CN113671608B - Antiglare film and polarizing plate having the same - Google Patents
Antiglare film and polarizing plate having the same Download PDFInfo
- Publication number
- CN113671608B CN113671608B CN202010587072.6A CN202010587072A CN113671608B CN 113671608 B CN113671608 B CN 113671608B CN 202010587072 A CN202010587072 A CN 202010587072A CN 113671608 B CN113671608 B CN 113671608B
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- China
- Prior art keywords
- acrylate
- meth
- antiglare
- antiglare film
- weight
- Prior art date
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 115
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
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- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims description 3
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 3
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- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 claims description 3
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- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
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- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 claims description 2
- FULIVAOPQQVMDQ-UHFFFAOYSA-N dimethoxymethane;propane Chemical compound CCC.COCOC FULIVAOPQQVMDQ-UHFFFAOYSA-N 0.000 claims 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 2
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 10
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
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- 238000000576 coating method Methods 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 5
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 5
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Optical Elements Other Than Lenses (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses an anti-dazzle film and a polarizing plate with the same, wherein the anti-dazzle film comprises a transparent base material and an anti-dazzle layer, the anti-dazzle layer comprises acrylic binder resin, surfactant containing acrylate-ether group and a plurality of silica nanoparticles, wherein the average secondary particle diameter of micron-sized floccules formed by the nanoparticles is between 1,600nm and 3,300nm under an optical microscope. The antiglare film can provide reliable antiglare properties at low haze.
Description
Technical Field
The present invention relates to an antiglare film useful for image display equipment, and more particularly, to an antiglare film that can provide reliable antiglare properties at low haze.
Background
With the increasing development of display technology, image display devices such as Liquid Crystal Displays (LCDs), organic light emitting diode displays (OLEDs), etc., demands for display performance such as high contrast ratio, wide viewing angle, high luminance, thin, large, high definition, and additional function diversification have been widely put forward.
In general, the display is used in an environment where an external light source is mostly present, which generates a reflection effect on the surface of the panel to cause glare and further reduce the visual and organoleptic viewing effects, so that an optical film with a surface treatment, such as an antiglare film or an antireflection film, is usually required to be added on the surface of the display to modulate light, reduce reflection and reduce the influence of the reflected light of external clutter on the displayed image.
In order to provide an antiglare film with excellent antiglare properties in a bright room environment and with high contrast in a dark room environment, a method is known in which a low-haze antiglare film can be developed using small-particle-diameter organic fine particles to achieve high contrast. In the related art, it has been suggested to apply an antiglare layer containing organic fine particles on a transparent substrate, and to form an uneven structure on a film surface when the organic fine particles are applied by aggregating the organic fine particles with nano particles to provide antiglare properties and achieve a low glare effect. However, the aggregation of organic microparticles and nanoparticles is not easily controlled, which tends to cause a less-than-expected uneven structure on the film surface, resulting in a decrease in antiglare properties or an increase in optical rotation. Further, an antiglare layer containing organic fine particles having a large particle diameter and/or micron-sized silica particles is coated on a transparent substrate, and the haze is high due to a strong light diffusion effect by the fine particles, so that an antiglare film having a low haze but good antiglare property is not provided.
Accordingly, there is a need for an antiglare film that has low haze but provides satisfactory antiglare properties.
Disclosure of Invention
The purpose of the present invention is to provide an antiglare film that has low haze but can provide satisfactory antiglare properties, and a polarizing plate having the antiglare film.
An object of the present invention is to provide an antiglare film comprising a transparent substrate and an antiglare film on the transparent substrate, wherein the antiglare layer has micron-sized flocs formed of silica nanoparticles thereon, which can provide reliable antiglare property at low haze. The antiglare film of the present invention comprises a transparent substrate and an antiglare layer on the transparent substrate, wherein the antiglare layer comprises an acrylic binder resin, an acrylate-ether-based surfactant, and a plurality of silica nanoparticles, wherein micron-sized flocs formed from the nanoparticles exhibit an average secondary particle size under an optical microscope of between 1,600nm and 3,300 nm.
The antiglare film of the present invention is low in haze, has a fine surface, and provides excellent antiglare properties. The antiglare film of the present invention has a haze of not more than 5%, preferably not more than 3%, and has an arithmetic mean height (Sa) of surface roughness of 0.02 μm to 0.25 μm, a maximum height (Sz) of 0.25 μm to 2.50 μm, a center line mean roughness (Ra) of 0.01 μm to 0.30 μm, a full roughness height (Ry) of 0.10 μm to 0.90 μm, a mean peak pitch (RSm) of 20 μm to 200 μm, and a square root slope (Rdq) of 0.80 DEG to 7.50 DEG by agglomerating silica nanoparticles.
According to the antiglare film of the present invention, in the antiglare layer, the average primary particle diameter of each silica nanoparticle is between 5nm and 150nm, and preferably between 5nm and 120 nm.
According to a preferred embodiment of the antiglare film of the present invention, the silica nanoparticles may be present in the antiglare layer in an amount of from 0.5 to 12 parts by weight, preferably from 0.8 to 10 parts by weight, per hundred parts by weight of the acrylic binder resin.
According to a preferred embodiment of the antiglare film of the present invention, the acrylate-ether group-containing surfactant may be present in the antiglare layer in an amount of from 0.01 to 8 parts by weight, preferably from 0.05 to 5 parts by weight, per hundred parts by weight of the acrylic binder resin. Furthermore, in the antiglare layer of the antiglare film of the present invention, the relative weight ratio of the silica nanoparticles to the acrylate-ether group-containing surfactant is from 0.5 to 100, preferably from 0.5 to 80.
In the antiglare layer of the antiglare film of the present invention, the acrylate-ether group-containing surfactant is a polymerized compound composed of one or more monofunctional or polyfunctional unsaturated monomers having a vinyl group or (meth) acryloyl group and one or more polyether monomers represented by the formula (I):
Wherein R1 is hydrogen or methyl, R2 is hydrogen, C1 to C10 hydrocarbon group, phenyl or (meth) acryl, a is 1 or an integer greater than 1, b is 0 or an integer greater than 0, wherein the total amount of polyether monomer represented by formula (I) in the acrylate-ether group-containing surfactant is 0.1 to 60 mole percent and the matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) of the acrylate-ether group-containing surfactant has an average molecular weight of between 200 to 6,000 and an average Ethylene Oxide number (EO) Unit of between 1 to 40.
In the antiglare film of the present invention, the antiglare layer may have a thickness of from 2 μm to 10 μm, preferably from 2 μm to 8 μm.
In the antiglare film of the present invention, the acrylic binder resin of the antiglare layer comprises a (meth) acrylate composition and an initiator, wherein the (meth) acrylate composition comprises 35 to 50 parts by weight of a urethane (meth) acrylate oligomer having a functionality of 6 to 15, 12 to 20 parts by weight of a (meth) acrylate monomer having a functionality of 3 to 6, and 1.5 to 12 parts by weight of a (meth) acrylate monomer having a functionality of less than 3, wherein the urethane (meth) acrylate oligomer having a functionality of 6 to 15 has a number average molecular weight (Mn) of 1,000 to 4,500.
