CN117178206A - Antireflection film and resin molded article using same - Google Patents
Antireflection film and resin molded article using same Download PDFInfo
- Publication number
- CN117178206A CN117178206A CN202280029025.7A CN202280029025A CN117178206A CN 117178206 A CN117178206 A CN 117178206A CN 202280029025 A CN202280029025 A CN 202280029025A CN 117178206 A CN117178206 A CN 117178206A
- Authority
- CN
- China
- Prior art keywords
- refractive index
- layer
- low refractive
- antireflection film
- index layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 44
- 239000011737 fluorine Substances 0.000 claims abstract description 43
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 42
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 38
- 239000010703 silicon Substances 0.000 claims abstract description 38
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 63
- 239000000377 silicon dioxide Substances 0.000 claims description 28
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- 239000000758 substrate Substances 0.000 claims description 11
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 8
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- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 3
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- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 229910003443 lutetium oxide Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- MPARYNQUYZOBJM-UHFFFAOYSA-N oxo(oxolutetiooxy)lutetium Chemical compound O=[Lu]O[Lu]=O MPARYNQUYZOBJM-UHFFFAOYSA-N 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001954 samarium oxide Inorganic materials 0.000 description 1
- 229940075630 samarium oxide Drugs 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 229910003451 terbium oxide Inorganic materials 0.000 description 1
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 210000001578 tight junction Anatomy 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 1
- 229940075624 ytterbium oxide Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- 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
- 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
- G02B1/14—Protective coatings, e.g. hard coatings
-
- 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
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
Abstract
According to the present invention, there is provided an antireflection film comprising, in order, a base layer, a hard coat layer and a low refractive index layer, wherein the base layer contains a thermoplastic resin, the hard coat layer is a cured coating layer, the low refractive index layer has a refractive index lower than that of the hard coat layer by 0.05 or more, the low refractive index layer has a thickness of 70 to 130nm, the antireflection film comprises a fluorine-containing leveling agent and a silicon-containing lubricant, the surface roughness of the surface of the low refractive index layer is 5.0nm or less, the intensity ratio I (Si)/I (F) of silicon to fluorine of the surface of the low refractive index layer is 0.8 or more and 3.2 or less, and the visual reflectance of the antireflection film is 3.0% or less.
Description
Technical Field
The present invention relates to an antireflection film including a base material layer, a hard coat layer, and a low refractive index layer, and a resin molded article using the antireflection film.
Background
A laminated film having a surface with low reflectance and capable of being used as an antireflection film is known in the related art (see patent document 1). Laminated films having low surface reflectance are used for applications such as computer screens, television screens, plasma display panels, surfaces of polarizing plates used in liquid crystal display devices, sunglasses lenses, spectacle lenses with power, camera lenses, covers for various instruments, automobile glass, trolley glass, display panels for vehicles, and housings for electronic devices.
Under such circumstances, in the above-mentioned applications, an antireflection film having low apparent reflectance and excellent resistance to abrasion by cloth and fingerprint wiping is demanded.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2014-41244
Disclosure of Invention
Problems to be solved by the invention
The invention provides an antireflection film having low apparent reflectance and excellent resistance to cloth scratch and fingerprint wiping.
Means for solving the problems
In order to solve the above problems, the inventors of the present invention have found as a result of intensive studies: the present invention has been completed by providing an antireflection film having low visual reflectance and excellent resistance to abrasion by cloth and fingerprint wiping by incorporating a combination of a specific additive in a low refractive index layer having a specific film thickness.
Namely, the present invention is as follows.
<1> an antireflection film comprising, in order, a base layer, a hard coat layer and a low refractive index layer, wherein the base layer contains a thermoplastic resin, the hard coat layer is a cured coating layer, the low refractive index layer has a refractive index lower than the refractive index of the hard coat layer by 0.05 or more,
the low refractive index layer has a thickness of 70-130 nm, and contains a fluorine-containing leveling agent and a silicon-containing lubricant,
The surface roughness of the surface of the low refractive index layer measured by an atomic force microscope is 5.0nm or less,
the intensity ratio I (Si)/I (F) of silicon to fluorine on the surface of the low refractive index layer is 0.8 to 3.2 as measured by a glow discharge emission spectrometer,
the visual reflectance of the antireflection film is 3.0% or less.
<2> the antireflection film according to the above <1>, wherein the antireflection film has a visual reflectance of 1.6 to 2.8%.
<3> the antireflection film according to the above <1> or <2>, wherein the low refractive index layer contains hollow silica.
<4> the antireflection film according to the above <3>, wherein the mass ratio of the hollow silica to the resin material contained in the low refractive index layer is 20:80 to 60:40.
<5> the antireflection film according to any one of the above <1> to <4>, wherein the silicon-containing lubricant is a polydimethylsiloxane-containing lubricant.
<6> the antireflection film according to any one of the above <1> to <5>, wherein the mass ratio of the silicon-containing lubricant to the fluorine-containing leveling agent contained in the low refractive index layer is 9:1 to 5:5.
<7> the antireflection film according to any one of the above <1> to <6>, wherein the oleic acid contact angle of the surface of the low refractive index layer is 55 ° or more.
<8> the antireflection film according to any one of the above <1> to <7>, wherein the antireflection film is used for insert molding applications.
<9> a resin molded article, wherein the surface of the resin molded article has the antireflection film according to any one of <1> to <8 >.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, an antireflection film having low apparent reflectance and excellent resistance to cloth scratch and fingerprint wiping is provided.
With such excellent characteristics, the antireflection film of the present invention can be applied to applications such as display units of computers, televisions, plasma displays, surfaces of polarizing plates used in liquid crystal display devices, sunglasses lenses, spectacle lenses with power, camera lenses, in-vehicle display panels, and electronic equipment housings.
Drawings
Fig. 1 is a schematic view showing the structure of a laminate of the antireflection film obtained in example 1.
FIG. 2 is a photograph showing the surface roughness Ra (nm) of the surface of the low refractive index layer measured by an Atomic Force Microscope (AFM).
Detailed Description
The present invention will be described in detail below. However, the present invention is not limited to the following embodiments, and may be modified and implemented arbitrarily within the scope of having the effect of the present invention.
[ antireflection film ]
An embodiment of the present invention relates to an antireflection film comprising, in order, a base material layer, a hard coat layer and a low refractive index layer, wherein the base material layer contains a thermoplastic resin, the hard coat layer is a cured coating layer, and the low refractive index layer has a refractive index lower than the refractive index of the hard coat layer by 0.05 or more.
