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CN111366994A - Anti-dazzle film and polarizing plate with same - Google Patents

Anti-dazzle film and polarizing plate with same Download PDF

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Publication number
CN111366994A
CN111366994A CN202010140803.2A CN202010140803A CN111366994A CN 111366994 A CN111366994 A CN 111366994A CN 202010140803 A CN202010140803 A CN 202010140803A CN 111366994 A CN111366994 A CN 111366994A
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China
Prior art keywords
meth
acrylate
antiglare film
weight percent
film
Prior art date
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Withdrawn
Application number
CN202010140803.2A
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Chinese (zh)
Inventor
陶尊圣
林志威
游国轩
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BenQ Materials Corp
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BenQ Materials Corp
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Filing date
Publication date
Application filed by BenQ Materials Corp filed Critical BenQ Materials Corp
Priority to CN202010140803.2A priority Critical patent/CN111366994A/en
Publication of CN111366994A publication Critical patent/CN111366994A/en
Priority to CN202011500008.6A priority patent/CN112540421B/en
Withdrawn legal-status Critical Current

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • 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
    • 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
    • C09D7/65—Additives macromolecular
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Abstract

The invention provides an anti-dazzle film and a polarizing plate with the anti-dazzle film, wherein the anti-dazzle film comprises a light-transmitting substrate; and an anti-glare hard coating layer formed on one side surface of the light-transmitting substrate, wherein the anti-glare hard coating layer comprises 75 to 90 weight percent of acrylic hard coating liquid, 0.01 to 10 weight percent of silica nanoparticles and 5 to 20 weight percent of organic microparticles. The invention provides a polarizing plate, which is provided with a polarizing element, wherein the anti-dazzle film is formed on the surface of the polarizing element, and the anti-dazzle film provides satisfactory anti-dazzle property and surface fineness, and simultaneously provides anti-dazzle and whitening blurring prevention effects, particularly the anti-dazzle property of a wide visual angle so as to increase the visibility of the whole display.

Description

Anti-dazzle film and polarizing plate with same
Technical Field
The invention relates to an anti-dazzle film for an image display device and a polarizing plate comprising the anti-dazzle film.
Background
With the development of display technology, for example, image display devices such as Liquid Crystal Displays (LCDs), organic light emitting diode displays (OLEDs), etc., demands for display performance such as high contrast, wide viewing angle, high luminance, thinness, large-scale, high definition, and diversification of additional functions are widely raised.
An antireflection film or an antiglare film is provided on the surface of the display to prevent the visibility of the image from being lowered. It is known that the antiglare effect of light diffusion is achieved by utilizing the surface roughness of an antiglare film, but increasing the surface roughness to improve the antiglare property causes white fogging of the antiglare layer, which leads to a problem of deterioration in visibility and contrast of a displayed image. On the other hand, with the development of high-resolution liquid crystal displays, the antiglare film for high-resolution displays requires a fine surface to prevent the sharpness of images from being affected, but this causes the whitening phenomenon of the display surface due to the reflection of external light on the display surface. Further, when light generated from the backlight inside the display passes through the antiglare film on the display surface, the light is internally reflected, and the image visibility is not good, which causes unevenness in the internal brightness of the display.
Further, when the high haze antiglare film is mounted on the surface of a display, it is difficult to simultaneously provide antiglare and whitening blur prevention effects, and color reproducibility or clarity at the time of display image presentation may be adversely affected, affecting the intended contrast.
Disclosure of Invention
In view of the problems in the prior art, the present invention provides an anti-glare film and a polarizing plate having the same to solve the above problems. The present invention provides an antiglare film for a liquid crystal display which can provide satisfactory antiglare properties and surface fineness while providing antiglare and whitening blur prevention effects, especially antiglare properties at a wide viewing angle to increase visibility of the display as a whole.
Accordingly, an object of the present invention is to provide an antiglare film comprising:
a light-transmitting substrate; and
an antiglare hard coat layer formed on one side surface of the light-transmitting substrate, wherein the antiglare hard coat layer comprises:
75 to 90 weight percent of acrylic hard coating liquid;
0.01 to 10 weight percent silica nanoparticles; and
5 to 20 weight percent of organic microparticles;
the glossiness of the anti-dazzle film at a viewing angle of 60 degrees is between 30% and 50%.