In still another aspect of the present invention, there is provided an antiglare film, which may further include organic fine particles in an antiglare layer to adjust haze, wherein the antiglare film comprises a transparent substrate and an antiglare layer, wherein the antiglare layer comprises an acrylic binder resin, an acrylate-ether group-containing surfactant, a plurality of silica nanoparticles, and a plurality of organic fine particles, wherein micron-sized flocs formed from the silica nanoparticles exhibit an average secondary particle diameter of between 1,600nm and 3,300nm under an optical microscope.
The antiglare film of the present invention containing organic fine particles in the antiglare layer may have a refractive index of each organic fine particle of between 1.4 and 1.6, and may have a particle diameter of each organic fine particle of between 0.5 μm and 6 μm, and preferably between 1 μm and 4 μm.
Another object of the present invention is to provide a method for preparing an antiglare film, which comprises uniformly mixing an acrylic binder resin, an acrylate-ether group-containing surfactant, and a plurality of silica nanoparticles to form an antiglare solution, coating the antiglare solution on a transparent substrate, drying the substrate coated with the antiglare solution, and then curing by radiation or electron beam to form the antiglare film.
Another object of the present invention is to provide a polarizing plate comprising a polarizing element and the antiglare film.
The antiglare film and the polarizing plate of the present invention have micron-sized floccules formed of silica nanoparticles in the antiglare layer, and thus can provide reliable antiglare properties at low haze.
The above summary is intended to provide a simplified summary of the disclosure so that the reader is a basic understanding of the disclosure. This summary is not an extensive overview of the disclosure and is intended to neither identify key/critical elements of the embodiments of the invention nor delineate the scope of the invention. Those skilled in the art to which the present invention pertains will readily appreciate the basic spirit and technical means and aspects of the present invention after reviewing the following description.
The invention will now be described in more detail with reference to the drawings and specific examples, which are not intended to limit the invention thereto.
Drawings
Fig. 1 is a light transmission image of the antiglare film of example 1 of the present invention at a magnification of 200 x in an optical microscope.
Fig. 2 is a graph showing the light transmission image of the antiglare film of example 4 according to the present invention at a magnification of 200 x in an optical microscope.
FIG. 3 is a Scanning Electron Microscope (SEM) 5,000 magnification image of a cross-section of an antiglare film according to example 4 of the invention.
Fig. 4 is a graph showing the light transmission image of the antiglare film of example 8 according to the present invention at a magnification of 200 x in an optical microscope.
Fig. 5 is a light transmission image of the antiglare film of example 10 of the present invention at a magnification of 200 x in an optical microscope.
Detailed Description
The advantages, features, and technical approaches to the present invention will be more fully understood by reference to the exemplary embodiments that now follow, and in fact may be practiced in different but not limited to the embodiments set forth herein, but rather, to the contrary, are provided to fully convey the scope of the invention to those skilled in the art, and are defined solely by the appended claims.
And unless otherwise defined, all terms (including technical and scientific terms) used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and terms such as commonly used dictionaries should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an excessively idealized or overly formal sense unless expressly so defined hereinafter.
In the present specification, the term "meth" acrylate refers to methacrylate and acrylate.
An object of the present invention is to provide an antiglare film that provides reliable antiglare properties at low haze, comprising a transparent substrate and an antiglare layer on the transparent substrate, wherein in the antiglare layer, micron-sized flocs formed of silica nanoparticles are present. The antiglare film of the present invention comprises a transparent substrate and an antiglare layer disposed on the transparent substrate, wherein the antiglare layer comprises an acrylic binder resin, an acrylate-ether-based surfactant, and a plurality of silica nanoparticles, wherein micron-sized flocs formed from the plurality of nanoparticles exhibit an average secondary particle size of between 1,600nm and 3,300nm under an optical microscope.
The antiglare film of the present invention is low in haze, has a fine surface, and provides excellent antiglare properties. In an antiglare film embodiment of the present invention, the antiglare film has a haze of not greater than 5%, preferably not greater than 3%. The antiglare film of the present invention has an arithmetic mean height (Sa) of surface roughness of 0.02 μm to 0.25 μm, a maximum height (Sz) of 0.25 μm to 2.50 μm, a center line mean roughness (Ra) of 0.01 μm to 0.30 μm, a full roughness height (Ry) of 0.10 μm to 0.90 μm, a mean peak pitch (RSm) of 20 μm to 200 μm, and a square root slope (Rdq) of 0.80 DEG to 7.50 deg. The antiglare film of the present invention achieves low haze by agglomeration of silica nanoparticles and provides excellent antiglare properties under fine surfaces of such roughness.
In a preferred embodiment of the antiglare film of the present invention, the antiglare film has an arithmetic mean height (Sa) of surface roughness of 0.03 μm to 0.20 μm, a maximum height (Sz) of 0.40 μm to 2.20 μm, a center line mean roughness (Ra) of 0.02 μm to 0.25 μm, a full roughness height (Ry) of 0.20 μm to 0.80 μm, a mean peak pitch (RSm) of 20 μm to 180 μm, and a square root slope (Rdq) of 1.00 ° to 6.50 °.
In an embodiment of the present invention, a suitable transparent substrate may be selected from a film material with good mechanical strength and light transmittance, which may be, but not limited to, polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), triacetyl cellulose (TAC), polyimide (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), or cyclic olefin Copolymer (COP), etc.
In the preferred embodiment of the present invention, the transparent substrate is preferably selected to have a light transmittance of 80% or more, more preferably 90% or more. And the thickness of the transparent substrate is about 10 μm to 500. Mu.m, preferably 15 μm to 250. Mu.m, more preferably 20 μm to 100. Mu.m.
In the antiglare film of the present invention, the antiglare layer may have a thickness of between 2 μm and 10 μm, and preferably between 2 μm and 8 μm.
In the antiglare film of the present invention, the average primary particle diameter of the silica nanoparticles used in the antiglare layer is in the range of 5nm to 150nm, preferably in the range of 5nm to 120nm, more preferably in the range of 5nm to 100 nm. In an embodiment of the present invention, the silica nanoparticles may be surface-unmodified or surface-modified silica nanoparticles, and the surface-modified silica nanoparticles may be silica nanoparticles modified with siloxane having alkyl, acryl or epoxy groups, and the silica nanoparticles are distributed inside the antiglare layer with polarity between the silica nanoparticles and the resin being close. The average primary particle size of the silica nanoparticles may be measured by the specific surface area method (BET) or dynamic light scattering method.