The low refractive index layer is characterized by having a thickness of 70-130 nm and comprising a fluorine-containing leveling agent and a silicon-containing lubricant. The surface roughness of the surface of the low refractive index layer measured by an atomic force microscope is 5.0nm or less, the intensity ratio I (Si)/I (F) of silicon to fluorine of the surface of the low refractive index layer measured by a glow discharge emission spectrometer is 0.8 to 3.2 inclusive, and the apparent reflectance of the antireflection film is 3.0% or less.
Each layered member included in the antireflection film as such a laminate will be described below.
[ Low refractive index layer (anti-reflection layer) ]
The low refractive index layer of the present invention has a refractive index lower than that of the hard coat layer by 0.05 or more, preferably by 0.07 or more, and more preferably by 0.08 to 0.12. When having a refractive index lower than that of the hard coat layer by 0.05 or more, it is preferable because satisfactory antireflection performance can be obtained.
The refractive index of the low refractive index layer is preferably in the range of 1.35 to 1.44, more preferably in the range of 1.38 to 1.42, and particularly preferably in the range of 1.39 to 1.41. When the refractive index is less than 1.35, it is sometimes difficult to obtain sufficient hardness; when the refractive index exceeds 1.44, however, it is sometimes difficult to obtain sufficient antireflection performance.
The film thickness of the low refractive index layer is 70 to 130nm, preferably 80 to 120nm, more preferably 90 to 110nm. When the film thickness of the low refractive index layer is less than 70nm, the wavelength region of light capable of antireflection is largely changed to the low wavelength side, resulting in deterioration of the apparent reflectance; on the other hand, when the film thickness exceeds 130nm, the wavelength region of the light which can be prevented from reflecting is largely changed to the high wavelength side, and the apparent reflectance is deteriorated.
In order to suppress reflection of the antireflection film, the low refractive index layer is preferably disposed on the outermost side of the antireflection film.
The low refractive index layer can be formed by applying a coating liquid composed of a composition for forming a low refractive index layer on the hard coat layer, and then irradiating ultraviolet rays to cure the coating liquid. The coating method and curing conditions thereof, and the viscosity-adjusting diluent solvent may be appropriately selected without particular limitation. The low refractive index layer forming composition may contain, for example, an ultraviolet curable resin, a fluorine-containing leveling agent, a silicon-containing lubricant, hollow silica particles, and a photopolymerization initiator.
< ultraviolet curable resin >
The type of the ultraviolet curable resin for forming the low refractive index layer is not particularly limited as long as it is a polyfunctional (meth) acrylate. As such a resin for forming a low refractive index layer in a film, in general, a resin using a reactive silicon compound such as γ -acryloxypropyl trimethoxysilane or the like as a starting material may be used in addition to the polyfunctional (meth) acrylate, and a composition containing an ultraviolet curable polyfunctional (meth) acrylate as a main component is preferable from the viewpoint of both productivity and hardness.
Examples of the polyfunctional (meth) acrylate include, but are not particularly limited to, (meth) acrylic acid derivatives of polyfunctional alcohols such as dipentaerythritol hexa (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 6-bis (3- (meth) acryloyloxy-2-hydroxypropoxy) hexane, polyethylene glycol di (meth) acrylate, and polyurethane (meth) acrylate. In the present invention, polyurethane (meth) acrylate is particularly preferably used.
In addition, the multifunctional (meth) acrylate may be a fluorine-containing monomer. The fluoromonomer having a structure in which a fluorine atom is introduced into a molecule in the form of a fluoromethylene group or a fluoromethylene group is a monomer in which almost all fluorine atoms are introduced into a molecule in the form of a fluoromethylene group or a fluoromethylene group, and any known monomer can be used as long as it is a polyfunctional monomer. That is, any one of two or more (multifunctional) monomers may be used, or a mixture thereof may be used. These fluorine-containing compounds can improve the strength and hardness of the cured coating film, and can improve the scratch resistance and abrasion resistance of the cured coating film surface. Among the fluorine-containing compounds, fluorine-containing multifunctional (meth) acrylates are preferable from the viewpoint of being capable of forming a crosslinked structure and having high strength and hardness of the cured coating film.
< fluorine-containing leveling Agents >
The fluorine-containing leveling agent contained in the low refractive index layer can smooth the layer and impart fingerprint erasability, and can weaken the adhesion of fingerprints as lipids attached when the surface of the low refractive index layer is contacted and improve fingerprint erasability. "leveling" refers to the property of a coating material to flow and form a smooth coating film after the coating material is applied. When the coated surface looks like brush marks, orange peel (look like orange surface peel), and microscopic undulations such as waviness are not great, it is judged that leveling property is good.
As the fluorine-containing leveling agent used in the present invention, there is preferably mentioned a leveling agent having C 2 ～C 7 Specifically, preferable examples of the perfluoroalkyl chain (meth) acrylate include OPTOOL DAC-HP manufactured by Dain industries, inc., and MEGAFACE RS-75 and RS-78 manufactured by DIC, inc. In the present specification, "(meth) acrylate" means both acrylate and methacrylate.
The fluorine-containing leveling agent is preferably contained in an amount of 1 to 20% by mass, more preferably 2.5 to 10% by mass, in the low refractive index layer-forming composition. When the content is less than 1 mass%, the adhesion of the fingerprint attached when contacting the surface of the low refractive index layer may not be impaired. On the other hand, when it exceeds 20 mass%, it is sometimes difficult to obtain sufficient hardness or antireflection property.
< Lubricant containing silicon >
The silicon-containing lubricant contained in the low refractive index layer can impart resistance to cloth scratch. The lubricant is an additive for preventing adhesion to a metal surface, preventing adhesion between materials, improving fluidity of materials, reducing friction inside materials or with a metal surface, and the like, ensuring physical stability of materials when the thermoplastic resin is subjected to a thermoforming process.
The silicon-containing lubricant used in the present invention is preferably polydimethylsiloxane, more preferably polyether-modified polydimethylsiloxane having an acryl group or polyester-modified polydimethylsiloxane having an acryl group. Specifically, BYK-UV3500, BYK-UV3530, BYK-UV3570, etc. manufactured by BYK Chemie Japan are preferably mentioned.
The silicon-containing lubricant is preferably contained in an amount of 5 to 20% by mass, more preferably 10 to 17.5% by mass, in the low refractive index layer-forming composition. When the content is less than 5% by mass, the cloth scratch resistance sometimes becomes insufficient; on the other hand, when it exceeds 20 mass%, it is sometimes difficult to obtain sufficient hardness or antireflection property.
