CN112540421B - Antiglare film and polarizing plate having the same - Google Patents

Antiglare film and polarizing plate having the same Download PDF

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Publication number
CN112540421B
CN112540421B CN202011500008.6A CN202011500008A CN112540421B CN 112540421 B CN112540421 B CN 112540421B CN 202011500008 A CN202011500008 A CN 202011500008A CN 112540421 B CN112540421 B CN 112540421B
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meth
acrylate
antiglare film
antiglare
weight
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CN112540421A (en
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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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    • 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

Disclosed is an antiglare film comprising a polyethylene terephthalate (PET) substrate; and a cured antiglare hard coat layer formed on one of the surfaces of the light-transmitting substrate, wherein the cured antiglare hard coat layer comprises 75 to 90 parts by weight of an acrylic binder resin, 0.01 to 10 parts by weight of silica nanoparticles, and 5 to 20 parts by weight of organic microparticles. The antiglare film has a total haze of 35% to 50% and a surface haze of 10% to 15%, and a gloss at 60-degree viewing angle of 30% to 50%. The antiglare film provides satisfactory antiglare properties and surface definition, especially wide viewing angle antiglare properties to increase the visibility of the display as a whole.

Description

Antiglare film and polarizing plate having the same
Technical Field
The present invention relates to an antiglare film useful for image display equipment and a polarizing plate comprising the antiglare film.
Background
With the increasing development of display technology, for example, image display devices such as Liquid Crystal Displays (LCDs), organic light emitting diode displays (OLEDs), demands for display performance such as high contrast ratio, wide viewing angle, high luminance, thin, large, high definition, and additional function diversification are widely put forward.
An antiglare effect of light diffusion is achieved by using an antiglare film with a rough surface on the surface of a display, but when the antiglare property is improved to increase the surface roughness, white haze of the antiglare layer is caused, and visibility and contrast of a display image are lowered. With the development of high-resolution liquid crystal displays, an antiglare film for a high-resolution display requires a fine surface to avoid the influence of the definition of an image, but this causes external light to be reflected at the display surface to generate a surface whitening phenomenon, and at the same time, when light generated by a backlight inside the display passes through a rough surface of the antiglare film on the display surface, a microlens effect is generated to cause a flicker phenomenon inside, which is unfavorable for the color reproducibility or definition when the display is imaged, and influences the intended contrast to cause poor image visibility.
It is known to coat organic microparticles and/or nanoparticles with triacetyl cellulose (Triacetyl cellulose, TAC) film to prepare antiglare film, but TAC film is easily hygroscopic and has poor weatherability, so polyethylene terephthalate (polyethylene terephthalate, PET) and polymethyl methacrylate (polymethyl methacrylate, PMMA) film having better weatherability and good light transmittance are currently used as the base material of optical film instead of TAC film. When the PMMA film is used as a base material, due to the film surface property of the PMMA film, the particles can easily approach the upper edge of the coating layer by the co-dissolution effect generated by the coating layer and the film surface when the particles are coated, so that the anti-dazzle property is achieved. However, when the PET film material is used, the co-dissolved layer is not easily generated on the film surface of the PET film, so that the sedimentation phenomenon of particles is easily generated, the particles are not easily protruded out of the film surface to lose the antiglare property, and the co-dissolved layer is not easily generated on the film surface of the PET film, so that the adhesion between the antiglare coating and the PET film is also possibly poor.
The present invention provides an antiglare film based on polyethylene terephthalate (PET) which can provide satisfactory antiglare properties and can achieve high definition, high resolution, no flicker, good visibility and good adhesion.