As an optional technical scheme, the average particle size of the organic microparticles is between 1 and 6 μm.
As an optional technical scheme, the average particle size of the organic microparticles is between 2 and 5 microns.
As an alternative solution, the silica nanoparticles have an average primary particle diameter (d)50) Between 5nm and 30nm and an average secondary particle diameter (d)50) Between 50nm and 120 nm.
As an optional technical solution, the usage amount of the organic fine particles is preferably between 7 weight percent and 15 weight percent.
As an optional technical solution, the amount of the silica nanoparticles used is between 0.05 weight percent and 7 weight percent.
As an optional technical solution, the organic fine particles are one or a combination 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, or polyvinyl fluoride resin fine particles, the surfaces of which are subjected to hydrophobic treatment or hydrophilic treatment.
As an optional technical scheme, 0.05 weight percent to 2 weight percent of leveling agent can be further added into the anti-dazzle hard coating.
As an optional technical scheme, the flatting agent is a polyether modified polysiloxane flatting agent.
As an alternative technical solution, the acrylic hard coating liquid comprises a (meth) acrylate composition and an initiator, the (meth) acrylate composition comprising:
35 to 50 weight percent of a urethane (meth) acrylate oligomer having a functionality of between 6 and 15;
12 to 20 weight percent of a (meth) acrylate monomer having a functionality of 3 to 6; and
1.5 to 12 weight percent of a meth) acrylate monomer having a functionality of less than 3.
As an alternative solution, the urethane (meth) acrylate oligomer with a functionality of 6 to 15 is an aliphatic urethane (meth) acrylate oligomer.
As an alternative embodiment, 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, 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 (dimpylpropane tetra (meth) acrylate, dtmpt m) a), and pentaerythritol tri (meth) acrylate (pentaerythritol tri (meth) acrylate, pet a), or a combination thereof.
As an alternative embodiment, the (meth) acrylate monomer having a functionality of less than 3 is selected from the group consisting of 2-ethylhexyl (meth) acrylate (2-ethylhexyl (meth) acrylate, 2-EH (M) A), 2-hydroxyethyl (meth) acrylate (2-hydroxyethoxy (meth) acrylate, 2-HE (M) A), 2-hydroxypropyl (meth) acrylate (2-hydroxypropyl (meth) acrylate, 2-HP (M) A), 2-hydroxybutyl (meth) acrylate (2-hydroxybutyl (meth) acrylate, 2-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, and trimethylolpropane (meth) acrylate (meth) acetal, CTF (M) A), 2-phenoxyethyl (meth) acrylate (2-phenoxyethyl (meth) acrylate, PHE (M) A), tetrahydrofuran (meth) acrylate (tetra hydrofuranyl (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) and isobornyl (meth) acrylate (isobornyl) acrylate, or a combination thereof.
As an optional technical solution, the initiator is at least one selected from the group consisting of acetophenone initiator, diphenyl ketone initiator, phenylpropanone initiator, dibenzoyl initiator, bifunctional α -hydroxy ketone initiator and acylphosphine oxide initiator, or a combination thereof.
Another object of the present invention is to provide a method for preparing an anti-glare film, which comprises uniformly mixing an acrylic hard coating solution with organic fine particles to form an anti-glare solution, coating the anti-glare solution on a light-transmitting substrate, drying the substrate coated with the anti-glare solution, and curing to form the anti-glare film.
Another object of the present invention is to provide a polarizing plate comprising a polarizing element, the polarizing element having the antiglare film on a surface thereof.
Compared with the prior art, the invention provides an anti-dazzle film and a polarizing plate with the anti-dazzle film, wherein the anti-dazzle film comprises a light-transmitting base material and an anti-dazzle hard coating, the anti-dazzle hard coating is formed on one side surface of the light-transmitting base material, and the anti-dazzle hard coating comprises 75-90 wt% of acrylic hard coating liquid, 0.01-10 wt% of silica nano particles and 5-20 wt% of organic micro particles. The invention provides a polarizing plate, which is provided with a polarizing element, wherein the anti-dazzle film is formed on the surface of the polarizing element, and the anti-dazzle film provides satisfactory anti-dazzle property and surface fineness, and simultaneously provides anti-dazzle and whitening blurring prevention effects, particularly the anti-dazzle property of a wide visual angle so as to increase the visibility of the whole display.