In the present invention, the mass ratio of the silicon-containing lubricant to the fluorine-containing leveling agent contained in the low refractive index layer is preferably 9:1 to 5:5, more preferably 7:1 to 5:5. When the mass ratio of the silicon-containing lubricant is higher than 9:1, it is sometimes difficult to obtain sufficient fingerprint erasability; on the other hand, when the mass ratio of the fluorine-containing leveling agent is more than 5:5, it is sometimes difficult to obtain sufficient resistance to abrasion by cloth.
< hollow silica >
The low refractive index layer in the present invention preferably contains hollow silica particles to lower the refractive index of the low refractive index layer. The hollow silica particles are silica (silicon dioxide, siO) 2 ) Particles which are substantially spherical and have a hollow portion in the outer shell thereof. The average grain diameter is 10-100 nm, the thickness of the shell is about 1-60 nm, the porosity of the hollow part is 40-45%, and the refractive index is as low as 1.20-1.29. Since the hollow portion contains air having a refractive index of 1.0, the cured coating film formed by curing the polyfunctional (meth) acrylate can achieve a low refractive index and a low reflectance, and the scratch resistance and abrasion resistance of the cured coating film can be improved by using inorganic fine particles such as silica fine particles.
When the porosity of the hollow portion is less than 40%, the air amount of the hollow portion is reduced, and the cured coating film cannot be reduced in refractive index and reflectance. On the other hand, when the porosity of the hollow portion exceeds 45%, it is necessary to make the outer shell thinner in order to increase the porosity, and the production thereof becomes difficult.
The hollow silica fine particles are preferably modified with a silane coupling agent as needed. Thus, it is possible to exhibit an excellent effect which is not exhibited by conventional ordinary (unmodified) silica particles or hollow silica particles, i.e., an effect of excellent compatibility with polyfunctional (meth) acrylates. Therefore, when the modified hollow silica fine particles are mixed with the multifunctional (meth) acrylate, aggregation of the modified hollow silica fine particles can be suppressed, and a cured coating film excellent in transparency without whitening can be obtained. Further, since the polymerizable double bond of the silane coupling agent and the polymerizable double bond of the polyfunctional (meth) acrylate are copolymerized (chemically bonded) in the cured coating film to form a firm cured coating film, the scratch resistance and abrasion resistance of the cured coating film can be dramatically improved.
The mass ratio of the hollow silica to the resin material (the low refractive index coating material in example 1 described later) contained in the low refractive index layer is preferably 20:80 to 60:40, more preferably 30:70 to 50:50. When the amount of hollow silica particles added is increased, the surface roughness may be increased, and it may be difficult to achieve both fingerprint wiping performance and cloth scratch resistance. This is because fingerprints are easily filled and particles are easily dropped.
< other Components >
The low refractive index layer may contain metal fluoride particles or the like to reduce the refractive index of the low refractive index layer. When fine metal fluoride particles are used, examples of the metal fluoride contained in the particles include magnesium fluoride, aluminum fluoride, calcium fluoride, lithium fluoride, and the like. The metal fluoride particles are preferably in the form of particles, and the particle diameter (diameter) thereof is not particularly limited, and may be, for example, 10 to 200nm, preferably 30 to 100nm, more preferably 35 to 80nm, and particularly preferably 45 to 65nm.
In order to improve scratch resistance, fine metal oxide particles (silica or the like) may be contained.
The low refractive index layer forming composition for forming a low refractive index layer preferably contains a photoinitiator (photopolymerization initiator). The low refractive index layer-forming composition may further contain a solvent.
[ hard coating ]
The antireflection film of the present invention has a hard coat layer between a base material layer and a low refractive index layer. By providing the hard coat layer, the surface hardness and scratch resistance of the antireflection film are improved.
In addition, in the antireflection film of the laminate structure including the low refractive index layer, the high refractive index layer, and the hard coat layer, the hard coat layer is preferably laminated between the base material layer and the high refractive index layer. That is, it is preferable that these layers are laminated in the order of the base material layer, the hard coat layer, the high refractive index layer, and the low refractive index layer.
In the antireflection film having such a laminate structure, a high antireflection effect is achieved, and the surface hardness, that is, the hardness of the surface on the opposite side from the base material layer is improved.
The hard coat layer is preferably formed by hard coat treatment performed on the surface of the base material layer or the like. That is, it is preferable to laminate the hard coat layer by applying a hard coat material capable of thermosetting or curing by active energy rays and then curing the material.
Examples of the coating material to be cured by active energy rays include a resin composition composed of one or more of monofunctional or polyfunctional acrylate monomers and oligomers, and more preferably a resin composition containing urethane acrylate oligomers. It is preferable to add a photopolymerization initiator as a curing catalyst to these resin compositions.
Examples of the thermosetting resin coating material include a polyorganosiloxane-based coating material, a crosslinked acrylic-based coating material, and the like. Such a resin composition is also commercially available as a hard coating agent for an acrylic resin or a polycarbonate resin, and can be appropriately selected in consideration of suitability for a coating line.
In addition to the organic solvent, various stabilizers such as ultraviolet absorbers, light stabilizers, antioxidants, and surfactants such as leveling agents, defoamers, thickeners, antistatic agents, and antifogging agents may be added to these paints as needed.
Examples of the hard coat paint cured by active energy rays include a paint prepared by mixing 40 to 95 mass% of a 6-functional urethane acrylate oligomer with, for example, 2- (2-ethyleneoxyethoxy) ethyl (meth) acrylate [ 2- (2-ethyleneoxyethoxy) ethyl acrylate: 100 parts by mass of a photopolymerizable resin composition obtained by mixing 5 to 60% by mass of (meth) acrylate such as VEEA ] and 1 to 10 parts by mass of a photopolymerization initiator are added.
As the photopolymerization initiator, a conventionally known one can be used. Specific examples thereof include benzoin, benzophenone, benzoin ethyl ether, benzoin isopropyl ether, 2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, azobisisobutyronitrile, benzoyl peroxide and the like.
The refractive index of the hard coat layer is preferably equal to the refractive index of the base material layer. Specifically, it is preferable that the hard coat layer has a refractive index in the range of 1.43 to 1.65. The refractive index of the hard coat layer is more preferably 1.47 to 1.60, and still more preferably 1.49 to 1.57.