Disclosure of Invention
In view of the problems in the prior art, the present invention provides an antiglare film to solve the above problems.
Accordingly, the present invention has been made to solve the problems occurring in the prior art, and it is an object of the present invention to provide an antiglare film comprising:
a polyethylene terephthalate (PET) substrate; and
A cured antiglare hard coat layer formed on the surface of the substrate, wherein the cured antiglare hard coat layer comprises:
75 to 90 parts by weight of an acrylic binder resin;
0.01 to 10 parts by weight of silica nanoparticles;
5 to 20 parts by weight of organic fine particles; and
0.05 to 2 parts by weight of a leveling agent;
the antiglare film has a total haze of 35% to 50% and a surface haze of 10% to 15%, and a gloss at a 60-degree viewing angle of 30% to 50%.
As an alternative embodiment, the antiglare film has a total haze of 40% to 50%, an internal haze of 27% to 40%, and a surface haze of 10% to 13%.
Alternatively, the organic microparticles have an average particle size of 2 μm to 6 μm.
Alternatively, the organic microparticles have an average particle size of 2 μm to 5 μm.
As an alternative solution, the silica nanoparticles have a primary particle diameter (d 50) of 5nm to 30nm and a secondary particle diameter (d 50) of 50nm to 120nm.
As an alternative, the acrylic binder resin is preferably used in an amount of 80 to 90 parts by weight.
As an alternative, the organic microparticles may be used in an amount of 7 to 15 parts by weight.
As an alternative, the silica nanoparticles may be used in an amount of 0.05 to 7 parts by weight.
As an alternative technical scheme, the leveling agent is used in an amount of 0.1 to 1 part by weight.
As an alternative technical scheme, the organic microparticles are polymethyl methacrylate resin microparticles, polystyrene resin microparticles, styrene-methyl methacrylate copolymer microparticles, polyethylene resin microparticles, epoxy resin microparticles, polysilicone resin microparticles, polyvinylidene fluoride resin or polyvinyl fluoride resin microparticles which are subjected to surface hydrophobic treatment or hydrophilic treatment.
Alternatively, the refractive index of the organic microparticles is 1.40 to 1.60.
As an alternative, the thickness of the cured antiglare hard coat layer is 3 μm to 9 μm.
As an alternative technical scheme, the leveling agent is a polyether modified polysiloxane leveling agent.
As an alternative embodiment, the acrylic binder resin comprises a (meth) acrylate composition and an initiator, the (meth) acrylate composition comprising:
35 to 50 parts by weight of a polyurethane (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 polyurethane (meth) acrylate oligomer has a molecular weight of 1,000 to 4,500.
Alternatively, the polyurethane (meth) acrylate oligomer having a functionality of 6 to 15 is an aliphatic polyurethane (meth) acrylate oligomer.
As an alternative solution, 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 (pentaerythritol tetra (meth) acrylate), dipentaerythritol penta (meth) acrylate (dipentaerythritol penta (meth) acrylate, DPP (M) a), dipentaerythritol hexa (meth) acrylate (dipentaerythritol hexa (meth) acrylate, DPH (M) a), trimethylolpropane tri (meth) acrylate (trimethylolpropane tri (meth) acrylate, TMPT (M) a), ditrimethylolpropane tetra (ditrimethylolpropane tetra (meth) acrylate, DTMPT (M) a) and pentaerythritol tri (meth) acrylate (pentaerythritol tri (meth) acrylate, PET (M) a), or a combination thereof.
As an alternative solution, the (meth) acrylate monomer with the functionality 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-hydroxyethyl (meth) acrylate,2-HE (M) A), 3-hydroxypropyl (meth) acrylate (3-hydroxypropyl (meth) acrylate,3-HP (M) A), 4-hydroxybutyl (meth) acrylate (4-hydroxybutyl (meth) acrylate,4-HB (M) A), 2-butoxyethyl (meth) acrylate (2-butoxyethyl (meth) acrylate), 1,6-hexanediol di (meth) acrylate, HDD (M) A), cyclotrimethylolpropane methylacrylate (cyclic trimethylolpropane formal (meth) acrylate, CTF (M) A), 2-phenoxyethyl (meth) acrylate (2-phenoxyethyl (meth) acrylate, PHE (M) A), tetrahydrofuran (meth) acrylate (tetrahydrofurfuryl (meth) acrylate, THF (M) A), lauryl (meth) acrylate (lauryl (meth) acrylate, at least one of the group consisting of L (M) a), diethylene glycol di (meth) acrylate (diethylene glycol di (meth) acrylate, DEGD (M) a), dipropylene glycol di (meth) acrylate (dipropylene glycol di (meth) acrylate, DPGD (M) a), tripropylene glycol di (meth) acrylate (tripropylene glycol di (meth) acrylate, TPGD (M) a) and isobornyl (meth) acrylate (isobornyl (meth) acrylate), or a combination thereof.