According to an embodiment of the antiglare film of the present invention, the silica nanoparticles in the antiglare layer are preferably in the range of 0.5 to 12 parts by weight, particularly 0.8 to 10 parts by weight, per hundred parts by weight of the acrylic binder resin. When the amount of the silica nanoparticles used is less than the aforementioned range, the antiglare property of the antiglare film may be insufficient. When the amount of the silica nanoparticles used is higher than the above range, there is a possibility that the haze of the antiglare film may be increased.
In the antiglare film of the present invention, the antiglare layer contains an acrylate-ether group-containing surfactant which is a polymerized compound formed by polymerizing one or more monofunctional or polyfunctional unsaturated monomers having a vinyl group or (meth) acryloyl group with one or more polyether monomers represented by the formula (I):
Wherein R1 is hydrogen or methyl, R2 is hydrogen, C1 to C10 hydrocarbon group, phenyl or (meth) acryl, a is 1 or an integer greater than 1, b is 0 or an integer greater than 0, wherein the total amount of polyether monomers represented by formula (I) is between 0.1 mole percent and 60 mole percent of the acrylate-ether group-containing surfactant. The average molecular weight of matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) of the surfactant containing the acrylate-ether group is between 200 and 6,000, and the average oxyethylene radical (EO) Unit is between 1 and 40.
The polyether monomer represented by the above formula (I), wherein a is an integer of 1 to 100, more preferably an integer of 1 to 40; and b is an integer from 0 to 100, preferably an integer from 0 to 40. Among the polyether monomers of the above formula (I), an oxyethylene (EO) Unit and an oxypropylene (Propylene Oxide (PO) Unit) are connected by random copolymerization, alternating copolymerization or block copolymerization. In the foregoing polyether monomer of formula (I), when R2 is a C1 to C10 hydrocarbyl group, the hydrocarbyl group may be a substituted C1 to C10 hydrocarbyl group, and the substituent may be a hydrocarbyl group, an alkenyl group, a hydroxyl group, a phenyl group, an alkoxy group, or an epoxy group.
In the preferred embodiment of the antiglare film of the present invention, the average molecular weight of the matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) containing the acrylate-ether surfactant is preferably from 200 to 4,500, more preferably from 200 to 3,000, and the average oxyethylene (EO) Unit is preferably from 1 to 35, more preferably from 1 to 30.
The monofunctional or polyfunctional unsaturated monomer having a vinyl group or a (meth) acryloyl group used for forming the acrylate-ether-containing surfactant of the present invention is preferably selected from one or more monofunctional unsaturated monomers having a vinyl group or a (meth) acryloyl group and one or more polyfunctional unsaturated monomers having a vinyl group or a (meth) acryloyl group.
Preferred examples of the monofunctional unsaturated monomer having a vinyl group or a (meth) acryloyl group suitable for forming the acrylate-ether-based surfactant of the present invention include, but are not limited to, styrene (Styrene), α -methylstyrene (α -METHYL STYRENE), vinyl ether monomers such as ethyl vinyl ether (ETHYL VINYL ETHER), n-Butyl vinyl ether (n-Butyl VINYL ETHER), and cyclohexyl vinyl ether (cyclohexyl VINYL ETHER), etc., ethyl (meth) acrylate, E (M) a), (n-Butyl (meth) acrylate, n-B (M) a), 2-ethylhexyl (meth) acrylate (2-ethylhexyl (meth) acrylate,2-EH (M) a), 2-hydroxyethyl (meth) acrylate (2-hydroxyethyl (meth) acrylate,2-HE (M) a), 2-ethoxyethyl (meth) acrylate (2-ethoxyethyl (meth)) acrylate, tetrahydrofuran (meth) acrylate (3-methyl) acrylate, THF (M) acrylate, isopropyl (35-35 o) acrylate, isopropyl (35 o (35) acrylate, PHE (M) A), perfluoroalkyl (perfluoroalkyl (meth)) acrylate, polydimethyl siloxane functionalized with (meth) acrylate groups, caprolactone and/or valerolactone modified hydroxyalkyl (meth) acrylate, and the like. Furthermore, the monofunctional unsaturated monomer may optionally be a chain transfer agent having vinyl groups for controlling the molecular weight, such as 2, 4-dicyanopent-1-ene, 2, 4-dicyano-4-methylpent-1-ene, 2, 4-diphenyl-4-methylpent-1-ene, 2-cyano-4-methyl-4-phenyl-pent-1-ene, dimethyl 2, 2-dimethyl-4-methylenepentane-1, 5-dicarboxylic acid, dibutyl 2, 2-dimethyl-4-methylenepentane-1, 5-dicarboxylic acid, and the like.
Preferred examples of the polyfunctional unsaturated monomer having a vinyl group or a (meth) acryloyl group suitable for forming the acrylate-ether-based surfactant of the present invention include, but are not limited to, ethylene glycol di (meth) acrylate (ethylene glycol di (meth) acrylate, EDG (M) A), diethylene glycol di (meth) acrylate (DIETHYLENE GLYCOL DI (meth) acrylate, DEGD (M) A), 1,6-hexanediol di (meth) acrylate (1, 6-hexanediol di (meth) acrylate, HDD (M) A), polyethylene glycol di (meth) acrylate (polyethylene glycol di (meth) acrylate), polypropylene glycol di (meth) acrylate (polypropylene glycol di (meth) acrylate), and the like.
The aforementioned surfactants containing acrylate-ether groups are selected from but not limited to BYK-3440, BYK-3441, BYK3560, BYK-3565, BYK-3566 and BYK-3535 (manufactured by BYK-Chemie Co., germany).
According to a preferred embodiment of the antiglare film of the present invention, the acrylate-ether group-containing surfactant may be present in the antiglare layer in an amount of from 0.01 to 8 parts by weight, preferably from 0.05 to 5 parts by weight, per hundred parts by weight of the acrylic binder resin. When the amount of the acrylic acid ester-ether group-containing surfactant used is less than the aforementioned range, the antiglare property of the antiglare film may be insufficient. When the amount of the acrylic acid ester-ether group-containing surfactant used is higher than the above range, there is a possibility that the haze of the antiglare film may be increased.
According to the antiglare film of the present invention, the acrylic ester-ether based surfactant contained in the antiglare layer flocculates silica nanoparticles to form micron-sized flocs having an average secondary particle diameter of 1,600nm to 3,300 nm. Without being bound by theory, in the antiglare layer of the antiglare film of the present invention, when the relative weight ratio of the silica nanoparticles to the acrylate-ether group-containing surfactant is between 0.5 and 100, the acrylate-ether group-containing surfactant facilitates flocculation of the silica nanoparticles to the aforementioned average secondary particle size, which can provide the antiglare film with excellent antiglare properties without affecting the film surface fineness of the antiglare film. When the relative ratio of the silica nanoparticles to the surfactant containing an acrylate-ether group is outside the above range, the size of the floccules of the silica nanoparticles cannot be controlled, and the antiglare film has defects such as low antiglare property, excessive haze, and appearance of the film surface. Furthermore, in a preferred embodiment of the antiglare film of the present invention, the relative weight ratio of the silica nanoparticles of the antiglare layer to the acrylate-ether group-containing surfactant is preferably from 0.5 to 80.