The difference between the refractive index of the base material layer and the refractive index of the hard coat layer is preferably 0.04 or less, more preferably 0.03 or less, and still more preferably 0.02 or less.
In order to make the refractive index of the hard coat layer close to that of the base material layer, a high refractive index material described later may be added to the hard coat layer paint as appropriate.
The thickness of the hard coat layer is not particularly limited, but is preferably 1 to 10. Mu.m, more preferably 2 to 8. Mu.m, and still more preferably about 2 to 6. Mu.m.
In order to reduce the surface tension of the coating film and to reduce the coating unevenness, it is preferable to use a leveling agent such as a silicone leveling agent and/or a fluorine leveling agent for the hard coat layer. Here, when a second cured layer is further formed on a first cured layer containing these leveling agents in order to improve the surface properties, the leveling agents present on the surface of the first cured layer may interfere with the interface between the first cured layer and the second cured layer, so that the first cured layer and the second cured layer cannot form tight junctions, and poor adhesion may occur. In addition, when the wettability of the first cured layer is low, repulsion occurs when the second cured layer is applied, and the second cured layer may not be formed. Therefore, it is necessary to select an appropriate leveling agent capable of solving these problems.
In addition, in the case where the first cured layer is not fully cured, the leveling agent may be extracted by the second cured layer forming liquid to ooze out on the second cured layer at the time of the second cured layer formation, thereby affecting the performance of the second cured layer surface.
[ substrate layer ]
The base material layer included in the antireflection film contains a thermoplastic resin. The type of thermoplastic resin is not particularly limited, and various resins such as acrylic resins such as Polycarbonate (PC) resin, polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyimide (PI), cyclic Olefin Copolymer (COC), norbornene-containing resin, polyethersulfone, cellophane, and aromatic polyamide can be used. The thermoplastic resin of the substrate layer preferably contains at least a polycarbonate resin in these options.
The type of the polycarbonate resin contained in the base layer is not particularly limited as long as it is a resin containing a- [ O-R-OCO ] -unit (R is an aliphatic group, an aromatic group, or a group having both an aliphatic group and an aromatic group and having a linear structure or a branched structure) containing a carbonate bond in a molecular main chain, and is preferably a polycarbonate having a bisphenol skeleton or the like, and particularly preferably a polycarbonate having a bisphenol a skeleton or a bisphenol C skeleton. As the polycarbonate resin, a mixture or copolymer of bisphenol a and bisphenol C may be used. The hardness of the base material layer can be increased by using a bisphenol C-based polycarbonate resin, for example, a polycarbonate resin containing only bisphenol C, or a polycarbonate resin of a mixture or copolymer of bisphenol C and bisphenol a.
The viscosity average molecular weight of the polycarbonate resin is preferably 15000 to 40000, more preferably 20000 to 35000, and even more preferably 22500 to 25000.
The acrylic resin contained in the base layer is not particularly limited, and examples thereof include polymethyl methacrylate (PMMA), homopolymers of various (meth) acrylates typified by Methyl Methacrylate (MMA), and copolymers of PMMA or MMA with other 1 or more monomers, and mixtures of a plurality of these resins. Examples of the monomer include a cyclic anhydride unit, an N-substituted maleimide unit, an aromatic vinyl compound unit, and an aliphatic vinyl compound unit. Among these, (meth) acrylic esters having a cyclic alkyl structure, which are excellent in low birefringence, low hygroscopicity and heat resistance, are preferred. Examples of the (meth) acrylic resin include, but are not limited to, acrypet (manufactured by Mitsubishi yang Co., ltd.), delpet (manufactured by Asahi chemical corporation), and Parapet (manufactured by Kurara Co., ltd.).
In addition, when a mixture containing a polycarbonate resin and the acrylic resin is used, it is preferable to increase the hardness of the base material layer, particularly the surface layer (layer on the low refractive index layer side) of the base material layer as a laminate.
The base material layer may contain an additive as a component other than the thermoplastic resin. Such as an additive selected from at least 1 of a heat stabilizer, an antioxidant, a flame retardant aid, an ultraviolet absorber, a mold release agent, and a colorant, and the like. Further, antistatic agents, fluorescent brighteners, antifogging agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, and the like may be added to the base material layer.
The base layer preferably contains 80 mass% or more of a thermoplastic resin, more preferably 90 mass% or more, and particularly preferably 95 mass% or more of a thermoplastic resin. The thermoplastic resin of the base layer preferably contains 50 mass% or more of a polycarbonate resin, more preferably 70 mass% or more, and particularly preferably 75 mass% or more of a polycarbonate resin.
The substrate layer preferably has a refractive index in the range of 1.49 to 1.65. The refractive index of the base material layer is more preferably about 1.49 to 1.60.
The thickness of the base material layer is not particularly limited, but is preferably 30 to 1000 μm (1 mm), more preferably 50 to 700 μm, and particularly preferably 100 to 500 μm. In addition, 2 or more base material layers may be provided in the antireflection film, and when a plurality of base material layers are provided, the total thickness of the base material layers is, for example, about 100 to 1000 μm, preferably about 200 to 500 μm.
As the above-mentioned substrate layer including a plurality of layers, that is, as a substrate layer of a multilayer laminate, for example, the following substrate layers are given: a base material layer in which the acrylic resin, for example, an acrylic resin layer such as a polymethyl (meth) acrylate resin (PMMA: polymethyl acrylate and/or polymethyl methacrylate), is laminated as a surface layer (layer on the low refractive index layer side) on the layer of the polycarbonate resin (PC), for example, bisphenol a, or the like; a base material layer having a resin layer formed of a copolymer of PMMA and 1 or more other monomers laminated thereon; a base material layer of a polycarbonate resin (PC) such as bisphenol C is laminated on a layer of a polycarbonate resin (PC) such as bisphenol a. In a laminate in which a layer of a polycarbonate resin (PC) containing bisphenol a and a polycarbonate resin (PC) containing bisphenol C are laminated, for example, a layer of a polycarbonate resin containing bisphenol C is used as a surface layer.
The surface layer is preferably a high-hardness layer, and particularly preferably a layer having a higher hardness than the other base material layer.
