosity of the solid silica particles was almost zero, and the porosity of the hollow silica particles was about 22%. The porosity was measured by a transmission electron microscope (TEM).
  • 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.
  • the coating layer was cured by irradiating the coating layer with ultraviolet rays for 5 seconds (metal halide lamp: light amount 1,000 mJ / cm 2) under a nitrogen atmosphere (oxygen concentration 1,000 ppm or less). This produced the resin film.
  • the average thickness of the resin film was about 110 nm.
  • the film thickness was measured using HORIBA's visible spectroscopic ellipsometer SMART SE, and the average thickness was defined as the arithmetic mean value of the maximum and minimum values of the measured values.
  • Example 1 Except having changed the content of each material and the average particle diameter of the solid silica particle, the process similar to Example 1 was performed and the resin film concerning Examples 2-16 and Comparative Examples 1-10 was created.
  • * 1 is a solid silica particle (Nissan Kagaku Co., Ltd. product: organosilica sol L type) of an average particle diameter of 40nm
  • * 2 is a solid silica particle (Nissan Kagaku Co., Ltd. an average particle diameter of 80nm)
  • Product: Organosilica sol ZL type) is used.
  • the height difference (h, upper end part 10b 'of the convex part-lower end part 10c' of the concave part) was measured about the resin film which confirmed the islands-in-sea structure.
  • the shape measurement microscope mentioned above was used for the measurement.
  • the number of measurement points was made into five.
  • 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 inclination of each point on the surface of the resin film and the angle which the surface direction makes
  • the initial contact angle (CA2) was measured by dropping 2 microliters of pure water on the board
  • the contact angle difference ( ⁇ CA) was calculated by substituting the values of CA1 and CA2 obtained in this manner into the following equation 1.
  • Fingerprints on the fingertips were pressed firmly onto 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, it was wiped with a Kimwipe 20 times circle. Kimwipe used Kimwiper wiper S-200 from Nippon Seishcresia. Then, the presence or absence of the fingerprint was visually confirmed. Thereafter, after wiping with the naked eye, it was confirmed whether or not the marks remain. The case where no marks are left is marked with " ⁇ " and the case with marks left is marked with "X".
  • the resin film 10 is bonded to the hollow silica particles 20a and the solid silica particles 20b distributed on the surface of the low refractive index layer 10a, and further, the binder resin 30 ) And the additive 40 which repels it. 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. Thereby, in this embodiment, the antifouling property, slipperiness
  • the islands structure is formed in the surface of the low-refractive-index layer 10a, the frictional force of the surface of the resin film 10 and another object can be reduced by this islands structure, Furthermore, the resin film The antifouling property, slipperiness, and scratch resistance of (10) can be improved.
  • the content ratio of the hollow silica particles 20a and the solid silica particles 20b it is possible to control the elevation difference of the islands structure.
  • the recessed part and convex part whose height difference becomes about 10 nm-about 65 nm can be formed more reliably in a low refractive index layer.
  • the additive 40 can be effectively bleeded out.
  • the additive 40 can be effectively bleeded out.
  • the weight average molecular weight of the thermopolymerizable fluoropolymer 42 is larger than the weight average molecular weight of the photopolymerizable fluoropolymer 41.
  • the additive 40 can be effectively bleed out.
  • the photopolymerizable fluoropolymer 41 functions as a compatibilizer, the solubility of the additive 40 in the solvent is improved.
  • the additive 40 can be effectively bleeded out.
  • the photopolymerizable fluoropolymer 41 functions as a compatibilizer, the solubility of the additive 40 in the solvent is improved.
  • the resin film 10 can be created only by apply