In the antiglare film of the present invention, the micron-sized floccules of the silica nanoparticles in the antiglare layer may be reagglomerated, disaggregated, or aggregated into a co-continuous network structure, and reagglomeration may help to improve the antiglare property again without reagglomerating and affecting the antiglare property.
In still another embodiment of the antiglare film of the present invention, other silica nanoparticles having a higher degree of hydrophobic modification may be added to the antiglare layer without affecting the physical properties of the antiglare film, so that the silica nanoparticles have a large difference in polarity from the resin and are distributed on the surface of the antiglare layer, thereby adjusting the physical properties of the antiglare film surface, for example, adding silica nanoparticles resistant to surface scratches.
In the antiglare film of the present invention, the acrylic binder resin used for the antiglare layer comprises a (meth) acrylate composition and an initiator, wherein the (meth) acrylate composition in the acrylic binder resin comprises 35 to 50 parts by weight of a urethane (meth) acrylate oligomer having a functionality of between 6 and 15, 12 to 20 parts by weight of a (meth) acrylate monomer having a functionality of 3 to 6, and 1.5 to 12 parts by weight of a (meth) acrylate monomer having a functionality of less than 3.
In a preferred embodiment of the present invention, the polyurethane (meth) acrylate oligomer having a functionality of between 6 and 15 has a molecular weight of not less than 1,000, preferably between 1,000 and 4,500. In a further preferred embodiment of the invention, urethane (meth) acrylate oligomers having a functionality of between 6 and 15 are preferably used, aliphatic urethane (meth) acrylate oligomers having a functionality of between 6 and 15 being preferred.
In a preferred embodiment of the present invention, the (meth) acrylate monomers having a functionality of 3 to 6 have a molecular weight of less than 1,000, preferably a molecular weight of less than 800. Suitable (meth) acrylate monomers for use in the present invention having a functionality of 3 to 6 may be, for example, one of pentaerythritol tetra (meth) acrylate (pentaerythritol tetra (meth) acrylate), dipentaerythritol penta (meth) acrylate (dipentaerythritol penta (meth) acrylate, DPP (M) a), dipentaerythritol hexa (meth) acrylate (dipentaerythritol hexa (meth) acrylate, DPH (M) a), trimethylolpropane tri (meth) acrylate (trimethylolpropane tri (meth) acrylate, TMPT (M) a), ditrimethylolpropane tetra (ditrimethylolpropane tetra (meth) acrylate, DTMPT (M) a), pentaerythritol tri (meth) acrylate (pentaerythritol tri (meth) acrylate, PET (M) a), or a combination thereof, but are not limited thereto. The (meth) acrylate monomer having a functionality of 3 to 6 is preferably one of pentaerythritol triacrylate (pentaerythritol triacrylate, PETA), dipentaerythritol hexaacrylate (dipentaerythritol hexaacrylate, DPHA), dipentaerythritol pentaacrylate (dipentaerythritol pentaacrylate, DPPA), or a combination thereof, but is not limited thereto.
In a preferred embodiment of the present invention, the (meth) acrylate monomer having a functionality of less than 3 may be a (meth) acrylate monomer having a functionality of 1 or 2, and a molecular weight of less than 500. (meth) acrylate monomers having a functionality of less than 3 suitable for use in the present invention may be, for example, 2-ethylhexyl (meth) acrylate (2-ethylhexyl (meth) acrylate,2-EH (M) A), 2-hydroxyethyl (meth) acrylate (2-hydroxyethyl (meth) acrylate,2-HE (M) A), 3-hydroxypropyl (meth) acrylate (3-hydroxypropyl (meth) acrylate,3-HP (M) A), 4-hydroxybutyl (meth) acrylate (4-hydroxybutyl (meth) acrylate,4-HB (M) A), 2-butoxyethyl (meth) acrylate (2-butoxyethyl (meth) acrylate), 1,6-hexanediol di (meth) acrylate (1, 6-hexanediol di (meth) acrylate, HDD (M) A), cyclotrimethylol propane methylacrylate (cyclic trimethylolpropane formal (meth) acrylate, CTF (M) A), 2-phenoxyethyl (meth) acrylate (2-phenoxyethyl (meth) acrylate, PHE (M) A), tetrahydrofuran (62) acrylate (meth) acrylate, l (M) a), diethylene glycol di (meth) acrylate (DIETHYLENE GLYCOL DI (meth) acrylate, DEGD (M) a), dipropylene glycol di (meth) acrylate (dipropylene glycol di (meth) acrylate, DPGD (M) a), tripropylene glycol di (meth) acrylate (tripropylene glycol di (meth) acrylate, TPGD (M) a), isobornyl (meth) acrylate (isobornyl (meth) acrylate, IBO (M) a), or combinations thereof, but are not limited thereto. The (meth) acrylate monomer having a functionality of less than 3 is preferably one of 1,6-hexanediol diacrylate (HDDA), cyclotrimethylol propane methylacrylate (CTFA), 2-phenoxyethyl acrylate (PHEA) or isobornyl acrylate (IBOA) or a combination thereof.
Suitable initiators for the acrylic binder resin of the present invention may be any of those known to the art and may be used, and are not particularly limited, and examples thereof include acetophenone type initiators, diphenyl ketone type initiators, propiophenone type initiators, dibenzoyl type initiators, bifunctional α -hydroxy ketone type initiators, and acylphosphine oxide type initiators. The aforementioned initiators may be used alone or in combination.
The anti-dazzle film can adjust the haze by adding organic particles according to the use environment and the visual angle requirement of a product, and particularly adjust the internal scattering effect of the haze in the anti-dazzle layer.
Accordingly, still another aspect of the present invention provides an antiglare film comprising a transparent substrate and an antiglare layer on the transparent substrate, wherein the antiglare layer has a micron-sized aggregate formed of a plurality of silica nanoparticles and a plurality of organic microparticles thereon. The antiglare film of the present invention comprises a transparent substrate and an antiglare layer on the transparent substrate, wherein the antiglare layer comprises an acrylic binder resin, an acrylate-ether-based surfactant, a plurality of silica nanoparticles, and a plurality of organic microparticles, wherein micron-sized floccules formed from the silica nanoparticles exhibit an average secondary particle size of between 1,600nm and 3,300nm under an optical microscope.
The organic fine particles suitable for the antiglare film of the present invention may be selected from organic fine particles having an appropriate refractive index and particle size, and the amount of the organic fine particles added may be controlled to adjust the haze of the antiglare film. Suitable organic microparticles may have a refractive index of between 1.4 and 1.6 and a particle size of between 0.5 μm and 6 μm, and preferably between 1 μm and 4 μm. In an embodiment of the antiglare film in which the organic fine particles adjust the haze, the haze may range from 1% to 50%, but is not limited thereto.
