CN113671608A - Anti-dazzle film and polarizing plate with same - Google Patents
Anti-dazzle film and polarizing plate with same Download PDFInfo
- Publication number
- CN113671608A CN113671608A CN202010587072.6A CN202010587072A CN113671608A CN 113671608 A CN113671608 A CN 113671608A CN 202010587072 A CN202010587072 A CN 202010587072A CN 113671608 A CN113671608 A CN 113671608A
- Authority
- CN
- China
- Prior art keywords
- acrylate
- meth
- antiglare film
- antiglare
- group
- 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.)
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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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- 230000003746 surface roughness Effects 0.000 claims description 23
- 239000003999 initiator Substances 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000011164 primary particle Substances 0.000 claims description 14
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 11
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
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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 2
- 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 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 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
- 230000001588 bifunctional effect Effects 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- 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 description 2
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- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 claims 1
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
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- 238000004519 manufacturing process Methods 0.000 description 14
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- 239000006185 dispersion Substances 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 13
- 230000005855 radiation Effects 0.000 description 13
- 239000002904 solvent Substances 0.000 description 11
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 9
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
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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 4
- 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 4
- 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 4
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- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
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- 239000003505 polymerization initiator Substances 0.000 description 1
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- 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
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- 238000003847 radiation curing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 238000004528 spin coating Methods 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
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- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 1
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Images
Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- 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
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- 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
Abstract
The invention discloses an anti-dazzle film and a polarizing plate with the anti-dazzle film, wherein the anti-dazzle film comprises a transparent base material and an anti-dazzle layer, wherein the anti-dazzle layer comprises acrylic binder resin, acrylate-ether-group-containing surfactant and a plurality of silicon dioxide nano particles, and the average secondary particle diameter of a micron-sized flocculating constituent formed by the nano particles under an optical microscope is between 1,600nm and 3,300 nm. The antiglare film can provide reliable antiglare properties at low haze.
Description
Technical Field
The present invention relates to an antiglare film which can be used for an image display device, and particularly to an antiglare film which can provide reliable antiglare properties at low haze.
Background
With the development of display technology, the requirements of display performance, such as high contrast, wide viewing angle, high brightness, thinness, large size, high definition and diversified additional functions, of image display devices, such as Liquid Crystal Displays (LCDs), organic light emitting diode displays (OLEDs), etc., have been widely developed.
In general, the display is usually provided with an optical film having a surface treatment, such as an anti-glare film or an anti-reflection film, on the surface thereof for modulating light and reducing the influence of reflected light of external stray light on the displayed image.
In order to provide an antiglare film with excellent antiglare properties in a bright room environment and high contrast in a dark room environment, a method for developing a low haze antiglare film using small-particle-size organic fine particles to achieve high contrast has been known. In the related art, it has been proposed to coat an anti-glare layer containing organic fine particles on a transparent substrate, and to form an uneven structure on a film surface by aggregating the organic fine particles and the nano particles when coating the organic fine particles, thereby providing anti-glare properties and achieving a low glare effect. However, since the size of the organic fine particles and nanoparticles is not easily controlled, the uneven structure of the film surface is not as desired, and the antiglare property is reduced or the optical rotation is improved. Further, since the antiglare layer containing organic fine particles having a relatively large particle diameter and/or silica particles of a micron order is coated on a transparent substrate, the light diffusion effect by the fine particles increases the haze to a higher degree, and an antiglare film having a low haze and a good antiglare property cannot be provided.
Therefore, there is a need for an antiglare film having low haze but providing satisfactory antiglare properties.
Disclosure of Invention
The invention aims to provide an anti-dazzle film with low haze and satisfactory anti-dazzle performance and a polarizing plate with the anti-dazzle 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, which can provide reliable antiglare properties at low haze. The anti-dazzle film comprises a transparent base material and an anti-dazzle layer positioned on the transparent base material, wherein the anti-dazzle layer comprises acrylic binder resin, acrylate-ether-group-containing surfactant and a plurality of silica nanoparticles, and micron-sized floccules formed by the nanoparticles have an average secondary particle size of 1,600nm to 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. The anti-glare film of the present invention has a haze of not more than 5%, preferably not more than 3%, by aggregation of silica nanoparticles, and has an arithmetic average height (Sa) of surface roughness of 0.02 to 0.25. mu.m, a maximum height (Sz) of 0.25 to 2.50. mu.m, a center line average roughness (Ra) of 0.01 to 0.30. mu.m, a total roughness height (Ry) of 0.10 to 0.90. mu.m, an average peak spacing (RSm) of 20 to 200. mu.m, and a square root mean slope (Rdq) of 0.80 to 7.50 °.
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 0.5 to 12 parts by weight, preferably 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, in the antiglare layer, the acrylate-ether-group-containing surfactant may be between 0.01 parts by weight and 8 parts by weight, preferably between 0.05 parts by weight and 5 parts by weight, per one hundred parts by weight of the acrylic binder resin. Furthermore, in the anti-glare layer of the anti-glare film of the present invention, the relative weight ratio of the silica nanoparticles to the acrylate-ether-group-containing surfactant is between 0.5 and 100, preferably between 0.5 and 80.
In the antiglare layer of the antiglare film of the present invention, the acrylate-ether-group-containing surfactant is a polymer compound of one or more monofunctional or polyfunctional unsaturated monomers having a vinyl group or a (meth) acryloyl group and one or more polyether monomers represented by the formula (I):
wherein R1 is hydrogen or methyl, R2 is hydrogen, a C1 to C10 hydrocarbon group, 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 contained in the acrylate-ether-group-containing surfactant in an amount of 0.1 to 60 mol% and the acrylate-ether-group-containing surfactant-containing matrix-assisted desorption laser ionization-time of flight mass spectrometry (MALDI-TOF MS) has an average molecular weight of 200 to 6,000 and an average oxyethylene group number (EO) Unit) of 1 to 40.