The polycarbonate resin used as the thermoplastic resin in the laminate is preferably the same as the polycarbonate resin forming the single-layer base material layer. For example, mixtures or copolymers of bisphenol A and bisphenol C may be used. The use of a bisphenol C-based polycarbonate resin, for example, a polycarbonate resin containing only bisphenol C, or a polycarbonate resin of a mixture or copolymer of bisphenol C and bisphenol a, can achieve an effect of improving the hardness of the surface layer (layer on the low refractive index layer side) of the substrate layer, in particular, of the laminate. In order to further increase the hardness, a mixture in which the acrylic resin is added to a polycarbonate resin, for example, a bisphenol C-based polycarbonate resin, may be used.
[ high refractive index layer (antireflection layer) ]
In the antireflection film of the present invention, it is preferable that a high refractive index layer is further provided between the low refractive index layer and the hard coat layer in order to further reduce the reflectance. The high refractive index layer has a refractive index higher than that of the base material layer, and has an antireflection function as in the low refractive index layer.
The high refractive index layer preferably contains a polymer containing a resin material of urethane (meth) acrylate and (meth) acrylate derived from fluorene diol, isocyanate and (meth) acrylate. That is, the high refractive index layer is preferably a mixture of urethane (meth) acrylate obtained by dehydrating and condensing at least three components of fluorene diol, isocyanate and (meth) acrylate, and (meth) acrylate.
In the resin material, the ratio of urethane (meth) acrylate to (meth) acrylate is preferably 99:1 to 50:50 (weight ratio), more preferably 95:5 to 70:30, still more preferably 93:7 to 80:20, particularly preferably 90:10 to 85:15.
The refractive index value of the high refractive index layer is higher than that of the base material layer, and the refractive index of the high refractive index layer is preferably 1.68 to 1.75, more preferably 1.69 to 1.74, and further preferably about 1.70 to 1.73.
The difference between the refractive index of the high refractive index layer and the refractive index of the base material layer is preferably at least 0.09, more preferably at least 0.12, still more preferably at least 0.15, and particularly preferably at least 0.17. The difference between the refractive index of the high refractive index layer and the refractive index of the base material layer is, for example, in the range of 0.03 to 0.70, preferably 0.10 to 0.50, and more preferably 0.15 to 0.26. In this way, by increasing the difference between the refractive index value of the high refractive index layer and the refractive index value of the base material layer, the reflectance of the surface of the antireflection film on the high refractive index layer side can be improved.
< high refractive index Material >
The high refractive index layer preferably contains a high refractive index material. The high refractive index material is added in order to increase the refractive index of the high refractive index layer. That is, by forming the high refractive index layer using a high refractive index material, the difference between the refractive indices of the high refractive index layer and the base material layer can be increased, and the reflectance of the antireflection film can be further reduced.
Examples of the high refractive index material include titanium oxide and zirconium oxide (ZrO 2 ) Zinc oxide, aluminum oxide, colloidal aluminum oxide, lead titanate, lead oxide, chrome yellow, zinc yellow, chromium oxide, iron black, copper oxide, magnesium hydroxide, strontium titanate, yttrium oxide, hafnium oxide, niobium oxide, tantalum oxide (Ta) 2 O 5 ) Barium oxide, indium oxide, europium oxide, lanthanum oxide, zircon, tin oxide, and lead oxide, and lithium niobate, potassium niobate, lithium tantalate, and aluminum-magnesium oxide (MgAl) as their composite oxides 2 O 4 ) Etc.
As the high refractive index material, rare earth oxide may be used, and for example, scandium oxide, yttrium oxide, lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, lutetium oxide, or the like may be used.
Among the above options, zircon (zirconia) is preferable as the high refractive index material.
The high refractive index material is preferably a particulate material. The particle diameter (diameter: average particle diameter) of the particulate high refractive index material is not particularly limited, and is, for example, 1 to 100nm, preferably 5 to 50nm, more preferably 7.5 to 30nm, particularly preferably 10 to 25nm.
In addition, for example, a high refractive index material in the form of particles is preferably a coating layer including an organic layer as a surface treatment layer for coating the outer side surface of a metal oxide or the like. By the coating layer of the organic layer, the compatibility of the high refractive index material with respect to the resin material forming the high refractive index layer is improved, and the high refractive index material and the resin material can be firmly bonded.
As the surface treatment layer, a coating layer of an organic layer having an ultraviolet-reactive (curable) functional group introduced on the surface thereof, and the like are preferable.
The high refractive index layer preferably contains the resin material and the high refractive index material in a weight ratio of 10:90 to 40:60, more preferably 15:85 to 35:65, and still more preferably 20:80 to 30:70.
The thickness of the high refractive index layer is not particularly limited, but is preferably 10 to 300nm, more preferably 30 to 250nm, further preferably 80 to 200nm, particularly preferably 130 to 170nm.
< other Components >
The high refractive index layer or the resin material forming the high refractive index layer preferably contains at least one of a photoinitiator and a leveling agent, and particularly preferably contains a photoinitiator. The resin material may further contain a solvent. Examples of the leveling agent include a fluorine-based leveling agent, an acrylic leveling agent, and an organosilicon leveling agent.
[ Properties of antireflection film ]
< reflectance (apparent reflectance) >
The apparent reflectance of the surface of the antireflection film on the low refractive index layer side is 3.0% or less, preferably 1.6 to 2.8%, and more preferably 1.6 to 2.5% as measured in accordance with JIS Z8701. In the present invention, as a method for measuring the apparent reflectance, the method described in examples described below can be used.
< surface roughness of Low refractive index layer surface >
The surface roughness of the low refractive index layer surface measured by Atomic Force Microscope (AFM) is 5.0nm or less, preferably 4.5nm or less, and more preferably 1.5 to 4.2nm. In the present invention, as a method for measuring the surface roughness of the surface of the low refractive index layer, the method described in examples described below can be used. FIG. 2 shows a photograph of the surface roughness Ra (nm) of the surface of the low refractive index layer measured by an Atomic Force Microscope (AFM).
< intensity ratio of silicon to fluorine at the surface of Low refractive index layer >
The intensity ratio I (Si)/I (F) of silicon to fluorine on the surface of the low refractive index layer measured by a glow discharge emission spectrometer is 0.8 to 3.2, preferably 0.8 to 2.5, more preferably 0.9 to 2.4. In the present invention, as a method for measuring the intensity ratio I (Si)/I (F), the method described in examples described below can be used.
< resistance to abrasion by cloth >
The surface of the antireflection film on the low refractive index layer side is preferably excellent in resistance to abrasion by cloth. Specifically, it is preferable to apply 100g/cm to 4-fold medical gauze (manufactured by Dagasaki medical Co., ltd.) 2 And the surface of the antireflection film of the present invention on the low refractive index layer side is reciprocated 100 times, thereby causing no macroscopic scratches.