When the haze of the antiglare film of the present invention is adjusted by using the organic fine particles, the amount of the organic fine particles to be added may be adjusted according to the haze actually required, and it is preferable to add between 0.5 and 15 parts by weight, particularly between 1 and 12 parts by weight, of the organic fine particles per hundred parts by weight of the acrylic binder resin.
Organic microparticles suitable for the antiglare layer of the antiglare film of the present invention are polymethyl methacrylate resin microparticles, polystyrene resin microparticles, styrene-methyl methacrylate copolymer microparticles, polyethylene resin microparticles, epoxy resin microparticles, polysiloxane resin microparticles, polyvinylidene fluoride resin microparticles, or polyvinyl fluoride resin microparticles. In the preferred embodiment of the present invention, polymethyl methacrylate resin fine particles, polystyrene resin fine particles or styrene-methyl methacrylate copolymer fine particles are preferably used.
On the film surface of the antiglare film of the present invention, other optical functional layers may also be optionally coated, for example, a low refractive layer to provide antireflection.
Another object of the present invention is to provide a method for producing an antiglare film. The preparation method of the antiglare film comprises the steps of uniformly mixing polyurethane (methyl) acrylate oligomer with the functionality of 6-15, at least one (methyl) acrylate monomer with the functionality of not less than 3, at least one (methyl) acrylate monomer with the functionality of less than 3 and an initiator with a proper solvent to form an acrylic adhesive resin; adding silicon dioxide nano particles and/or organic microparticles, a surfactant containing acrylate-ether groups and an organic solvent into acrylic binder resin, and uniformly mixing to form an anti-dazzle solution; the antiglare film is obtained by coating an antiglare solution on a transparent substrate, drying the substrate coated with the antiglare solution, and forming an antiglare layer on the transparent substrate after irradiation or electron beam curing.
The solvent used in the method for producing an antiglare film of the present invention may be an organic solvent generally used in this technical field, for example, ketones, aliphatic or cycloaliphatic hydrocarbons, aromatic hydrocarbons, ethers, esters or alcohols, etc. One or more organic solvents may be used in both the acrylate composition and the antiglare solution, and suitable solvents include, but are not limited to, acetone, butanone, cyclohexanone, methyl isobutyl ketone, hexane, cyclohexane, methylene chloride, dichloroethane, toluene, xylene, propylene glycol methyl ether, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isopropyl alcohol, n-butanol, isobutyl alcohol, cyclohexanol, diacetone alcohol, propylene glycol methyl ether acetate, tetrahydrofuran, and the like, or the like.
In other embodiments of the present invention, additives such as antistatic agents, colorants, flame retardants, ultraviolet absorbers, antioxidants, surface modifiers, leveling agents without polyether modification, and defoamers may be added to the prepared antiglare solution as desired to provide different functional properties.
The method for applying the antiglare solution may be, for example, a roll coating method, a doctor blade coating method, a dip coating method, a roll coating method, a spin coating method, a spray coating method, or a slit coating method, which are coating methods generally used in the art.
Another object of the present invention is to provide a polarizing plate including a polarizing element, wherein the polarizing plate has the antiglare film on the surface of the polarizing element.
The following examples are provided to further illustrate the invention, but the invention is not limited thereto.
Examples
Preparation example 1: preparation of acrylic binder resin I
42 Parts by weight of urethane acrylate (functionality 6, available from Miwon, korea), 4.5 parts by weight of pentaerythritol triacrylate (PETA), 12 parts by weight of dipentaerythritol hexaacrylate (DPHA), 3 parts by weight of isobornyl acrylate (IBOA), 4 parts by weight of a monomolecular polymerization initiator (Chemcure-481, available from constant bridge industry, taiwan, china), 24.5 parts by weight of Ethyl Acetate (EAC), and 10 parts by weight of n-butyl acetate (nBAC) were mixed and stirred for 1 hour to form the acrylic adhesive resin I.
Example 1: preparation of antiglare film
220 Parts by weight of an acrylic binder resin I, 10 parts by weight of a silica nanoparticle dispersion sol (MEK-AC-4130Y, solid content: 30% and solvent: butanone, commercially available from Nissan chemical, japan), 7.5 parts by weight of an acrylate-ether group-containing surfactant (BYK-UV 3535, solid content: 10% and solvent: ethyl acetate, commercially available from BYK, germany), 60 parts by weight of Ethyl Acetate (EAC) and 120 parts by weight of n-butyl acetate (nBAC) were mixed and stirred for 1 hour to uniformly disperse them, thereby forming an antiglare solution. The antiglare solution was applied to a polyethylene terephthalate (PET) substrate of 80 μm, dried, and then photocured under a nitrogen atmosphere by a UV lamp with a radiation dose of 80mJ/cm2 to form an antiglare layer of 3.4 μm in thickness on the PET substrate.
The obtained antiglare film was subjected to the measurement of transmittance, haze, gloss and clarity by the optical measurement method described later, and the secondary particle diameter and aggregation area size measurement of silica nanoparticles, the surface roughness and the antiglare property were evaluated, and the results are shown in table 1.
The obtained antiglare film was observed under an optical microscope 200 magnification, and an obtained light transmission image is shown in fig. 1.
Example 2: preparation of antiglare film
An antiglare solution was prepared as in example 1, except that 7.5 parts by weight of an acrylate-ether group-containing surfactant (BYK-3440, a solid content of 10%, and dipropylene glycol monomethyl ether as a solvent, available from BYK, germany) was used instead to form the antiglare solution.
The antiglare solution was coated on an 80 μm PET substrate, and the resultant was photocured under a nitrogen atmosphere by a UV lamp having a radiation dose of 80mJ/cm2 to form an antiglare layer having a thickness of 3.3. Mu.m.
The obtained antiglare film was subjected to the measurement of transmittance, haze, gloss and clarity by the optical measurement method described later, and the secondary particle diameter and aggregation area size measurement of silica nanoparticles, the surface roughness and the antiglare property were evaluated, and the results are shown in table 1.
Example 3: preparation of antiglare film
An antiglare solution was prepared as in example 1 except that 7.5 parts by weight of a silica nanoparticle dispersion sol (MEK-AC-2140Z, solid content 40%, solvent butanone, commercially available from Nissan chemical, japan) having an average primary particle diameter of 10nm to 15nm was used instead to form an antiglare solution.
The antiglare solution was applied to a 80 μm PET substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp having a radiation dose of 80mJ/cm2 to form an antiglare layer having a thickness of 3.4. Mu.m.
The obtained antiglare film was subjected to the measurement of transmittance, haze, gloss and clarity by the optical measurement method described later, and the secondary particle diameter and aggregation area size measurement of silica nanoparticles, the surface roughness and the antiglare property were evaluated, and the results are shown in table 1.