In the antiglare film of the present invention, the thickness of the antiglare layer may be between 2 μm and 10 μm, preferably between 2 μm and 8 μm.
In the anti-glare film of the present invention, the acrylic binder resin of the anti-glare 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 number average molecular weight (Mn) of the urethane (meth) acrylate oligomer having a functionality of 6 to 15 is between 1,000 and 4,500.
In still another aspect of the present invention, an anti-glare film may further include organic fine particles in an anti-glare layer to adjust haze, wherein the anti-glare film includes a transparent base material and the anti-glare layer, wherein the anti-glare layer includes an acrylic binder resin, an acrylate-ether-group-containing surfactant, a plurality of silica nanoparticles, and a plurality of organic fine particles, and wherein the silica nanoparticles form micro-sized aggregates having an average secondary particle size ranging from 1,600nm to 3,300nm under an optical microscope.
The anti-glare film containing organic particles in the anti-glare layer of the present invention may have a refractive index of 1.4 to 1.6 per organic particle, and a particle size of 0.5 μm to 6 μm, preferably 1 μm to 4 μm per organic particle.
Another object of the present invention is to provide a method for preparing an anti-glare film, which comprises uniformly mixing an acrylic binder resin, an acrylate-ether-group-containing surfactant, and a plurality of silica nanoparticles to form an anti-glare solution, coating the anti-glare solution on a transparent substrate, drying the substrate coated with the anti-glare solution, and then performing radiation curing or electron beam curing to form the anti-glare film.
It is still another object of the present invention to provide a polarizing plate including a polarizing element and the antiglare film.
The antiglare film and the polarizing plate of the present invention have a micron-sized floc formed of silica nanoparticles in the antiglare layer, and thus can provide reliable antiglare properties at low haze.
The summary is intended to provide a simplified summary of the disclosure so that the reader can obtain 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 nor delineate the scope of the embodiments. The basic spirit of the present invention and the technical means and embodiments adopted by the present invention will be easily understood by those skilled in the art after referring to the following embodiments.
The invention is described in detail below with reference to the drawings and specific examples, but the invention is not limited thereto.
Drawings
FIG. 1 is a light transmission image of the antiglare film of example 1 of the invention at 200 magnifications of an optical microscope.
FIG. 2 is a light transmission image of the antiglare film of example 4 of the invention at 200 magnifications of an optical microscope.
FIG. 3 is a Scanning Electron Microscope (SEM)5,000-magnification image of a cross-section of an antiglare film of example 4 of the present invention.
FIG. 4 is a light transmission image of the antiglare film of example 8 under an optical microscope at 200 magnifications.
FIG. 5 is a light transmission image of the antiglare film of example 10 under an optical microscope at 200 magnifications.
Detailed Description
The advantages, features, and advantages of the present invention will be more readily understood by reference to the following detailed description of exemplary embodiments and the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein but, on the contrary, as will be apparent to those of ordinary skill in the art, the embodiments are provided so as to fully convey the scope of the invention and the present invention is defined only by the appended claims.
Unless otherwise defined, all terms (including technical and scientific terms) and terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and terms such as those defined in 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 overly idealized or overly formal sense unless expressly so defined herein.
In this specification, the term "(meth) acrylate" refers to both methacrylate and acrylate.
An object of the present invention is to provide an antiglare film which can provide reliable antiglare properties at low haze, comprising a transparent base material and an antiglare layer on the transparent base material, wherein the antiglare layer has micron-sized flocs formed of silica nanoparticles therein. The anti-dazzle film comprises a transparent base material and an anti-dazzle layer positioned on the transparent base material, wherein the anti-dazzle layer comprises acrylic binder resin, acrylate-ether-group-containing surfactant and a plurality of silica nanoparticles, and micron-sized floccules formed by the nanoparticles have an average secondary particle size of 1,600nm to 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 the embodiment of the antiglare film of the present invention, the haze of the antiglare film is not more than 5%, preferably not more than 3%. The anti-glare film of the present invention has an arithmetic average height (Sa) of surface roughness of 0.02 to 0.25. mu.m, a maximum height (Sz) of 0.25 to 2.50. mu.m, a center line average roughness (Ra) of 0.01 to 0.30. mu.m, a full roughness height (Ry) of 0.10 to 0.90. mu.m, a mean peak spacing (RSm) of 20 to 200. mu.m, and a root-mean-square slope (Rdq) of 0.80 to 7.50 °. The antiglare film of the present invention achieves low haze by aggregation of silica nanoparticles and provides excellent antiglare properties under such a fine surface of roughness.
In a preferred embodiment of the antiglare film of the present invention, the surface roughness of the antiglare film has an arithmetic average height (Sa) of from 0.03 μm to 0.20 μm, a maximum height (Sz) of from 0.40 μm to 2.20 μm, a center line average roughness (Ra) of from 0.02 μm to 0.25 μm, a full roughness height (Ry) of from 0.20 μm to 0.80 μm, an average peak pitch (RSm) of from 20 μm to 180 μm, and a root mean square slope (Rdq) of from 1.00 ° to 6.50 °.
In an embodiment of the present invention, a suitable transparent substrate may be a film having good mechanical strength and light transmittance, which may be, but not limited to, a resin film of 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).
In the preferred embodiment of the present invention, the selected transparent substrate preferably has a light transmittance of 80% or more, and more preferably 90% or more. The thickness of the transparent substrate is between about 10 μm and 500 μm, preferably between about 15 μm and 250 μm, and more preferably between about 20 μm and 100 μm.