< fingerprint erasability >
The surface of the antireflection film on the low refractive index layer side is preferably excellent in fingerprint erasability. Specifically, it is preferable that the test described in the examples below be performed so that the test can be completely erased within 5 times.
< contact Angle of oleic acid >
The oleic acid contact angle of the low refractive index layer surface of the antireflection film is preferably 55 ° or more, more preferably 58 ° to 75 °. In the present invention, the method for measuring the contact angle of oleic acid can be the method described in examples described below.
[ method for producing antireflection film ]
In producing the antireflection film, it is preferable to form the base layer first. In the production of the base material layer, materials such as a resin composition are processed into a layer (sheet) according to a conventional method. For example, extrusion molding or casting molding is used. As an example of extrusion molding, there is a method of forming a sheet by melt-kneading pellets, flakes, or powder of a resin composition in an extruder, extruding the resultant semi-molten sheet through a T die or the like, and cooling and solidifying the sheet by nip-pressing the sheet with a roll.
Then, the above resin material is applied to the outer side surface of the single or plural base material layers and cured, thereby forming a hard coat layer, a low refractive index layer, and the like. As a method for curing the resin material, a method such as photo-curing or thermal curing can be used.
[ resin molded article ]
Another embodiment of the present invention is a resin molded article having the antireflection film on a surface thereof. The resin molded article of the present invention is obtained by molding a resin by insert molding and welding, and integrating an antireflection film on the surface of the resin molded article. For example, by holding the antireflection film in a cavity in an injection molding die and injecting a molten resin into the die, a resin molded article having the antireflection film integrated on the surface can be obtained.
Examples of the resin molded product include films adhered to surfaces of computer screens, television screens, and plasma display panels, and films used for surfaces of polarizing plates, sunglasses lenses, spectacle lenses with power, camera lenses, covers for various instruments, glass for automobiles, glass for electric vehicles, display panels for vehicles, and electronic equipment cases used for liquid crystal display devices.
Examples
Hereinafter, examples are given to more specifically explain the present invention. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented within a range not departing from the gist of the present invention.
Example 1
As the substrate, a transparent substrate layer (DF 02, total thickness 254 μm, manufactured by MGC fil kohl) in which a methacrylic resin layer was laminated on a polycarbonate resin layer made of 2, 2-bis (4-hydroxyphenyl) propane (bisphenol a) was used. The refractive index of the transparent base layer was measured by the method described below, and as a result, the refractive index was 1.498.
A hard coat paint was prepared by mixing urethane acrylate UN-954 (manufactured by Gen Kagaku Co., ltd.), 1-hydroxycyclohexyl phenyl ketone (manufactured by IGM Resin Co., ltd. Omnirad-184) as a photoinitiator in an amount of 5% by mass, ftergent 681 (manufactured by Neos Co., ltd.) as a leveling agent, and a solvent (propylene glycol monomethyl ether) to adjust the concentration so that the solid content became 25% by mass.
To form a hard coat layer, the above hard coat layer coating was applied so that the dry film thickness became 3 μm, and dried at 80℃for 2 minutes. Then the ultraviolet curing device irradiates ultraviolet rays to ensure that the accumulated light quantity reaches 200mJ/cm 2 A hard coat film a was obtained. The refractive index of the obtained hard coat film a was measured according to the method described below, and was found to be 1.501.
Next, a curable low refractive index coating material was prepared as follows. First, dry air was introduced into a five-necked flask equipped with a stirrer, a thermometer, a cooler, a monomer dropping funnel and a dry air introduction tube, and the inside of the system was dried. Then, 58.9 parts by mass of 2, 3-tetrafluoro-1, 4-butanediol (C4 DIOL manufactured by Exfluor Research Corporation), 279.8 parts by mass of pentaerythritol triacrylate, 0.5 parts by mass of dibutyltin laurate as a polymerization catalyst, and 500 parts by mass of butanone as a solvent were charged into a five-neck flask, and the temperature was raised to 60 ℃. Then, 161.3 parts by mass of isophorone diisocyanate was added, and then the reaction was performed at 60 to 70 ℃. The infrared absorption spectrum was used to confirm that the isocyanate residue in the reactant was consumed and the reaction was terminated to obtain a hexafunctional urethane acrylate oligomer.
The acrylic acid-2- (2-ethyleneoxyethoxy) ethyl ester (VEEA) and the urethane acrylate oligomer (urethane acrylate solution) were mixed in a ratio of urethane acrylate liquid/veea=90/10 (mass%).
Hollow silica (THRULYA 4320, manufactured by riyaku catalyst corporation) was added to the low refractive index paint (liquid component of resin material) thus obtained, and the mixture was mixed at a ratio of hollow silica/resin material=30/70 (mass%). Then, 4 mass% of 1-hydroxycyclohexyl phenyl ketone (Omnirad-184, manufactured by IGM Resin Co., ltd.), 17.5 mass% of BYK-UV3500 (manufactured by Pick chemical Co., ltd.) as a silicon-containing lubricant, and 2.5 mass% of RS-78 (manufactured by DIC Co., ltd.) as a fluorine-containing leveling agent were added as photoinitiators to dissolve the materials, and the concentration was adjusted by adding a solvent (propylene glycol monomethyl ether) so that the solid content concentration became 3 mass%. The resulting low refractive index coating was low refractive index coating B-1. The amounts of the respective materials in examples and comparative examples described below are each expressed as mass% of the solid content.
A low refractive index coating material B-1 was applied to the hard coat film A to give a dry film of 100nm, and the film was dried at 80℃for 2 minutes. Then the ultraviolet curing device is used for irradiation to ensure that the accumulated light quantity of ultraviolet rays reaches 400mJ/cm 2 The low refractive index coating is cured. Thus, a low refractive index layer having a thickness of 100nm was formed on the outer surface of the hard coat film a to prepare an antireflection film C-1 (see fig. 1: lr layer=low refractive index layer; HC layer=hard coat layer).
Example 2
An antireflection film C-2 was produced in the same manner as in example 1, except that the low refractive index paint B-2 was used in which the concentration of the fluorine-containing leveling agent (RS-78) in the low refractive index paint B-1 was changed to 10 mass% and the concentration of the silicon-containing lubricant (BYK-UV 3500) was changed to 10 mass%.