Example 4: preparation of antiglare film
The same procedure as in example 3 was conducted except that 15 parts by weight of a silica nanoparticle dispersion sol (MEK-ST-UP, solid content 20%, solvent butanone, commercially available from Nissan chemical, japan) having an average primary particle diameter of 9nm to 15nm and a chain-like structure of 40nm to 100nm was used instead of the silica nanoparticle dispersion sol to form an antiglare solution.
The antiglare solution was applied to a 80 μm PET substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp having a radiation dose of 80mJ/cm2 to form an antiglare layer having a thickness of 3.6 μm on the PET substrate.
The obtained antiglare film was subjected to the measurement of transmittance, haze, gloss and clarity by the optical measurement method described later, and the secondary particle diameter and aggregation area size measurement of silica nanoparticles, the surface roughness and the antiglare property were evaluated, and the results are shown in table 1.
The obtained antiglare film was observed under an optical microscope at a magnification of 200, an obtained light transmission image was shown in fig. 2, and a cross section was observed under a Scanning Electron Microscope (SEM) at a magnification of 5,000, and an obtained image was shown in fig. 3.
Example 5: preparation of antiglare film
The same procedure as in example 3 was conducted except that 7.5 parts by weight of a silica nanoparticle dispersion sol (ELCOM V-8804, 40% solids content, propylene glycol methyl ether as a solvent, commercially available from solar volatile catalyst formation, japan) having an average primary particle diameter of 12nm was used instead to form an antiglare solution.
The antiglare solution was applied to a 80 μm PET substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp having a radiation dose of 80mJ/cm2 to form an antiglare layer having a thickness of 3.6 μm on the PET substrate.
The results of measuring the transmittance, haze, gloss and clarity of the obtained antiglare film by the optical measurement method described later are shown in table 1, and the secondary particle diameter and aggregation area size measurement of silica nanoparticles, the surface roughness and the antiglare property were evaluated, and the results are shown in table 2.
Example 6: preparation of antiglare film
The procedure was as in example 5, except that 20 parts by weight of a silica nanoparticle dispersion sol having an average primary particle diameter of 12nm and a secondary particle diameter of 80nm to 120nm (MEK-5630X, solid content: 30%, solvent butanone, commercially available from the national silica industry, taiwan, china) was used instead, and 15 parts by weight of an acrylate-ether group-containing surfactant (BYK-UV 3535) was used to form an antiglare solution.
The antiglare solution was applied to a 80 μm PET substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp having a radiation dose of 80mJ/cm2 to form an antiglare layer having a thickness of 3.6 μm on the PET substrate.
The obtained antiglare film was subjected to the measurement of transmittance, haze, gloss and clarity by the optical measurement method described later, and the secondary particle diameter and aggregation area size measurement of silica nanoparticles, the surface roughness and the antiglare property were evaluated, and the results are shown in table 1.
Example 7: preparation of antiglare film
The same procedure as in example 4 was conducted except that 30 parts by weight of a silica nanoparticle dispersion sol (MEK-ST-UP) having an average primary particle diameter of 9nm to 15nm and a chain-like structure having a length of 40nm to 100nm was used, and 1.5 parts by weight of an acrylate-ether group-containing surfactant (BYK-3560, solid content 10%, solvent ethyl acetate, available from BYK, germany) was used instead of the acrylate-ether group-containing surfactant to form an antiglare solution.
The antiglare solution was applied to a 80 μm PET substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp having a radiation dose of 80mJ/cm2 to form an antiglare layer having a thickness of 3.5. Mu.m.
The obtained antiglare film was subjected to the measurement of transmittance, haze, gloss and clarity by the optical measurement method described later, and the secondary particle diameter and aggregation area size measurement of silica nanoparticles, the surface roughness and the antiglare property were evaluated, and the results are shown in table 1.
Example 8: preparation of antiglare film
The procedure was as in example 1, except that 40 parts by weight of a silica nanoparticle dispersion sol (MEK-AC-4130Y) having an average primary particle diameter of 40nm to 50nm was used, and that 30 parts by weight of an acrylate-ether group-containing surfactant (BYK-3560) was used instead to form an antiglare solution.
The antiglare solution was applied to a 80 μm PET substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp having a radiation dose of 80mJ/cm2 to form an antiglare layer having a thickness of 3.3 μm on the PET substrate.
The obtained antiglare film was subjected to the measurement of transmittance, haze, gloss and clarity by the optical measurement method described later, and the secondary particle diameter and aggregation area size measurement of silica nanoparticles, the surface roughness and the antiglare property were evaluated, and the results are shown in table 1.
The obtained antiglare film was observed under an optical microscope 200 magnification, and an obtained light transmission image is shown in fig. 4.
Example 9: preparation of antiglare film
The procedure was as in example 2, except that 5 parts by weight of a silica nanoparticle dispersion sol (MEK-AC-4130Y) having an average primary particle diameter of 40nm to 50nm and 3.75 parts by weight of an acrylate-ether group-containing surfactant (BYK-3440) were used to form an antiglare solution.
The antiglare solution was applied to a 80 μm PET substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp having a radiation dose of 80mJ/cm2 to form an antiglare layer having a thickness of 3.2 μm on the PET substrate.
The obtained antiglare film was subjected to the measurement of transmittance, haze, gloss and clarity by the optical measurement method described later, and the secondary particle diameter and aggregation area size measurement of silica nanoparticles, the surface roughness and the antiglare property were evaluated, and the results are shown in table 1.
Example 10: preparation of antiglare film
The same procedure as in example 3 was conducted except that 10 parts by weight of a silica nanoparticle dispersion sol (MEK-ST-ZL) having an average primary particle diameter of 70nm to 100nm was used instead to form an antiglare solution.
The antiglare solution was applied to a 80 μm PET substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp having a radiation dose of 80mJ/cm2 to form an antiglare layer having a thickness of 3.3 μm on the PET substrate.
The obtained antiglare film was subjected to the measurement of transmittance, haze, gloss and clarity by the optical measurement method described later, and the secondary particle diameter and aggregation area size measurement of silica nanoparticles, the surface roughness and the antiglare property were evaluated, and the results are shown in table 1.
The obtained antiglare film was observed under an optical microscope 200 magnification, and an obtained light transmission image is shown in fig. 5.
Example 11: preparation of antiglare film
The procedure was as in example 9, except that 10 parts by weight of the silica nanoparticle dispersion sol (MEK-AC-4130Y) was used instead and 0.75 parts by weight of the acrylate-ether group-containing surfactant (BYK-3440) was used instead to form an antiglare solution.
The antiglare solution was applied to a 80 μm PET substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp having a radiation dose of 80mJ/cm2 to form an antiglare layer having a thickness of 4.1 μm on the PET substrate.
The obtained antiglare film was subjected to the measurement of transmittance, haze, gloss and clarity by the optical measurement method described later, and the secondary particle diameter and aggregation area size measurement of silica nanoparticles, the surface roughness and the antiglare property were evaluated, and the results are shown in table 1.