Detailed Description
In order to further understand the objects, structures, features and functions of the present invention, the following embodiments are described in detail; it is not intended to be the only form in which the embodiments of the invention may be practiced or utilized. The various embodiments disclosed below may be combined with or substituted for one another where appropriate, and additional embodiments may be added to one embodiment without further recitation or description.
The advantages, features, and technical solutions of the present invention will be described in greater detail with reference to exemplary embodiments for easier understanding, and the present invention may be embodied in different forms, so should not be construed as limited to the embodiments set forth herein, but rather as provided for a more complete and complete understanding of the scope of the present invention by those skilled in the art.
Unless otherwise defined, all terms (including technical and scientific terms) and 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 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.
Further, in this document, the term "meth (acrylate)" refers to both methacrylate and acrylate. Average primary particle diameter (d) of particles50) The particle diameter of the particles corresponds to the cumulative particle size distribution of the original particles of 50%, and the average secondary particle diameter (d) of the particles50) Refers to the corresponding particle size when the cumulative particle size distribution of the secondary particles formed after the particle agglomeration reaches 50%.
The present invention provides an antiglare film comprising a light-transmitting substrate; and an anti-glare hard coating layer formed on one side surface of the light-transmitting substrate, wherein the anti-glare hard coating layer comprises 75-90 wt% of acrylic hard coating liquid, 0.01-10 wt% of silica nanoparticles and 5-20 wt% of organic microparticles, and the glossiness of the anti-glare film at an angle of 60 degrees is between 30% and 50%. The antiglare film provides satisfactory antiglare properties and surface fineness, while providing antiglare and whitening blur prevention effects, particularly antiglare properties at a wide viewing angle to increase visibility of the display as a whole.
The total haze of the anti-glare film disclosed by the invention is between 40% and 50%, the internal haze is between 28% and 40%, and the surface haze is between 10% and 13%.
In a preferred embodiment of the present invention, the light-transmitting substrate of the antiglare film is a film having good mechanical strength and light transmittance, which includes, but is not limited to, resin films of triacetyl cellulose (TAC), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), Polycarbonate (PC), Polyimide (PI), Polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cyclic olefin Copolymer (COP), and the like.
In one embodiment of the present invention, the light-transmitting substrate of the anti-glare film has a light transmittance of 80% or more, preferably 90% or more, and the thickness of the light-transmitting substrate is between 10 μm and 250 μm, preferably between 20 μm and 100 μm.
In one embodiment of the present invention, the thickness of the hard coating layer of the anti-glare film is between 2 μm and 10 μm, preferably between 3 μm and 9 μm, and more preferably between 4 μm and 7 μm. If the thickness is too low, the problem of insufficient hardness of the antiglare film tends to occur. If the thickness is too high, the antiglare film tends to curl excessively after curing, and the antiglare hard coat layer tends to be brittle when processed.
In the anti-glare film disclosed by the invention, the anti-glare hard coating layer comprises organic particles and silica nanoparticles, wherein the organic particles are used for providing the light diffusion function of the anti-glare hard coating layer and providing proper internal haze to homogenize the light emitted from the interior of the display. The internal haze of the anti-glare film of the present invention can be adjusted according to the refractive index, particle size and addition amount of the selected organic fine particles. The refractive index of the organic fine particles suitable for use in the present invention is between 1.49 and 1.60, and the average particle size is between 1 μm and 6 μm, preferably between 2 μm and 5 μm. The organic fine particles are used in an amount of 5 to 20 wt%, preferably 7 to 15 wt%. If the amount of the organic fine particles used is too low, a sufficient light scattering effect cannot be provided, the antiglare property of the antiglare film is insufficient, and the display is easily affected by light reflection from an external light source, resulting in a problem of deterioration in display quality. If the amount of organic fine particles used is too high, the light scattering effect of the antiglare film becomes too high, and the display image of the display tends to have problems of whitening and contrast deterioration.
Suitable organic fine particles are 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, or polyvinyl fluoride resin fine particles. The organic microparticles may be hydrophilic or hydrophobic. The organic particles can be resin fine particles containing a styrene group, or organic particles whose surfaces are hydrophilically treated with, for example, 2-hydroxyethyl (meth) acrylate (2-HE (M) A) or (meth) acrylonitrile (meth) acrylate.