In the antiglare film of the present invention, the thickness of the antiglare layer may be 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 between 5nm and 150nm, and preferably between 5nm and 120nm, more preferably between 5nm and 100 nm. In the embodiment of the invention, the silica nanoparticles can be selected from silica nanoparticles with unmodified surface or modified surface, the silica nanoparticles with modified surface can be silica nanoparticles modified by siloxane with alkyl, acryloyl or epoxy, and the polarity between the silica nanoparticles and resin is close and the silica nanoparticles are distributed in the anti-dazzle layer. The average primary particle size of the silica nanoparticles may be measured by a specific surface area method (BET) or a dynamic light scattering method.
According to an embodiment of the antiglare film of the present invention, the silica nanoparticles in the antiglare layer are between 0.5 parts by weight and 12 parts by weight, preferably between 0.8 parts by weight and 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 aforementioned range, 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 polymer compound formed by polymerizing one or more monofunctional or polyfunctional unsaturated monomers having a vinyl group or a (meth) acryloyl group with one or more polyether monomers represented by the formula (I):
wherein R1 is hydrogen or methyl, R2 is hydrogen, a C1 to C10 hydrocarbyl group, phenyl or (meth) acryloyl group, 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 matrix assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) containing acrylate-ether surfactant has an average molecular weight of 200-6,000 and an average vinyl Oxide (EO) Unit of 1-40.
A polyether monomer represented by the aforementioned formula (I), wherein a is an integer of 1 to 100, more preferably an integer of 1 to 40; and b is an integer of 0 to 100, preferably 0 to 40. In the polyether monomer of the formula (I), an oxyethylene group (EO) Unit and an oxypropylene group (PO) Unit are connected by random copolymerization, alternating copolymerization or block copolymerization. In the polyether monomer of the aforementioned formula (I), when R2 is a C1 to C10 hydrocarbon group, the hydrocarbon group may be a substituted C1 to C10 hydrocarbon group, and the substituent may be a hydrocarbon group, an alkenyl group, a hydroxyl group, a phenyl group, an alkoxy group, or an epoxy group.
In a preferred embodiment of the antiglare film of the present invention, the average molecular weight of the above matrix assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) containing acrylate-ether based surfactant is preferably 200 to 4,500, more preferably 200 to 3,000, and the average number of Ethylene Oxide (EO) units is preferably 1 to 35, more preferably 1 to 30.
The monofunctional or polyfunctional unsaturated monomer having a vinyl group or a (meth) acryloyl group used for forming the acrylate-ether group-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 monofunctional unsaturated monomers having a vinyl group or (meth) acryloyl group suitable for forming the acrylate-ether-group-containing surfactant of the present invention include, but are not limited to, Styrene (Styrene), α -methylstyrene (α -methyl Styrene), vinyl ether-based monomers such as ethyl vinyl ether (ethyl vinyl ether), n-Butyl vinyl ether (n-Butyl vinyl ether) and cyclohexyl vinyl ether (cyclohexyl vinyl ether), 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-hydroxy) acrylate, 2-HE (M) A), 2-ethoxyethyl (meth) acrylate (2-ethoxyyethyl (meth) acrylate), tetrahydrofuran (meth) acrylate (tetrahydrofuran (meth) acrylate, THF (M) A), isobornyl (meth) acrylate (isobornyl (meth) acrylate, IBO (M) A), 2-phenoxyethyl (meth) acrylate (2-phenoxyethyl (meth) acrylate, PHE (M) A), perfluoroalkyl (meth) acrylate, (meth) acrylate group-functionalized polydimethylsiloxane, caprolactone and/or valerolactone-modified hydroxyalkyl (meth) acrylate, and the like. Furthermore, the aforementioned monofunctional unsaturated monomers may optionally be used with a vinyl group-containing chain transfer agent 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-dicarboxylate, and dibutyl 2, 2-dimethyl-4-methylenepentane-1, 5-dicarboxylate.
Examples of the polyfunctional unsaturated monomer having a vinyl group or (meth) acryloyl group suitable for forming the acrylate-ether-group-containing surfactant of the present invention include, but are not limited to, ethylene glycol di (meth) acrylate (edg (m) a), 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 acrylate-ether group-containing surfactants can be selected from, but are not limited to, BYK-3440, BYK-3441, BYK3560, BYK-3565, BYK-3566 and BYK-3535 (manufactured by BYK-Chemie, Germany).
According to a preferred embodiment of the anti-glare film of the present invention, the acrylate-ether-group-containing surfactant may be present in the anti-glare layer in an amount of 0.01 to 8 parts by weight, preferably 0.05 to 5 parts by weight, per hundred parts by weight of the acrylic binder resin. When the amount of the acrylate-ether group-containing surfactant used is less than the above range, the antiglare property of the antiglare film may be insufficient. When the amount of the acrylate-ether group-containing surfactant used is more than the above range, the haze of the antiglare film may be increased.
According to the anti-dazzle film, the anti-dazzle layer contains the acrylate-ether surfactant which can flocculate the silicon dioxide nano particles, so that the silicon dioxide nano particles form micron-sized flocculating constituents with the average secondary particle size of 1,600nm to 3,300 nm. Without being bound by theory, in the anti-glare layer of the anti-glare 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, so that the anti-glare film has excellent anti-glare properties without affecting the fineness of the film surface of the anti-glare film. When the relative ratio of the silica nanoparticles to the acrylate-ether group-containing surfactant is outside the above range, the size of the flocs of the silica nanoparticles cannot be controlled, and the antiglare property of the antiglare film is low, the haze is excessively high, or the film surface appearance is defective. Furthermore, in a preferred embodiment of the anti-glare film of the present invention, the relative weight ratio of the silica nanoparticles and the acrylate-ether-group-containing surfactant in the anti-glare layer is preferably between 0.5 and 80.