Example 12: preparation of antiglare film
The same procedure as in example 4 was conducted except that 2.3 parts by weight of methyl methacrylate polymer particles (SSX-102, available from water-logging end product Co., ltd., japan) having an average primary particle diameter of 2 μm and a refractive index of 1.49 was further added to the antiglare solution in addition to the silica nanoparticle dispersed sol (MEK-ST-UP).
The antiglare solution was applied to a 80 μm PET substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp having a radiation dose of 80mJ/cm2 to form an antiglare layer having a thickness of 5.7. Mu.m.
The obtained antiglare film was subjected to the measurement of transmittance, haze, gloss and clarity by the optical measurement method described later, and the secondary particle diameter and aggregation area size measurement of silica nanoparticles, the surface roughness and the antiglare property were evaluated, and the results are shown in table 1.
Example 13: preparation of antiglare film
The same procedure as in example 12 was conducted except that 9.5 parts by weight of methyl methacrylate polymer particles (SSX-102) in the antiglare solution was used instead, 33 parts by weight of silica nanoparticle dispersion sol (MEK-ST-UP) was used instead, and 2.8 parts by weight of acrylate-ether group-containing surfactant (BYK-3535) was used instead to form an antiglare solution.
The antiglare solution was coated on a 60 μm TAC substrate, dried, and then light-cured under a nitrogen atmosphere with a UV lamp having a radiation dose of 80mJ/cm2 to form an antiglare layer having a thickness of 4.7 μm on the TAC substrate.
The results of measuring the transmittance, haze, gloss and clarity of the obtained antiglare film by the optical measurement method described later are shown in table 1, and the secondary particle diameter and aggregation area size measurement of silica nanoparticles, the surface roughness and the antiglare property were evaluated, and the results are shown in table 2.
Optical measuring method
The antiglare film prepared in the foregoing examples was optically measured as follows.
Measurement of light transmittance: light transmittance was evaluated in accordance with the description of JIS K7361 using an NDH-2000 haze meter (manufactured by Nippon electric color industry Co., ltd.).
Measurement of haze: haze was evaluated according to the description of JIS K7136 using an NDH-2000 haze meter (manufactured by Nippon electric color industry Co., ltd.).
Measurement of gloss: the antiglare film was glued on a black acrylic plate, and measured according to the description of JIS Z8741 using a BYK Micro-Gloss meter, and Gloss values of 20, 60 and 85 degrees were selected.
Measurement of definition: the hard coat optical film having antiglare properties was cut into a size of 5x 8cm2, and measured according to the description of JIS K7374 using a SUGA ICM-IT image clarity meter, and the measured values of the slits of 0.125mm, 0.25mm, 0.50mm, 1.00mm and 2.00mm were summed up.
Optical property measuring method
Measurement of secondary particle size and aggregate area size of silica nanoparticles: cutting the anti-dazzle film into proper size, placing the anti-dazzle film in a Mitutoyo SV-320 high-magnification optical microscope, taking light penetration images of the anti-dazzle film by means of CCD camera at a magnification of 10 times of an eyepiece and 20 times of an objective lens, and calculating the secondary particle size and the aggregation area size of the silicon dioxide nano particles by image measuring software.
Measurement of surface roughness: an antiglare film was attached to a black acrylic plate via a transparent optical adhesive, and four 3D surface roughness images were taken using an OLYMPUS LEXT OLS5000-SAF 3D laser conjugate focus microscope for 256x 256 μm2 area, and arithmetic average height (Sa) and maximum height (Sz) were calculated from the surface roughness description of ISO 25178, or center line average roughness (Ra), full roughness height (Ry), average peak pitch (RSm), and square root slope (tilt angle) (Rdq) were calculated from the line roughness description of ISO 4287.
Measurement of antiglare properties: the antiglare film was glued to a black acrylic plate, 2 fluorescent tubes were projected onto the surface of the antiglare film, and the antiglare properties of the antiglare film were evaluated on the following 5 grades by visually comparing the degree of blooming of the fluorescent tubes. And judging that the antiglare property is more than Lv.2 to be qualified.
Lv.1: the separated 2 fluorescent tubes can be clearly seen, and the outline of the fluorescent tube can be clearly distinguished to be linear;
Lv.2: the separated 2 fluorescent tubes can be clearly seen, but the outline is slightly blurred;
lv.3: 2 separated fluorescent tubes can be seen, the outline can be seen in a fuzzy manner, but the shape of the fluorescent tubes can be distinguished;
Lv.4: 2 fluorescent tubes can be seen, but the shape cannot be distinguished;
lv.5: the separated 2 fluorescent tubes cannot be seen, and the shape of the fluorescent tubes cannot be distinguished.
The optical measurement results of the antiglare films of examples 1 to 13 of the present invention are shown in table 1.
Table 1: optical measurement results of antiglare films of examples 1 to 13
The measurement results of the optical properties such as the secondary particle diameter and the size of the aggregation area, the surface roughness, and the antiglare property evaluation of the silica nanoparticles of the antiglare films of examples 1 to 13 of the present invention are shown in table 2.
Table 2: optical measurement results of antiglare films of examples 1 to 13
The antiglare films prepared in examples 1 to 11 of the present invention, in which silica nanoparticles are formed into silica micron-sized floccules by the action between the silica nanoparticles and an acrylate-ether-based surfactant, the flocculated silica nanoparticles have an average secondary particle diameter of 1,600nm to 3,300nm and an average secondary particle aggregation area of 293.mu.m2 to 709.mu.m2 or aggregate into a co-continuous network structure, provide excellent antiglare properties and have a haze of 1.0% to 2.0%. Meanwhile, the antiglare films prepared in examples 1 to 11 of the present invention have fine surfaces, and have an arithmetic mean height Sa of 0.043 to 0.180 μm, a maximum height Sz of 0.413 to 2.104 μm, a center line average roughness Ra of 0.040 to 0.243 μm, a full roughness height Ry of 0.231 to 0.621 μm, a mean peak pitch RSm of 31.542 to 154.665 μm, and a square root slope (tilt angle) Rdq of 1.132 to 6.413 degrees. The antiglare films produced in examples 1 to 11 of the present invention exhibited satisfactory fineness in surface roughness and had excellent antiglare properties.
In addition, examples 12 and 13 illustrate that the antiglare film disclosed in the present invention further comprises organic fine particles to adjust the haze to 1.9% and 2.4%, respectively. The antiglare film having haze adjusted by adding organic fine particles still maintains satisfactory glossiness and sharpness, and has satisfactory fineness of surface roughness and excellent antiglare property.
Although the present invention has been described with reference to the above embodiments, it should be understood that the invention is not limited thereto, but may be modified and practiced by those skilled in the art without departing from the spirit and scope of the present invention.
Claims (19)
1. An antiglare film, characterized by comprising:
a transparent substrate; and
An antiglare layer comprising an acrylic binder resin, an acrylate-ether group-containing surfactant, and a plurality of silica nanoparticles, the plurality of silica nanoparticles being in a weight ratio of 4 to 100 relative to the acrylate-ether group-containing surfactant;
wherein the micron-sized floccules formed by the plurality of silica nanoparticles exhibit an average secondary particle size of between 1,600nm and 3,300nm under an optical microscope.