In the antiglare film of the present invention, the silica nanoparticles contained in the antiglare hard coat layer can prevent the sedimentation of organic particles and increase the fineness of the surface of the antiglare hard coat layer. The average primary particle diameter (d) of the silica nanoparticles suitable for use in the present invention50) About 5nm to 30nm and an average secondary particle diameter (d)50) About 50nm to 120nm, and the amount of the silica nanoparticles is 0.01 wt% to 10 wt%, preferably 0.05 wt% to 7 wt%. If the amount of the silica nanoparticles used is too low, the organic fine particles cannot be effectively prevented from settling, and the surface irregularities on the antiglare film cannot be appropriately provided to increase the fineness. If the amount of the silica nanoparticles used is too high, the haze of the antiglare film tends to be increased due to the decrease in the dispersibility of the nanoparticles, and problems such as whitening and decrease in contrast occur in the display.
0.05 to 2 weight percent of leveling agent can be further added into the anti-dazzle hard coating of the anti-dazzle film. The addition of the leveling agent to the antiglare hard coat layer can make the coating surface good, and the antiglare hard coat layer has surface lubricity, antifouling property, scratch resistance and the like after coating or drying and molding. The leveling agent which can be used for the antiglare film of the present invention may be a fluorine-based or organosilicon-based leveling agent such as polysiloxane, fluorine-based surfactant, etc., and preferably contains polyether-modified polysiloxane.
The leveling agent, such as polyether modified polysiloxane, suitable for use in the antiglare hard coat layer of the antiglare film of the present invention is used in an amount of 0.05 to 2 weight percent, preferably 0.5 to 1 weight percent. If the amount of the leveling agent used is too low, the content of the leveling agent on the surface of the antiglare film becomes insufficient, and drying defects are likely to occur during coating. If the amount of the leveling agent used is too high, the leveling agent generates excessive micelles inside the antiglare film, and the physical properties of the antiglare film are degraded.
In the anti-glare film of the present invention, the acrylic hard coat coating liquid of the anti-glare hard coat layer comprises a (meth) acrylate composition and an initiator, wherein the (meth) acrylate composition comprises 35 to 50 weight percent of urethane (meth) acrylate oligomer having a functionality of 6 to 15, 12 to 20 weight percent of (meth) acrylate monomer having a functionality of 3 to 6, and 1.5 to 12 weight percent of (meth) acrylate monomer having a functionality of less than 3, wherein the molecular weight of the urethane (meth) acrylate oligomer is between 1,000 and 4,500. The anti-dazzle hard coating has good adhesion with the PET substrate, good weather resistance, sufficient surface hardness and scratch resistance.
In one 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 1,500 to 4,500. In a preferred embodiment of the present invention, the urethane (meth) acrylate oligomer having a functionality of 6 to 15 is preferably an aliphatic urethane (meth) acrylate oligomer having a functionality of 6 to 15.
In one 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.
In one 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), 2-hydroxypropyl (meth) acrylate (2-hydroxypropyl (meth) acrylate, 2-HP (M) A), 2-hydroxybutyl (meth) acrylate (2-hydroxybut (meth) acrylate, 2-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 (DPgd (m) a), tripropylene glycol di (meth) acrylate (tripropylene glycol di (meth) acrylate, tpgd (m) a), isobornyl (meth) acrylate (isobornyl) acrylate, or a combination thereof. The (meth) acrylate monomer having a functionality of less than 3 is preferably 1,6-hexanediol diacrylate (HDDA), cyclotrimethylolpropane formal acrylate (CTFA), 2-phenoxyethyl acrylate (PHEA), or a combination thereof.
Suitable initiators in the acrylic hard coat coating liquid of the present invention may employ initiators which have been widely used in this technical field, and are not particularly limited, and for example, acetophenone type initiators, benzophenone type initiators, acetophenone type initiators, dibenzoyl type initiators, bifunctional α -hydroxyketone type initiators or acylphosphine oxide type initiators, and the like may be employed.
In another embodiment of the present invention, additives such as antistatic agent, colorant, flame retardant, uv absorber, antioxidant, surface modifier, etc. may be added to the acrylic hard coating liquid as required.
Other optical function layers, such as a low refractive layer, may also be selectively coated on the antiglare film of the present invention to provide antireflection properties.