Furthermore, in the antiglare film of the present invention, the micron-sized flocs of the silica nanoparticles in the antiglare layer may be aggregated again, may not be aggregated, or may be aggregated into a co-continuous network structure, and may not be aggregated again and may not affect the generation of antiglare properties, and the re-aggregation may help to improve antiglare properties again.
In another embodiment of the antiglare film of the present invention, the antiglare layer may further comprise other silica nanoparticles having a high degree of hydrophobic modification without affecting the physical properties of the antiglare film, so that the silica nanoparticles and the resin have a large polarity difference and are distributed on the surface of the antiglare layer, thereby adjusting the physical properties of the surface of the antiglare film, for example, silica nanoparticles capable of resisting surface scratches may be added.
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 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.
In a preferred embodiment of the present invention, the molecular weight of the urethane (meth) acrylate oligomer having a functionality of 6 to 15 is not less than 1,000, preferably 1,000 to 4,500. In a further preferred embodiment of the present invention, the urethane (meth) acrylate oligomer having a functionality of between 6 and 15 is preferably an aliphatic urethane (meth) acrylate oligomer having a functionality of between 6 and 15.
In a preferred embodiment of the present invention, the (meth) acrylate monomer having a functionality of 3 to 6 has a molecular weight of less than 1,000, preferably less than 800. The (meth) acrylate monomer having a functionality of 3 to 6 suitable for use in the present invention may be, for example, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate (dipentaerythritol penta (meth) acrylate, dpp (m) a), dipentaerythritol hexa (meth) acrylate, dph (m) a, trimethylolpropane tri (meth) acrylate (trimethyolpropane tri (meth) acrylate, tmpt (m) a), ditrimethylolpropane tetra (meth) acrylate (DTMPT (m) a), pentaerythritol tri (meth) acrylate (pentaerythrytol tri (meth) acrylate, PET (m) a), or a combination thereof, but is not limited thereto. The (meth) acrylate monomer having a functionality of 3 to 6 is preferably one of pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), 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. Suitable (meth) acrylate monomers having a functionality of less than 3 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-hydroxyethoxy (meth) acrylate, 2-HE (M) A), 3-hydroxypropyl (meth) acrylate (3-hydroxypropyl (meth) acrylate, 3-HP (M) A), 4-hydroxybutyl (meth) acrylate (4-hydroxybut (meth) acrylate, 4-HB (M) A), 2-butoxyethyl (meth) acrylate (2-butoxyethoxy (meth) acrylate), 1,6-hexanediol di (meth) acrylate (1, 6-cyclohexanediol (meth) acrylate, cyclic methacrylate (M) acrylate, trimethylolpropane (meth) acrylate, ctf (m) a), 2-phenoxyethyl (meth) acrylate (2-phenoxyethyl (meth) acrylate, phe (m) a), tetrahydrofuran (meth) acrylate (tetrahydrofuran (meth) acrylate, thf (m) a, lauryl (meth) acrylate, l (m) a, diethylene glycol di (meth) acrylate, degd (m) a), dipropylene glycol di (meth) acrylate (di (meth) acrylate, dpgd (m) a), tripropylene glycol di (meth) acrylate (tri (meth) acrylate, tpgd (m) a), isobornyl (meth) acrylate (isobornyl) acrylate, o, or combinations thereof, but is not limited thereto. The (meth) acrylate monomer having a functionality of less than 3 is preferably one of 1,6-hexanediol diacrylate (HDDA), cyclotrimethylolpropane formal acrylate (CTFA), 2-phenoxyethyl acrylate (PHEA) or isobornyl acrylate (IBOA), or a combination thereof.
Suitable initiators in the acrylate-based binder resin of the present invention may be those generally known in the art, and are not particularly limited, and for example, acetophenone-based initiators, benzophenone-based initiators, phenylpropenone-based initiators, dibenzoyl-based initiators, bifunctional α -hydroxy ketone-based initiators, acylphosphine oxide-based initiators, or the like may be used. The aforementioned initiators may be used alone or in admixture.
The anti-dazzle film can adjust the haze according to the using environment and the visual angle requirement of a product by adding the organic microparticles, and particularly adjusts the internal scattering effect of the internal haze of the anti-dazzle layer.
Therefore, in another aspect, the present invention provides an anti-glare film comprising a transparent substrate and an anti-glare layer on the transparent substrate, wherein the anti-glare layer comprises a micro-scale flocculent formed of a plurality of silica nanoparticles and a plurality of organic microparticles. The anti-dazzle film comprises a transparent base material and an anti-dazzle layer positioned on the transparent base material, wherein the anti-dazzle layer comprises acrylic binder resin, an acrylate-ether-group-containing surfactant, a plurality of silica nano particles and a plurality of organic micro particles, wherein micron-sized floccules formed by the silica nano particles have an average secondary particle size of between 1,600nm and 3,300nm under an optical microscope.
Organic particles having an appropriate refractive index and particle size can be selected as the organic particles suitable for the antiglare film of the present invention, and the haze of the antiglare film can be adjusted by controlling the addition amount of the organic particles. Suitable organic microparticles may have a refractive index of 1.4 to 1.6, and a particle size of 0.5 μm to 6 μm, and preferably 1 μm to 4 μm. In the embodiment of the anti-glare film with haze adjusted by organic fine particles, the haze can range from 1% to 50%, but is not limited thereto.
When the anti-glare film of the present invention uses organic fine particles to adjust the haze, the amount of the organic fine particles may be adjusted according to the actual haze, and preferably, the amount of the organic fine particles is 0.5 to 15 parts by weight, more preferably 1 to 12 parts by weight, per hundred parts by weight of the acrylic binder resin.
Organic fine particles suitable for the antiglare layer of the antiglare film of the present invention are polymethyl methacrylate resin fine particles, polystyrene resin fine particles, styrene-methyl methacrylate copolymer fine particles, polyethylene resin fine particles, epoxy resin fine particles, polysiloxane resin fine particles, polyvinylidene fluoride resin fine particles, or polyvinyl fluoride resin fine particles. 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.