Example 3
An antireflection film C-3 was produced in the same manner as in example 1, except that a low refractive index coating material B-3 was used in which the ratio of hollow silica to resin material in the low refractive index coating material B-1 was changed to 40/60 (mass%).
Example 4
An antireflection film C-4 was produced in the same manner as in example 1, except that a low refractive index coating material B-4 was used in which the ratio of hollow silica to resin material in the low refractive index coating material B-1 was changed to 40/60 (mass%), the concentration of fluorine-containing leveling agent (RS-78) was changed to 10 mass%, and the concentration of silicon-containing lubricant (BYK-UV 3500) was changed to 10 mass%.
Example 5
An antireflection film C-5 was produced in the same manner as in example 1, except that a low refractive index coating material B-5 was used in which the ratio of hollow silica to resin material in the low refractive index coating material B-1 was changed to 40/60 (mass%), the concentration of fluorine-containing leveling agent (RS-78) was changed to 10 mass%, and the concentration of silicon-containing lubricant (BYK-UV 3500) was changed to 5 mass%.
Example 6
An antireflection film C-6 was produced in the same manner as in example 1, except that a low refractive index coating material B-6 was used in which the ratio of the hollow silica/resin material in the low refractive index coating material B-1 was changed to 40/60 (mass%), the concentration of the fluorine-containing leveling agent (RS-78) was changed to 20 mass%, and the concentration of the silicon-containing lubricant (BYK-UV 3500) was changed to 10 mass%.
Example 7
An antireflection film C-7 was produced in the same manner as in example 1, except that a low refractive index coating material B-7 was used in which the ratio of hollow silica to resin material in the low refractive index coating material B-1 was changed to 50/50 (mass%).
Example 8
An antireflection film C-8 was produced in the same manner as in example 1, except that a low refractive index coating material B-8 was used in which the ratio of the hollow silica/resin material in the low refractive index coating material B-1 was changed to 50/50 (mass%), the concentration of the fluorine-containing leveling agent (RS-78) was changed to 10 mass%, and the concentration of the silicon-containing lubricant (BYK-UV 3500) was changed to 10 mass%.
Comparative example 1
An antireflection film C-9 was produced in the same manner as in example 1, except that a low refractive index paint B-9 was used in which the concentration of the fluorine-containing leveling agent (RS-78) in the low refractive index paint B-1 was changed to 20% by mass and the concentration of the silicon-containing lubricant (BYK-UV 3500) was changed to 0% by mass.
Comparative example 2
An antireflection film C-10 was produced in the same manner as in example 1, except that the low refractive index paint B-10 was used in which the concentration of the fluorine-containing leveling agent (RS-78) in the low refractive index paint B-1 was changed to 5 mass% and the concentration of the silicon-containing lubricant (BYK-UV 3500) was changed to 15 mass%.
Comparative example 3
An antireflection film C-11 was produced in the same manner as in example 1, except that the low refractive index coating material B-11 was used, in which the ratio of the hollow silica/resin material in the low refractive index coating material B-1 was changed to 40/60 (mass%), the concentration of the fluorine-containing leveling agent (RS-78) was changed to 20 mass%, and the concentration of the silicon-containing lubricant (BYK-UV 3500) was changed to 0 mass%.
Comparative example 4
An antireflection film C-12 was produced in the same manner as in example 1, except that the low refractive index paint B-12 was used in which the ratio of the hollow silica/resin material in the low refractive index paint B-1 was changed to 40/60 (mass%), the concentration of the fluorine-containing leveling agent (RS-78) was changed to 5 mass%, and the concentration of the silicon-containing lubricant (BYK-UV 3500) was changed to 15 mass%.
Comparative example 5
An antireflection film C-13 was produced in the same manner as in example 1, except that a low refractive index coating material B-13 was used in which the ratio of the hollow silica/resin material in the low refractive index coating material B-1 was changed to 50/50 (mass%), the concentration of the fluorine-containing leveling agent (RS-78) was changed to 20 mass%, and the concentration of the silicon-containing lubricant (BYK-UV 3500) was changed to 0 mass%.
Comparative example 6
An antireflection film C-14 was produced in the same manner as in example 1, except that the low refractive index coating material B-14 was used, in which the ratio of the hollow silica/resin material in the low refractive index coating material B-1 was changed to 50/50 (mass%), the concentration of the fluorine-containing leveling agent (RS-78) was changed to 5 mass%, and the concentration of the silicon-containing lubricant (BYK-UV 3500) was changed to 15 mass%.
Comparative example 7
An antireflection film C-15 was produced in the same manner as in example 1, except that the low refractive index coating material B-15 was used in which the ratio of the hollow silica/resin material in the low refractive index coating material B-1 was changed to 70/30 (mass%), the concentration of the fluorine-containing leveling agent (RS-78) was changed to 15 mass%, and the concentration of the silicon-containing lubricant (BYK-UV 3500) was changed to 5 mass%.
Comparative example 8
An antireflection film C-16 was produced in the same manner as in example 1, except that the low refractive index paint B-16 was used, in which the ratio of the hollow silica/resin material in the low refractive index paint B-1 was changed to 70/30 (mass%), the concentration of the fluorine-containing leveling agent (RS-78) was changed to 10 mass%, and the concentration of the silicon-containing lubricant (BYK-UV 3500) was changed to 10 mass%.
Comparative example 9
An antireflection film C-17 was produced in the same manner as in example 1, except that a low refractive index paint B-17 was used in which the ratio of the hollow silica/resin material in the low refractive index paint B-1 was changed to 0/100 (mass%), the concentration of the fluorine-containing leveling agent (RS-78) was changed to 10 mass%, and the concentration of the silicon-containing lubricant (BYK-UV 3500) was changed to 10 mass%.
The physical properties of the antireflection films of examples 1 to 8 and comparative examples 1 to 9 thus produced were measured as follows.
< refractive index >
The refractive index value (nD) was measured at 20℃using a D-line having a wavelength of 589nm using an Abbe refractometer (model: NAR-3T) manufactured by Eben Co., ltd. Wherein, in the solvent-containing solution, the refractive index is directly measured in the solvent-containing state, and the value of the refractive index of the solution excluding the solvent is calculated from the measured value and the dilution ratio of the solvent.
< surface roughness of Low refractive index layer surface >
The surface roughness of the surface of the low refractive index layer was measured using a scanning probe microscope E-sweep (manufactured by SII Nano Technology Co., ltd.) under the following conditions.
Cantilever arm: si cantilever (Hitachi high technology Co., ltd.)