The preparation method of the anti-dazzle film comprises the steps of uniformly mixing polyurethane (methyl) acrylate oligomer with the functionality of 6-15, a (methyl) acrylate monomer with the functionality of 3-6, a (methyl) acrylate monomer with the functionality of less than 3, an initiator and a proper solvent to form acrylic hard coating liquid; adding organic microparticles and/or silica nanoparticles, a leveling agent, an additive, an organic solvent and the like into the acrylic hard coating liquid, 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 then forming an anti-dazzle hard coating on the substrate after radiation curing or electron beam curing 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 the hard coating solution, and suitable solvents may be, for example, acetone, butanone, cyclohexanone, methyl isobutyl ketone, hexane, cyclohexane, dichloromethane, 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, or the like, but are not limited thereto.
The methods for applying the anti-glare solution may be roll coating, knife coating, dip coating, roll coating, spin coating, slit coating, or the like, which are commonly used in the art.
The antiglare film of the present invention can be combined with other functional optical films to form a composite optical film. A functional optical film such as a polarizing plate may be used, wherein the polarizing plate may be located on the other side of the transparent substrate of the antiglare film with respect to the antiglare hard coat layer.
According to the anti-glare film disclosed in the above embodiment of the present invention, in another embodiment, the present invention further provides a polarizing plate comprising a polarizing element, wherein the anti-glare film disclosed in the above embodiment of the present invention is provided on a surface of the polarizing element.
The following examples are intended to further illustrate the invention, but the invention is not limited thereto.
Examples
Preparation example 1: preparation of acrylic hard coat coating liquid I
An acrylic hardcoat coating I was formed after mixing and stirring 42 weight percent urethane acrylate (functionality 6, viscosity about 30,000cps (25 ℃), available from IGM, taiwan), 4.5 weight percent pentaerythritol triacrylate (PETA), 12 weight percent dipentaerythritol hexaacrylate (DPHA), 3 weight percent cyclotrimethylolpropane formal acrylate (CTFA), 4 weight percent polymerization initiator (Chemcure-481, available from the bridge industry, taiwan), 24.5 weight percent Ethyl Acetate (EAC), and 10 weight percent n-butyl acetate (nBAC) for 1 hour.
Preparation example 2: preparation of acrylic hard coat coating liquid II
An acrylic hardcoat coating solution II was formed after mixing and stirring 40.5 weight percent of urethane acrylate oligomer (functionality 9, molecular weight about 2,000, viscosity about 86,000cps (25 ℃), available from Allnex, usa), 4.5 weight percent of pentaerythritol triacrylate (PETA), 10.5 weight percent of dipentaerythritol hexaacrylate (DPHA), 4.5 weight percent of hexanediol diacrylate (HDDA), 1.5 weight percent of 2-phenoxyethyl acrylate (PHEA), 3.5 weight percent of polymerization initiator (Chemcure-481, available from the constant bridge industry, taiwan), 0.5 weight percent of polymerization initiator (TR-PPI-One, available from new strength materials, hong kong), 24.5 weight percent of Ethyl Acetate (EAC), and 10 weight percent of n-butyl acetate (nBAC) for 1 hour.
Example 1
199 parts by weight of the hard coat coating solution I, 7.4 parts by weight of a hydrophobically modified silica nanoparticle dispersion sol (NanoBYK-3650, having a solid content of 31%, and a solvent of propylene glycol methyl ether acetate/propylene glycol monomethyl ether solution, available from BYK, Germany), 5.3 parts by weight of a polyether modified polydimethylsiloxane leveling agent (BYK-333, having a solid content of 10%, and a solvent of ethyl acetate, available from BYK, Germany), 19.6 parts by weight of polystyrene particles (SSX-303ABE, having an average particle diameter of 3.0 μm, a refractive index of 1.59, available from a product of hydration, Japan), 48.3 parts by weight of propylene glycol methyl ether acetate (PMA) and 100 parts by weight of n-propyl acetate (nPAC) were mixed and stirred for 1 hour to form an anti-hard coat solution.
The anti-glare solution was coated on one side surface of a polyethylene terephthalate (PET) substrate having a thickness of 80 μm, dried, and then photo-cured under a nitrogen atmosphere with a UV lamp at a radiation dose of 80mJ/cm2 to form an anti-glare hard coating film having a thickness of 4.2 μm on one side surface of the PET substrate, and an anti-glare film was obtained.