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Abstract

Selon ses modes de réalisation, la présente invention concerne un film de résine dans lequel la différence de hauteur entre une partie concave et une partie convexe de sa surface la plus à l'extérieur est d'environ 10 nm à environ 65 nm et la différence d'angle de contact (△CA) représentée par la formule 1 ci-dessous est inférieure à environ 10°. Par ailleurs, la présente invention concerne, selon ses modes de réalisation, une composition pour former un film de résine et un procédé de fabrication d'un film de résine, afin de fournir le film de résine : [Formule 1] △CA = ｜CA2-CA1｜dans laquelle CA1 est l'angle de contact des gouttelettes d'eau après 500 tests d'abrasion en va-et-vient à l'aide d'un effaceur tout en appliquant une charge de 500 g/㎠ à la surface revêtue d'un substrat revêtu d'un film de résine, et CA2 est l'angle de contact initial des gouttelettes d'eau avant les tests d'abrasion en va-et-vient. Grâce aux modes de réalisation, il est possible de fournir un nouveau film de résine, amélioré, ainsi qu'un procédé de préparation d'un film de résine, apte à améliorer les propriétés antisalissure et la glissance et améliorer la résistance du film.
PCT/KR2014/011911 2013-12-05 2014-12-05 Film de résine et procédé de fabrication de film de résine WO2015084097A1 (fr)

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CN201480066313.5A CN105793741B (zh) 2013-12-05 2014-12-05 树脂膜、树脂膜组成物以及树脂膜的制造方法
JP2016557860A JP6494654B2 (ja) 2013-12-05 2014-12-05 樹脂膜及び樹脂膜の製造方法
US15/101,405 US10450465B2 (en) 2013-12-05 2014-12-05 Resin film and method for manufacturing resin film

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JP2013251682A JP2015108733A (ja) 2013-12-05 2013-12-05 樹脂膜及び樹脂膜の製造方法
JP2013-251682 2013-12-05
KR1020140165598A KR101813748B1 (ko) 2013-12-05 2014-11-25 수지막 및 수지막의 제조 방법
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EP3333598A4 (fr) * 2015-08-05 2018-06-13 Panasonic Intellectual Property Management Co., Ltd. Composition pour films optiques, base comprenant un film optique, corps moulé, et procédé de fabrication d'un corps moulé
US11901589B2 (en) 2017-12-07 2024-02-13 Lg Energy Solution, Ltd. Cylindrical secondary battery module

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US5081165A (en) * 1988-04-15 1992-01-14 Daikin Industries, Ltd. Antifouling coating composition containing fluorinated (meth)acrylates
JPH09100111A (ja) * 1995-10-03 1997-04-15 Japan Synthetic Rubber Co Ltd 反応性シリカ粒子、その製法および用途
KR20110013751A (ko) * 2009-08-03 2011-02-10 동우 화인켐 주식회사 저굴절층 형성용 조성물, 이를 이용한 반사 방지 필름, 편광판 및 표시 장치
WO2012165766A2 (fr) * 2011-05-30 2012-12-06 백산철강(주) Composite creux à faible indice de réfraction, son procédé de fabrication et liquide de revêtement en contenant
WO2013141442A1 (fr) * 2012-03-19 2013-09-26 한국기계연구원 Substrat antireflet et son procédé de fabrication

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5081165A (en) * 1988-04-15 1992-01-14 Daikin Industries, Ltd. Antifouling coating composition containing fluorinated (meth)acrylates
JPH09100111A (ja) * 1995-10-03 1997-04-15 Japan Synthetic Rubber Co Ltd 反応性シリカ粒子、その製法および用途
KR20110013751A (ko) * 2009-08-03 2011-02-10 동우 화인켐 주식회사 저굴절층 형성용 조성물, 이를 이용한 반사 방지 필름, 편광판 및 표시 장치
WO2012165766A2 (fr) * 2011-05-30 2012-12-06 백산철강(주) Composite creux à faible indice de réfraction, son procédé de fabrication et liquide de revêtement en contenant
WO2013141442A1 (fr) * 2012-03-19 2013-09-26 한국기계연구원 Substrat antireflet et son procédé de fabrication

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3333598A4 (fr) * 2015-08-05 2018-06-13 Panasonic Intellectual Property Management Co., Ltd. Composition pour films optiques, base comprenant un film optique, corps moulé, et procédé de fabrication d'un corps moulé
US11901589B2 (en) 2017-12-07 2024-02-13 Lg Energy Solution, Ltd. Cylindrical secondary battery module

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