Other optical function layers, such as a low refractive layer, may also be selectively coated on the film surface of the antiglare film of the present invention to provide antireflection properties.
Another object of the present invention is to provide a method for preparing an antiglare film. The preparation method of the anti-dazzle 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, an initiator and a proper solvent to form acrylic adhesive resin; adding silicon dioxide nano particles and/or organic micro particles, acrylate-ether-group-containing surfactant and organic solvent into acrylic adhesive resin, and uniformly mixing to form an anti-dazzle solution; and (3) coating the anti-dazzle solution on a transparent substrate, drying the substrate coated with the anti-dazzle solution, and curing by radiation or electron beams to form an anti-dazzle layer on the transparent substrate to obtain the anti-dazzle film.
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. One or more organic solvents may be used in both the acrylate composition and the anti-glare solution, and suitable solvents may include, but are not limited to, acetone, methyl ethyl ketone, 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.
In other embodiments of the present invention, additives such as antistatic agents, coloring agents, flame retardants, ultraviolet absorbers, antioxidants, surface modifiers, leveling agents without polyether modification, and antifoaming agents may also be added to the prepared antiglare solution as needed to provide different functional properties.
The method for applying the antiglare solution may be a coating method generally used in the art, for example, a roll coating method, a knife coating method, a dip coating method, a roll coating method, a spin coating method, a spray coating method, or a slit coating method.
It is still another object of the present invention to provide a polarizing plate comprising a polarizing element, wherein the surface of the polarizing element has the antiglare film.
The following examples are intended to further illustrate the invention, and the invention is not limited thereto.
Examples
Preparation example 1: preparation of acrylic Binder resin I
An acrylic adhesive resin I was formed by mixing and stirring 42 parts by weight of urethane acrylate (functionality of 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 the constant bridge industry, taiwan), 24.5 parts by weight of Ethyl Acetate (EAC), and 10 parts by weight of n-butyl acetate (nBAC) for 1 hour.
Example 1: production of antiglare film
An antiglare solution was formed by mixing and stirring 220 parts by weight of an acrylic binder resin I, 10 parts by weight of a silica nanoparticle dispersion sol (MEK-AC-4130Y having a solid content of 30% and a solvent of methyl ethyl ketone available from nippon chemical, japan) having an average primary particle diameter of 40nm to 50nm, 7.5 parts by weight of an acrylate-ether-group-containing surfactant (BYK-UV3535 having a solid content of 10% and a solvent of ethyl acetate available from BYK, germany), 60 parts by weight of Ethyl Acetate (EAC) and 120 parts by weight of n-butyl acetate (nBAC) for 1 hour to uniformly disperse them. The antiglare solution was coated on a 80 μm polyethylene terephthalate (PET) substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp at a radiation dose of 80mJ/cm2 to form an antiglare layer having a thickness of 3.4 μm on the PET substrate.
The results of the obtained antiglare film on transmittance, haze, gloss and clarity by the optical measurement method described later are shown in table 1, and the measurements of the secondary particle size and the size of the aggregated area of the silica nanoparticles, the surface roughness and the antiglare property were performed, and the results are shown in table 2.
The obtained antiglare film was observed under an optical microscope at 200 magnifications, and the obtained light transmission image is shown in fig. 1.
Example 2: production of antiglare film
An anti-glare solution was prepared according to example 1, except that an acrylate-ether-group-containing surfactant (BYK-3440, solid content 10%, solvent dipropylene glycol monomethyl ether available from BYK, Germany) was used in an amount of 7.5 parts by weight to form an anti-glare solution.
The antiglare solution was coated on an 80 μm PET substrate, and photocured with a UV lamp at a radiation dose of 80mJ/cm2 in a nitrogen atmosphere to form an antiglare layer having a thickness of 3.3 μm on the PET substrate.
The results of the obtained antiglare film on transmittance, haze, gloss and clarity by the optical measurement method described later are shown in table 1, and the measurements of the secondary particle size and the size of the aggregated area of the silica nanoparticles, the surface roughness and the antiglare property were performed, and the results are shown in table 2.
Example 3: production of antiglare film
An antiglare solution was prepared according to example 1 except that 7.5 parts by weight of a silica nanoparticle dispersion sol having an average primary particle diameter of 10nm to 15nm (MEK-AC-2140Z, solid content of 40%, solvent was methyl ethyl ketone, available from japanese chemical, japan) was used instead to form the antiglare solution.
The antiglare solution was coated on a 80 μm PET substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp at a radiation dose of 80mJ/cm2 to form an antiglare layer having a thickness of 3.4 μm on the PET substrate.
The results of the obtained antiglare film on transmittance, haze, gloss and clarity by the optical measurement method described later are shown in table 1, and the measurements of the secondary particle size and the size of the aggregated area of the silica nanoparticles, the surface roughness and the antiglare property were performed, and the results are shown in table 2.
Example 4: production of antiglare film
The procedure was carried out as in example 3 except that 15 parts by weight of a silica nanoparticle dispersion sol having an average primary particle diameter of 9nm to 15nm and being linked in a chain shape having a length of 40nm to 100nm (MEK-ST-UP, solid content of 20%, solvent of methyl ethyl ketone, available from Nissan Chemicals, Japan) was used instead to form an antiglare solution.
The antiglare solution was coated on a 80 μm PET substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp at 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 the obtained antiglare film on transmittance, haze, gloss and clarity by the optical measurement method described later are shown in table 1, and the measurements of the secondary particle size and the size of the aggregated area of the silica nanoparticles, the surface roughness and the antiglare property were performed, and the results are shown in table 2.