The obtained antiglare film was evaluated for transmittance, total haze, internal haze, surface haze, gloss, clarity and antiglare property by the optical measurement method described later, and the results are shown in table 1, and the scratch resistance measurement, hardness measurement, and adhesion to the substrate were performed, and the test results are shown in table 2.
Example 2
199 parts by weight of the hard coat coating solution B, 0.5 part by weight of a hydrophobically modified silica nanoparticle dispersion sol (NanoBYK-3650, solid content 31%, solvent propylene glycol methyl ether acetate/propylene glycol methyl ether solution, available from BYK, Germany), 5.2 parts by weight of a polyether modified polydimethylsiloxane leveling agent (BYK-333, solid content 10%, solvent ethyl acetate, available from BYK, Germany), 16.3 parts by weight of polystyrene particles (XX-35IK, average particle size 3.8 μm, refractive index 1.59, available from a hydrated product, Japan), 37.4 parts by weight of Ethyl Acetate (EAC) and 112 parts by weight of methyl isobutyl ketone (MIBK) were mixed and stirred for 1 hour to form an anti-glare hard coat solution.
The anti-glare solution was coated on one side surface of a polyethylene terephthalate (PET) substrate having a thickness of 80 μm, dried, and then photo-cured under a nitrogen atmosphere with a UV lamp at a radiation dose of 80mJ/cm2 to form an anti-glare hard coating film having a thickness of 5.0 μm on one side surface of the PET substrate, and an anti-glare film was obtained.
The obtained antiglare film was subjected to the test as in example 1, and the results are shown in tables 1 and 2.
Example 3
After 212 parts by weight of the hard coat liquid II, 21.6 parts by weight of a silica nanoparticle dispersion sol (MEK-9130X, 30% by solid content, butanone as a solvent, purchased from Union silica, Taiwan), 5.4 parts by weight of a polyether-modified polydimethylsiloxane leveling agent (BYK-307, 10% by solid content, ethyl acetate as a solvent, purchased from BYK, Germany), 16.2 parts by weight of polystyrene particles (XX-29IK, 3.5 μm in average particle size, 1.59 in refractive index, purchased from a product of hydration, Japan), 39.45 parts by weight of n-butyl acetate (nBAC), 39.45 parts by weight of n-propyl acetate (nPAC), and 72.5 parts by weight of methyl isobutyl ketone (MIBK), were mixed and stirred for 1 hour, a hard coat solution having resistance was formed.
The hard coating solution having anti-glare property was coated on one side surface of a polyethylene terephthalate (PET) substrate having a thickness of 80 μm, dried, and then photo-cured under a nitrogen atmosphere with a UV lamp at a radiation dose of 80mJ/cm2 to form a hard coating film having anti-glare property having a thickness of 4.4 μm on one side surface of the substrate, and an anti-glare film was obtained.
The obtained antiglare film was subjected to the test as in example 1, and the results are shown in tables 1 and 2.
Example 4
199 parts by weight of the hard coat coating solution II, 3.6 parts by weight of a hydrophobically modified silica nanoparticle dispersion sol (NanoBYK-3650, with a solid content of 31%, and a solvent of propylene glycol methyl ether acetate/propylene glycol monomethyl ether solution, available from BYK, Germany), 5.3 parts by weight of a polyether modified polydimethylsiloxane leveling agent (BYK-333, with a solid content of 10%, and a solvent of ethyl acetate, available from BYK, Germany), 16.3 parts by weight of polystyrene particles (SSX-303ABE, with an average particle size of 3.0 μm, a refractive index of 1.59, available from a product of hydration, Japan), 36.8 parts by weight of Ethyl Acetate (EAC) and 112 parts by weight of methyl isobutyl ketone (MIBK) were mixed and stirred for 1 hour to be uniformly dispersed, and a hard coat solution with anti-glare properties was formed.
Coating the hard coating solution with anti-glare property on one side surface of polyethylene terephthalate (PET) substrate with thickness of 80 μm, drying, and performing nitrogen atmosphere at 80mJ/cm2A UV lamp of a radiation dose was subjected to photocuring to form a hard coat layer having an antiglare property with a thickness of 4.3 μm on one of the surfaces of the PET substrate, and an antiglare film was obtained.
The obtained antiglare film was subjected to the test as in example 1, and the results are shown in tables 1 and 2.