Measurement range: 1 μm by 1 μm
< intensity ratio of silicon to fluorine at the surface of Low refractive index layer >
The surface of the low refractive index layer was measured in a thermal relaxation low-speed pulse sputtering mode by glow discharge emission spectrometer GD-Profiler2 (manufactured by horiba, inc.). To confirm the element ratio at the outermost surface, the silicon detection intensity I (Si), fluorine detection intensity I (F) and the silicon-to-fluorine detection intensity ratio I (Si)/I (F) calculated from the ratio of both were calculated at the shortest sputtering time of 0.02 seconds.
Gas species: high purity Ne gas
Electrode diameter: 4mm of
Pulse frequency: 1000Hz
Sampling seconds: after 0.02 seconds
< resistance to abrasion by cloth >
100g/cm of a 4-fold medical gauze (manufactured by Dagasaki medical Co., ltd.) was applied 2 After 100 rounds of the surface of each of the films of examples and comparative examples on the low refractive index layer side, whether or not scratches were present was visually judged, and the evaluation was performed according to the following criteria.
And (2) the following steps: no scratch
X: has more than one scratch
< reflectance (apparent reflectance) >
The measurement was performed in accordance with JIS Z8701 by using SD7000 manufactured by Nippon Denshoku Kogyo Co. In the measurement, in order to prevent reflection from the back surface (substrate layer side) of the films of each of examples and comparative examples, a black aerosol was applied to the opposite surface of the low refractive index layer and dried, followed by measurement.
< fingerprint erasability >
After dropping an artificial fingerprint solution (oleic acid) on the surface of the sample, the artificial fingerprint solution was spread to a diameter of about 11mm with a silica gel pad. The artificial fingerprint solution was applied with a load of 500g using a 3M Japan Scotch-Brite No.5000 cloth, in which state it was passed over the sample. The above test was repeated until the wiping was performed, and the sample that could be completely wiped out within 5 times was evaluated as having good fingerprint wiping performance (o), and the case where it was required for 6 times or more was evaluated as having poor fingerprint wiping performance (x).
< contact Angle of Water and oleic acid >
Contact angles were measured using an automatic contact angle meter DMo-601 (manufactured by Kyowa Kagaku Co., ltd.) using test liquids of water and oleic acid under the following conditions, respectively.
Liquid amount: 2.0 mu L
The analysis method comprises the following steps: theta/2 process
The results of measuring the properties of the antireflection films of examples 1 to 8 and comparative examples 1 to 9 are shown in tables 1 and 2 below.
TABLE 1
TABLE 2
/>
Claims (9)
1. An antireflection film, characterized in that,
the substrate layer comprises a thermoplastic resin, a hard coating layer which is a cured coating layer, and a low refractive index layer which has a refractive index lower than that of the hard coating layer by 0.05 or more,
the low refractive index layer has a thickness of 70-130 nm, and contains a fluorine-containing leveling agent and a silicon-containing lubricant,
the surface roughness of the surface of the low refractive index layer measured by an atomic force microscope is 5.0nm or less,
the intensity ratio I (Si)/I (F) of silicon to fluorine of the surface of the low refractive index layer measured by a glow discharge emission spectrometer is 0.8 to 3.2,
the visual reflectance of the antireflection film is 3.0% or less.
2. The antireflection film according to claim 1, wherein,
The visual reflectance of the antireflection film is 1.6-2.8%.
3. The antireflection film according to claim 1 or 2, wherein,
the low refractive index layer contains hollow silica.
4. The antireflection film according to claim 3, wherein,
the mass ratio of the hollow silica to the resin material contained in the low refractive index layer is 20:80-60:40.
5. The antireflection film according to any one of claims 1 to 4,
the silicon-containing lubricant is a polydimethylsiloxane-containing lubricant.
6. The antireflection film according to any one of claims 1 to 5,
the mass ratio of the silicon-containing lubricant to the fluorine-containing leveling agent in the low refractive index layer is 9:1-5:5.
7. The antireflection film according to any one of claims 1 to 6,
the oleic acid contact angle of the surface of the low refractive index layer is above 55 degrees.
8. The antireflection film according to any one of claims 1 to 7,
the anti-reflective coating is used for insert molding applications.
9. A resin molded article characterized in that,
the antireflection film according to any one of claims 1 to 8 provided on the surface of the resin molded article.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-077242 | 2021-04-30 | ||
| JP2021077242 | 2021-04-30 | ||
| PCT/JP2022/018650 WO2022230789A1 (en) | 2021-04-30 | 2022-04-25 | Anti-reflective film and resin molded article using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117178206A true CN117178206A (en) | 2023-12-05 |
Family
ID=83847248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280029025.7A Pending CN117178206A (en) | 2021-04-30 | 2022-04-25 | Antireflection film and resin molded article using same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2022230789A1 (en) |
| KR (1) | KR20240001120A (en) |
| CN (1) | CN117178206A (en) |
| TW (1) | TW202311037A (en) |
| WO (1) | WO2022230789A1 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8611010B2 (en) * | 2008-09-30 | 2013-12-17 | 3M Innovative Properties Company | Substrate comprising unmatched refractive index primer at optically significant thickness |
| JP6101017B2 (en) | 2012-08-22 | 2017-03-22 | 東レフィルム加工株式会社 | Molded laminated film |
| JP2015178550A (en) * | 2014-03-19 | 2015-10-08 | 株式会社豊田自動織機 | Film containing silicone-based surface conditioner and/or fluorine-based surface conditioner |
| WO2017170246A1 (en) * | 2016-03-30 | 2017-10-05 | 日本ペイント・オートモーティブコーティングス株式会社 | Laminate film for molded decoration |
| CN113226742A (en) * | 2018-12-26 | 2021-08-06 | 东山薄膜株式会社 | Antireflection film and method for producing same |
-
2022
- 2022-04-25 JP JP2023517494A patent/JPWO2022230789A1/ja active Pending
- 2022-04-25 KR KR1020237031753A patent/KR20240001120A/en unknown
- 2022-04-25 CN CN202280029025.7A patent/CN117178206A/en active Pending
- 2022-04-25 WO PCT/JP2022/018650 patent/WO2022230789A1/en active Application Filing
- 2022-04-25 TW TW111115563A patent/TW202311037A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| KR20240001120A (en) | 2024-01-03 |
| JPWO2022230789A1 (en) | 2022-11-03 |
| TW202311037A (en) | 2023-03-16 |
| WO2022230789A1 (en) | 2022-11-03 |
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