The obtained antiglare film was observed with an optical microscope at 200 magnifications, and the obtained light transmission image was shown in fig. 2, and the cross-section was observed with a Scanning Electron Microscope (SEM) at 5,000 magnifications, and the obtained image was shown in fig. 3.
Example 5: production of antiglare film
The procedure was carried out as in example 3 except that 7.5 parts by weight of a dispersion sol of silica nanoparticles having an average primary particle diameter of 12nm (ELCOM V-8804 having a solid content of 40% and propylene glycol methyl ether as a solvent, available from Japanese catalytic conversion) was used instead to form an antiglare solution.
The antiglare solution was coated on a 80 μm PET substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp at 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 the obtained antiglare film on transmittance, haze, gloss and clarity by the optical measurement method described later are shown in table 1, and the measurements of the secondary particle size and the size of the aggregated area of the silica nanoparticles, the surface roughness and the antiglare property were performed, and the results are shown in table 2.
Example 6: production of antiglare film
The procedure was as in example 5, except that the silica nanoparticle dispersion sol was changed to 20 parts by weight of a silica nanoparticle dispersion sol (MEK-5630X, solid content 30%, solvent methyl ethyl ketone, available from Union silicon, Taiwan, China) having an average primary particle diameter of 12nm and dispersed to an average secondary particle diameter of 80nm to 120nm, and 15 parts by weight of an acrylate-ether group-containing surfactant (BYK-UV3535) was used to form an anti-glare solution.
The antiglare solution was coated on a 80 μm PET substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp at 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 the obtained antiglare film on transmittance, haze, gloss and clarity by the optical measurement method described later are shown in table 1, and the measurements of the secondary particle size and the size of the aggregated area of the silica nanoparticles, the surface roughness and the antiglare property were performed, and the results are shown in table 2.
Example 7: production of antiglare film
The procedure was as in example 4, 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 being linked in a chain shape with a length of 40nm to 100nm and an acrylate-ether-group-containing surfactant were used instead of 1.5 parts by weight of an acrylate-ether-group-containing surfactant (BYK-3560, solid content of 10%, solvent of ethyl acetate, available from BYK, Germany) to form an antiglare solution.
The antiglare solution was coated on a 80 μm PET substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp at a radiation dose of 80mJ/cm2 to form an antiglare layer having a thickness of 3.5 μm on the PET substrate.
The results of the obtained antiglare film on transmittance, haze, gloss and clarity by the optical measurement method described later are shown in table 1, and the measurements of the secondary particle size and the size of the aggregated area of the silica nanoparticles, the surface roughness and the antiglare property were performed, and the results are shown in table 2.
Example 8: production of antiglare film
The procedure was as in example 1, except that 40 parts by weight of the silica nanoparticle dispersion sol (MEK-AC-4130Y) having an average primary particle diameter of 40nm to 50nm was used and the acrylate-ether-group-containing surfactant was changed to 30 parts by weight of the acrylate-ether-group-containing surfactant (BYK-3560) to form an antiglare solution.
The antiglare solution was coated on a 80 μm PET substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp at a radiation dose of 80mJ/cm2 to form an antiglare layer having a thickness of 3.3 μm on the PET substrate.
The results of the obtained antiglare film on transmittance, haze, gloss and clarity by the optical measurement method described later are shown in table 1, and the measurements of the secondary particle size and the size of the aggregated area of the silica nanoparticles, the surface roughness and the antiglare property were performed, and the results are shown in table 2.
The obtained antiglare film was observed under an optical microscope at 200 magnifications, and the obtained light transmission image is shown in fig. 4.
Example 9: production of antiglare film
The procedure was as in example 2, except that an anti-glare solution was formed using 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).
The antiglare solution was coated on a 80 μm PET substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp at a radiation dose of 80mJ/cm2 to form an antiglare layer having a thickness of 3.2 μm on the PET substrate.
The results of the obtained antiglare film on transmittance, haze, gloss and clarity by the optical measurement method described later are shown in table 1, and the measurements of the secondary particle size and the size of the aggregated area of the silica nanoparticles, the surface roughness and the antiglare property were performed, and the results are shown in table 2.
Example 10: production of antiglare film
The procedure was carried out as in example 3, except that 10 parts by weight of a silica nanoparticle dispersion sol having an average primary particle diameter of 70nm to 100nm (MEK-ST-ZL) was used instead to form an antiglare solution.
The antiglare solution was coated on a 80 μm PET substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp at a radiation dose of 80mJ/cm2 to form an antiglare layer having a thickness of 3.3 μm on the PET substrate.
The results of the obtained antiglare film on transmittance, haze, gloss and clarity by the optical measurement method described later are shown in table 1, and the measurements of the secondary particle size and the size of the aggregated area of the silica nanoparticles, the surface roughness and the antiglare property were performed, and the results are shown in table 2.
The obtained antiglare film was observed under an optical microscope at 200 magnifications, and the obtained light transmission image is shown in fig. 5.
Example 11: production of antiglare film
The procedure was carried out in the same manner as in example 9, except that 10 parts by weight of the silica nanoparticle dispersion sol (MEK-AC-4130Y) and 0.75 part by weight of the acrylate-ether group-containing surfactant (BYK-3440) were used instead to form the antiglare solution.
The antiglare solution was coated on a 80 μm PET substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp at a radiation dose of 80mJ/cm2 to form an antiglare layer having a thickness of 4.1 μm on the PET substrate.
The results of the obtained antiglare film on transmittance, haze, gloss and clarity by the optical measurement method described later are shown in table 1, and the measurements of the secondary particle size and the size of the aggregated area of the silica nanoparticles, the surface roughness and the antiglare property were performed, and the results are shown in table 2.