Example 5
212 parts by weight of a hard coating solution II, 32.4 parts by weight of a silica nanoparticle dispersion sol (MEK-9130X, 30% by solid content, butanone as a solvent, purchased from Union silica, Taiwan), 5.4 parts by weight of a polyether modified polydimethylsiloxane leveling agent (BYK-307, 10% by solid content, ethyl acetate, purchased from BYK, Germany), 13 parts by weight of polystyrene particles (XX-31IK, 3.8 μm in average particle diameter, 1.59 in refractive index, purchased from a product of hydration, Japan), 39.45 parts by weight of n-butyl acetate (nBAC), 39.45 parts by weight of n-propyl acetate (nPAC) and 72.5 parts by weight of methyl isobutyl ketone (MIBK) were mixed and stirred for 1 hour to be uniformly dispersed, thereby forming a hard coating solution having anti-glare properties.
Coating the hard coating solution with anti-glare property on one side surface of polyethylene terephthalate (PET) substrate with thickness of 80 μm, drying, and introducing into nitrogen atmosphere at a flow rate of 80mJ/cm2A UV lamp of a radiation dose was subjected to photocuring to form a hard coat layer having an antiglare property with a thickness of 4.6 μm on one side surface of the PET substrate, and an antiglare film was obtained.
The obtained antiglare film was subjected to the test as in example 1, and the results are shown in tables 1 and 2.
Optical measurement method
The antiglare films obtained in the above examples were measured optically according to the measurement method of the Japanese Industrial Standard (JIS).
Light transmittance measurement: measured by a measurement method of JIS K7361 using an NDH-2000 haze meter (manufactured by Nippon Denshoku industries Co., Ltd.).
Measurement of haze: the haze was evaluated according to the description of JISK7136 using NDH-2000 (Nippon Denshoku Corp., Japan).
Measurement of internal and surface haze: in the state where a triacetyl cellulose substrate (T40UZ, thickness 40 μm, fuji film company) was attached to the surface of the antiglare film using a transparent optical adhesive tape so that the uneven surface of the antiglare film became flat, the haze was evaluated according to the description of JISK7136 using an NDH-2000 haze meter (manufactured by japan electro-chromatic industries, inc.) to obtain an internal haze value, and then the internal haze value was subtracted from the total haze value to obtain a surface haze value.
Measurement of gloss: the antiglare film was bonded to a black acrylic plate, measured using a BYK Micro-Gloss glossmeter according to the description of JIS Z8741, and Gloss values at viewing angles of 25, 60, and 85 degrees were selected.
Measurement of resolution Using a SUGA ICM-IT image resolution instrument, measurement was performed in accordance with the description of JIS K7374, and values measured at slits of 0.125mm, 0.25mm, 0.50mm, 1.00mm and 2.00mm were added.
Measurement of anti-glare property: the antiglare film was bonded to a black acrylic plate, and the antiglare property of the antiglare film was evaluated in the following 5 grades by reflecting 2 daylight lamp light on the surface of the antiglare film and visually checking the degree of blooming of the daylight lamp.
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.
TABLE 1 optical measurement results of the antiglare films of examples 1 to 5:
Figure BDA0002399018400000171
method for measuring scratch resistance, hardness and adhesion with substrate
Measurement of scratch resistance: on the surface of the antiglare film, steel wool #0000 at 250gf/cm was used2Is rubbed back and forth 10 times under the rubbing load, and then, whether scratches are left on the surface of the antiglare layer is observed with eyes
Measuring the pencil hardness: pencil standard of 2H hardness of Mitsubishi film material by using mechanical pencil hardness meter
Measured according to JIS K-5400
Measurement of adhesion: the adhesion measurement was carried out using a hundred-grid knife in accordance with the description of JIS K5600-5-6. TABLE 2 results of the measurement of scratch resistance, pencil hardness, and adhesiveness of the antiglare films of examples 1 to 5:
Figure BDA0002399018400000172
Figure BDA0002399018400000181
as is clear from tables 1 and 2, the antiglare film of the present invention has not only good optical properties of antiglare property but also good adhesion to a polyethylene terephthalate (PET) substrate, and provides excellent scratch resistance on the film surface.