2. The antiglare film according to claim 1, wherein: the antiglare film has an arithmetic average height of surface roughness of 0.02 μm to 0.25 μm, a maximum height of 0.25 μm to 2.50 μm, a center line average roughness of 0.01 μm to 0.30 μm, a full roughness height of 0.10 μm to 0.90 μm, an average peak pitch of 20 μm to 200 μm, and a square root slope of 0.80 DEG to 7.50 deg.
3. The antiglare film according to claim 1, wherein: the matrix-assisted laser desorption ionization-time-of-flight mass spectrometry average molecular weight of the acrylate-ether surfactant is between 200 and 6000, and the average oxyethylene base number is between 1 and 40.
4. The antiglare film according to claim 3, wherein: the average molecular weight of the matrix-assisted laser desorption ionization-time-of-flight mass spectrometry of the acrylate-ether surfactant is between 200 and 4500, and the average oxyethylene group number is between 1 and 35.
5. The antiglare film according to claim 3, wherein: the acrylate-ether group-containing surfactant is a polymerized compound composed of one or more monofunctional or polyfunctional unsaturated monomers having a vinyl group or (meth) acryloyl group and one or more polyether monomers represented by the formula (I):
Wherein R1 is hydrogen or methyl, R2 is hydrogen, C1 to C10 hydrocarbon group, phenyl or (meth) acryl, a is 1 or an integer greater than 1, b is 0 or an integer greater than 0, wherein the total amount of polyether monomer represented by formula (I) is contained in the acrylate-ether group-containing surfactant in an amount of 0.1 to 60 mole percent.
6. The antiglare film according to claim 1, wherein: the acrylate-ether group-containing surfactant is present in an amount of between 0.01 and 8 parts by weight per hundred parts by weight of the acrylic binder resin.
7. The antiglare film according to claim 1, wherein: the plurality of silica nanoparticles is between 0.5 parts by weight and 12 parts by weight per hundred parts by weight of the acrylic binder resin.
8. The antiglare film according to claim 1, wherein: the average primary particle diameter of each silica nanoparticle is between 5nm and 150 nm.
9. The antiglare film according to claim 1, wherein: the acrylic binder resin comprises a (meth) acrylate composition and an initiator, wherein the (meth) acrylate composition comprises:
35 to 50 parts by weight of a polyurethane (meth) acrylate oligomer having a functionality of between 6 and 15;
12 to 20 parts by weight of a (meth) acrylate monomer having a functionality of 3 to 6; and
1.5 To 12 parts by weight of a (meth) acrylate monomer having a functionality of less than 3.
10. The antiglare film according to claim 9, wherein: the polyurethane (meth) acrylate oligomer having a functionality of between 6 and 15 is an aliphatic polyurethane (meth) acrylate oligomer.
11. The antiglare film according to claim 9, wherein: the (meth) acrylate monomer having a functionality of 3 to 6 is at least one selected from the group consisting of pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, or a combination thereof.
12. The antiglare film according to claim 9, wherein: the (meth) acrylate monomer having a functionality of less than 3 is at least one selected from the group consisting of 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, cyclotrimethylol propane methylal (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydrofuran (meth) acrylate, lauryl (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, isobornyl (meth) acrylate, or a combination thereof.
13. The antiglare film according to claim 9, wherein: the initiator is at least one or a combination of acetophenone initiator, diphenyl ketone initiator, propiophenone initiator, dibenzoyl initiator, difunctional alpha-hydroxy ketone initiator and acyl phosphine oxide initiator.
14. An antiglare film, characterized by comprising:
a transparent substrate; and
An antiglare layer comprising an acrylic binder resin, an acrylate-ether group-containing surfactant, a plurality of silica nanoparticles, and a plurality of organic microparticles, the weight ratio of the plurality of silica nanoparticles to the acrylate-ether group-containing surfactant being between 4 and 100,
Wherein the micron-sized floccules formed by the plurality of nano-particles have an average secondary particle size of between 1,600nm and 3,300nm under an optical microscope.
15. The antiglare film according to claim 14, wherein: the particle size of each organic microparticle is between 0.5 μm and 6 μm.
16. The antiglare film according to claim 14, wherein: the refractive index of each organic microparticle is between 1.4 and 1.6.
17. The antiglare film according to claim 14, wherein: the plurality of organic microparticles is 0.5 to 15 parts by weight per hundred parts by weight of the acrylic binder resin.
18. The antiglare film according to claim 14, wherein: the plurality of organic microparticles are at least one selected from the group consisting of polymethyl methacrylate resin microparticles, polystyrene resin microparticles, styrene-methyl methacrylate copolymer microparticles, polyethylene resin microparticles, epoxy resin microparticles, polysiloxane resin microparticles, polyvinylidene fluoride resin and polyvinyl fluoride resin microparticles, or a combination thereof.
19. A polarizing plate, characterized by comprising:
A polarizing assembly; and
The antiglare film of any one of claims 1 to 18, which is formed on a surface of the polarizing component.
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| CN202010587072.6A CN113671608B (en) | 2020-06-24 | 2020-06-24 | Antiglare film and polarizing plate having the same |
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| CN202010587072.6A CN113671608B (en) | 2020-06-24 | 2020-06-24 | Antiglare film and polarizing plate having the same |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107840982A (en) * | 2017-11-09 | 2018-03-27 | 合肥乐凯科技产业有限公司 | A kind of anti-dazzle optical hardening film of fine definition |
| CN109337106A (en) * | 2018-08-27 | 2019-02-15 | 明基材料有限公司 | Hard conating optical film, polarizer and image display |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101273789B1 (en) * | 2012-04-19 | 2013-06-11 | 다이니폰 인사츠 가부시키가이샤 | Anti-glare film, polarizer and image display device |
| CN108431639B (en) * | 2016-03-09 | 2020-08-18 | 株式会社Lg化学 | Anti-reflection film |
| CN108663732B (en) * | 2018-05-10 | 2021-09-14 | 明基材料有限公司 | Low-haze anti-dazzle film and polarizing plate |
| TWI667303B (en) * | 2018-08-02 | 2019-08-01 | 明基材料股份有限公司 | Hard coating layered optical film , polarizer comprising the same, and image display comprising the hard coating layered optical film and/or the polarizer comprising the same |
| CN110119004B (en) * | 2019-06-03 | 2022-05-31 | 明基材料有限公司 | Anti-dazzle film and polarizing plate with same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107840982A (en) * | 2017-11-09 | 2018-03-27 | 合肥乐凯科技产业有限公司 | A kind of anti-dazzle optical hardening film of fine definition |
| CN109337106A (en) * | 2018-08-27 | 2019-02-15 | 明基材料有限公司 | Hard conating optical film, polarizer and image display |
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