Example 12: production of antiglare film
The procedure of example 4 was repeated except that the silica nanoparticle dispersion sol (MEK-ST-UP) was added to the antiglare solution, and 2.3 parts by weight of methyl methacrylate polymer particles (SSX-102, available from Hydrochemical Co., Ltd., Japan) having an average primary particle diameter of 2 μm and a refractive index of 1.49 were added thereto.
The antiglare solution was coated on a 80 μm PET substrate, dried, and then photocured under a nitrogen atmosphere with a UV lamp at a radiation dose of 80mJ/cm2 to form an antiglare layer having a thickness of 5.7 μm on the PET substrate.
The results of the obtained antiglare film on transmittance, haze, gloss and clarity by the optical measurement method described later are shown in table 1, and the measurements of the secondary particle size and the size of the aggregated area of the silica nanoparticles, the surface roughness and the antiglare property were performed, and the results are shown in table 2.
Example 13: production of antiglare film
The procedure was carried out in the same manner as in example 12 except that 9.5 parts by weight of the methyl methacrylate polymer particles (SSX-102) in the antiglare solution was used instead, 33 parts by weight of the silica nanoparticle dispersion sol (MEK-ST-UP) was used instead, and 2.8 parts by weight of the acrylate-ether group-containing surfactant (BYK-3535) was used instead to form an antiglare solution.
The anti-glare solution was coated on a 60 μm TAC substrate, dried, and then photo-cured with a UV lamp at a dose of 80mJ/cm2 under a nitrogen atmosphere to form an anti-glare layer having a thickness of 4.7 μm on the TAC substrate.
The results of the obtained antiglare film on transmittance, haze, gloss and clarity by the optical measurement method described later are shown in table 1, and the results of the measurements of the secondary particle diameter and the size of the aggregated area of the nanoparticles, the surface roughness and the antiglare property by the silica are shown in table 2.
Optical measurement method
The antiglare films obtained in the preceding examples were optically measured by the following methods.
Measurement of light transmittance: the light transmittance was evaluated using an NDH-2000 haze meter (manufactured by Nippon Denshoku industries Co., Ltd.) according to the description of JIS K7361.
Measurement of haze: the haze was evaluated according to the description of JIS K7136 using an NDH-2000 haze meter (manufactured by Nippon Denshoku industries Co., Ltd.).
Measurement of gloss: the antiglare film was glued to a black acrylic plate and measured using a BYK Micro-Gloss meter according to the description of JIS Z8741, and angle Gloss values of 20, 60, and 85 degrees were selected.
And (3) measuring the definition: the hard coat optical film having antiglare property was cut into a size of 5 × 8cm2, measured using a SUGA ICM-IT image clarity apparatus in accordance with the description of JIS K7374, and the values measured for slits of 0.125mm, 0.25mm, 0.50mm, 1.00mm and 2.00mm were added up.
Optical property measuring method
Measurement of secondary particle size and aggregation area size of silica nanoparticles: the anti-dazzle film is cut into a proper size and placed in a Mitutoyo SV-320 high-magnification optical microscope, the light penetrating image of the anti-dazzle film is shot by a CCD camera with the magnification of 10 times that of an eyepiece and 20 times that of an objective lens, and the secondary particle size and the size of the gathering area of the silicon dioxide nano particles are calculated by image measuring software.
Measurement of surface roughness: an anti-glare film was attached to a black acryl plate via a transparent optical adhesive, four 3D surface roughness images were taken of a 256 × 256 μm2 area using an OLYMPUS LEXT OLS5000-SAF 3D laser confocal microscope, and the arithmetic average height (Sa) and the maximum height (Sz) were calculated according to the surface roughness description of ISO 25178, or the center line average roughness (Ra), the total roughness height (Ry), the average peak distance (RSm), and the square root slope (inclination angle) (Rdq) were calculated according to the line roughness description of ISO 4287.
Measurement of anti-glare property: the antiglare film was bonded to a black acrylic plate, and the antiglare properties of the antiglare film were evaluated in 5 ranks as follows by reflecting 2 fluorescent tubes on the surface of the antiglare film and visually checking the degree of blooming of the fluorescent tubes. The antiglare property of more than lv.2 was judged to be acceptable.
Lv.1: 2 separated fluorescent tubes can be clearly seen, and the outline can be clearly distinguished to be linear;
lv.2: the 2 separated 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 way, but the shape of the fluorescent tubes can be distinguished;
lv.4: 2 fluorescent tubes can be seen, but the shapes can not be distinguished;
lv.5: the separated 2 fluorescent tubes cannot be seen, and the shape thereof 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 the antiglare films of examples 1 to 13
The measurement results of the optical properties such as the secondary particle diameter and the aggregate area size of the silica nanoparticles, the surface roughness, and the antiglare property evaluation of the antiglare films of examples 1 to 13 of the present invention are shown in table 2.
Table 2: optical measurement results of the antiglare films of examples 1 to 13
The anti-glare films prepared in examples 1 to 11 of the present invention formed silica nanoparticles into silica micro-sized aggregates by the interaction between the silica nanoparticles and the acrylate-ether-group-containing surfactant, wherein the average secondary particle size of the aggregated silica nanoparticles was between 1,600nm and 3,300nm, and the average aggregated area of the secondary particles was between 293 μm2 and 709 μm2, or aggregated into a co-continuous network structure, thereby providing excellent anti-glare properties and a haze of between 1.0% and 2.0%. Meanwhile, the antiglare films prepared in examples 1 to 11 of the present invention had fine surfaces, and had an arithmetic average height Sa of 0.043 to 0.180. mu.m, a maximum height Sz of 0.413 to 2.104. mu.m, a center line average roughness Ra of 0.040 to 0.243. mu.m, a full roughness height Ry of 0.231 to 0.621. mu.m, an average peak pitch RSm of 31.542 to 154.665. mu.m, and a root mean square slope (inclination angle) Rdq of 1.132 to 6.413 degrees. The surface roughness of the antiglare films obtained in examples 1 to 11 of the present invention exhibited satisfactory fineness and had excellent antiglare properties.