The invention provides an anti-dazzle film and a polarizing plate with the anti-dazzle film, wherein the anti-dazzle film comprises a light-transmitting base material and an anti-dazzle hard coating, the anti-dazzle hard coating is formed on one side surface of the light-transmitting base material, and the anti-dazzle hard coating comprises 75-90 wt% of acrylic hard coating liquid, 0.01-10 wt% of silicon dioxide nano particles and 5-20 wt% of organic micro particles. The invention provides a polarizing plate comprising a polarizing element, wherein an anti-glare film is formed on the surface of the polarizing element, and the anti-glare film provides satisfactory anti-glare property and surface fineness, and simultaneously provides anti-glare and whitening blur prevention effects, especially anti-glare property at wide viewing angle to increase visibility of the whole display
The present invention has been described in relation to the above embodiments, which are only exemplary of the implementation of the present invention. It should be noted that the disclosed embodiments do not limit the scope of the invention. Rather, it is intended that all such modifications and variations be included within the spirit and scope of this invention.

Claims (15)

1. An antiglare film, comprising:
a light-transmitting substrate; and
an antiglare hard coat layer formed on one side surface of the light-transmitting substrate, wherein the antiglare hard coat layer comprises:
75 to 90 weight percent of acrylic hard coating liquid;
0.01 to 10 weight percent silica nanoparticles; and
5 to 20 weight percent of organic microparticles;
the glossiness of the anti-dazzle film at a viewing angle of 60 degrees is between 30% and 50%.
2. The antiglare film of claim 1, wherein the organic fine particles have an average particle size of from 1 μm to 6 μm.
3. The antiglare film of claim 2, wherein the organic fine particles have an average particle size of from 2 μm to 5 μm.
4. The antiglare film of claim 1, wherein the silica nanoparticles have an average primary particle diameter (d)50) Between 5nm and 30nm and an average secondary particle diameter (d)50) Between 50nm and 120 nm.
5. The antiglare film of claim 1, wherein the organic microparticles are preferably used in an amount of from 7 to 15 wt%.
6. The anti-glare film according to claim 1, wherein the silica nanoparticles are used in an amount of 0.05 to 7 weight percent.
7. The antiglare film of claim 1, wherein the organic fine particles are one or a combination 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, and polyvinyl fluoride resin fine particles, the surfaces of which are hydrophobic-treated or hydrophilic-treated.
8. The antiglare film of claim 1, wherein 0.05 to 2 weight percent of a leveling agent may be further added to the antiglare hard coat layer.
9. The antiglare film of claim 1, wherein the leveling agent is a polyether-modified polysiloxane-based leveling agent.
10. The antiglare film of claim 1, wherein the acrylic hard coat layer coating liquid comprises a (meth) acrylate composition and an initiator, the (meth) acrylate composition comprising:
35 to 50 weight percent of a urethane (meth) acrylate oligomer having a functionality of between 6 and 15;
12 to 20 weight percent of a (meth) acrylate monomer having a functionality of 3 to 6; and
1.5 to 12 weight percent 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, dpp (m) a, dipentaerythritol hexa (meth) acrylate, dph (m) a, trimethylolpropane tri (meth) acrylate, tmpt (m) a, ditrimethylolpropane tetra (meth) acrylate, dtmpt (m) a, and pentaerythritol tri (meth) acrylate, pet (pet) a, 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-ethylhexyl (meth) acrylate, 2-EH (M) A), 2-hydroxyethyl (meth) acrylate (2-hydroxyethoxy (meth) acrylate, 2-HE (M) A), 2-hydroxypropyl (meth) acrylate (2-hydroxypropyl (meth) acrylate, 2-HP (M) A), 2-hydroxybutyl (meth) acrylate (2-hydroxybutyl (meth) acrylate, 2-HB (M) A), 2-butoxyethyl (meth) acrylate (2-butoxyethoxy (meth) acrylate), 1,6-hexanediol di (meth) acrylate (1,6-hexanediol di (meth) acrylate, HDD (M) A), cyclotrimethyolpropane formal (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 (DPGD (M) A), tripropylene glycol di (meth) acrylate (triethylene glycol di (meth) acrylate, TPGD (M) A, isobornyl (meth) acrylate, or a combination thereof.
14. The antiglare film of claim 10, wherein said initiator is at least one selected from the group consisting of acetophenone initiator, benzophenone initiator, phenylpropanone initiator, dibenzoyl initiator, difunctional α -hydroxyketone initiator and acylphosphine oxide initiator or a combination thereof.
15. A polarizing plate comprising a polarizing element, wherein the polarizing element has an antiglare film according to any one of claims 1 to 14 on a surface thereof.
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