In addition, examples 12 and 13 illustrate that organic fine particles are further added to the antiglare film disclosed by the invention to adjust the haze, which is 1.9% and 2.4%, respectively. The antiglare film in which the haze is adjusted by adding organic fine particles still retains satisfactory glossiness and clarity, and the surface roughness exhibits satisfactory fineness and has excellent antiglare properties.
Although the present invention has been described with reference to the above embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention.
Claims (20)
1. An antiglare film, characterized by comprising:
a transparent substrate; and
an anti-glare layer comprising an acrylic binder resin, an acrylate-ether group-containing surfactant, and a plurality of silica nanoparticles;
wherein the micron-sized floccule formed by the plurality of silica nano-particles has an average secondary particle size of 1,600nm to 3,300nm under an optical microscope.
2. The antiglare film of claim 1, wherein: the surface roughness of the anti-dazzle film has an arithmetic average height of 0.02-0.25 mu m, a maximum height of 0.25-2.50 mu m, a center line average roughness of 0.01-0.30 mu m, a full roughness height of 0.10-0.90 mu m, an average peak pitch of 20-200 mu m and a square root slope of 0.80-7.50 degrees.
3. The antiglare film of claim 1, wherein: the matrix-assisted laser desorption ionization-time-of-flight mass spectrometry of the acrylate-ether-group-containing surfactant has an average molecular weight of 200-6000 and an average oxyethylene number of 1-40.
4. The antiglare film of claim 3, wherein: the average molecular weight of the matrix-assisted laser desorption ionization-time-of-flight mass spectrometry containing the acrylate-ether-based surfactant is between 200 and 4500, and the average oxyethylene number is between 1 and 35.
5. The antiglare film of claim 3, wherein: the acrylate-ether-group-containing surfactant is a polymer compound of one or more monofunctional or polyfunctional unsaturated monomers having a vinyl group or a (meth) acryloyl group and one or more polyether monomers represented by the formula (I):
wherein R1 is hydrogen or methyl, R2 is hydrogen, a C1 to C10 hydrocarbon group, phenyl group or (meth) acryloyl group, a is 1 or an integer greater than 1, b is 0 or an integer greater than 0, wherein the total amount of the polyether monomer represented by formula (I) is contained in the acrylate-ether group-containing surfactant in an amount of 0.1 to 60 mol%.
6. The antiglare film of claim 1, wherein: the acrylate-ether group-containing surfactant is 0.01 to 8 parts by weight per hundred parts by weight of the acrylic binder resin.
7. The antiglare film of 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 of claim 1, wherein: the weight ratio of the silica nano-particles to the acrylate-ether group-containing surfactant is between 0.5 and 100.
9. The antiglare film of claim 1, wherein: the average primary particle diameter of each silica nanoparticle is between 5nm and 150 nm.
10. The antiglare film of claim 1, wherein: the acrylic binder resin includes a (meth) acrylate composition and an initiator, wherein the (meth) acrylate composition includes:
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.
11. The antiglare film of claim 10, wherein: the urethane (meth) acrylate oligomer having a functionality of between 6 and 15 is an aliphatic urethane (meth) acrylate oligomer.
12. The antiglare film of claim 10, 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.
13. The antiglare film of claim 10, wherein: the (meth) acrylate monomer having a functionality of less than 3 is 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, cyclotrimethylolpropane formal (meth) acrylate, at least one selected from the group consisting of 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, and combinations thereof.
14. The antiglare film of claim 10, wherein: the initiator is at least one selected from the group consisting of acetophenone initiator, diphenyl ketone initiator, phenylpropanone initiator, dibenzoyl initiator, bifunctional alpha-hydroxy ketone initiator and acylphosphine oxide initiator, or their combination.
15. An antiglare film, characterized by comprising:
a transparent substrate; and
an anti-glare layer comprising an acrylic binder resin, an acrylate-ether group-containing surfactant, a plurality of silica nanoparticles, and a plurality of organic microparticles,
wherein the micron-sized floccule formed by the plurality of nano-particles has an average secondary particle size of 1,600nm to 3,300nm under an optical microscope.
16. The antiglare film of claim 15, wherein: the particle size of each organic microparticle is between 0.5 μm and 6 μm.
17. The antiglare film of claim 15, wherein: the refractive index of each organic microparticle is between 1.4 and 1.6.
18. The antiglare film of claim 15, wherein: the plurality of organic fine particles is 0.5 to 15 parts by weight per one hundred parts by weight of the acrylic binder resin.
19. The antiglare film of claim 15, wherein: the plurality of organic fine particles are at least one selected from the group consisting of polymethyl methacrylate resin fine particles, polystyrene resin fine particles, styrene-methyl methacrylate copolymer fine particles, polyethylene resin fine particles, epoxy resin fine particles, silicone resin fine particles, polyvinylidene fluoride resin fine particles, and polyvinyl fluoride resin fine particles, or a combination thereof.
20. A polarizing plate, comprising:
a polarizing component; and
the antiglare film of any one of claims 1 to 19, formed on the surface of the polarizing component.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010587072.6A CN113671608A (en) | 2020-06-24 | 2020-06-24 | Anti-dazzle film and polarizing plate with same |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010587072.6A CN113671608A (en) | 2020-06-24 | 2020-06-24 | Anti-dazzle film and polarizing plate with same |
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| CN113671608A true CN113671608A (en) | 2021-11-19 |
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| CN103376479A (en) * | 2012-04-19 | 2013-10-30 | 大日本印刷株式会社 | Antiglare film, polarizer and image display device |
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