As an alternative technical scheme, the initiator is at least one selected from the group consisting of acetophenone initiator, diphenyl ketone initiator, propiophenone initiator, dibenzoyl initiator, difunctional alpha-hydroxy ketone initiator and acyl phosphine oxide initiator or a combination thereof.
The invention also provides a polarizing plate, which is provided with a polarizing component, and the polarizing plate is provided with the anti-dazzle film on at least one surface of the polarizing component.
Compared with the prior art, the anti-dazzle film and the surface haze of the polarizing plate with the anti-dazzle film can effectively reduce the flicker of the surface of a display, and the proper internal haze damages the internal scattering of an anti-dazzle layer, so that satisfactory anti-dazzle property is provided, and high definition, no flicker and good visibility can be achieved. The antiglare film and the polarizing plate having the antiglare film disclosed by the invention also provide excellent display quality at a wide viewing angle, and antiglare property at a wide viewing angle is used to increase the visibility of the whole display. The antiglare film and the polarizing plate with the antiglare film have good adhesion between the antiglare layer and the base material.
The present invention will be described in detail with reference to specific examples, but is not limited thereto.
Detailed Description
For a more complete and thorough description of the present disclosure, the following illustrative descriptions of embodiments and examples of the present invention are presented; this is not the only form of practicing or implementing the invention as embodied. The embodiments disclosed below may be combined with or substituted for each other as advantageous, and other embodiments may be added to one embodiment without further description or illustration.
The advantages, features, and technical approaches to the present invention will be more readily understood by reference to the following detailed description of exemplary embodiments and may be embodied in various forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed to provide a thorough and complete understanding of the present disclosure by those skilled in the art, and will only be defined by the appended claims.
Unless otherwise defined, all terms (including technical and scientific terms) used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and terms such as those defined in commonly used dictionaries should be interpreted as having a meaning that is consistent with the context of the relevant art and will not be interpreted in an excessively idealized or overly formal sense unless expressly so defined hereinafter.
In the present specification, the term "meth" acrylate refers to methacrylate and acrylate. The average primary particle diameter (d 50) of the particles is the particle diameter corresponding to the case where the cumulative particle size distribution of the primary particles reaches 50%, and the average secondary particle diameter (d 50) of the particles is the particle diameter corresponding to the case where the cumulative particle size distribution of the secondary particles formed after the aggregation of the particles reaches 50%.
An object of the present invention is to provide an antiglare film comprising a polyethylene terephthalate (PET) substrate; and a cured antiglare hard coat layer formed on the surface of the substrate, wherein the cured antiglare hard coat layer comprises 75 to 90 parts by weight of an acrylic binder resin, 0.01 to 10 parts by weight of silica nanoparticles, 5 to 20 parts by weight of organic fine particles, and 0.05 to 2 parts by weight of a leveling agent, the antiglare film has a total haze of 35 to 50% and a surface haze of 10 to 15%, and a gloss at 60 degrees of 30 to 50%.
The antiglare film of the present invention preferably has a total haze of 40% to 50%, an internal haze of 27% to 40% and a surface haze of 10% to 13%. The surface haze of the antiglare film of the present invention can effectively reduce flicker of the display surface and appropriate internal haze damages internal scattering of the antiglare layer to provide satisfactory antiglare properties and can achieve high definition, high resolution, no flicker and good visibility.
The antiglare film disclosed in the present invention has a glossiness of 30 to 50% at 60 degrees viewing angle, in addition to providing satisfactory antiglare property and surface definition, and the glossiness in this range can provide excellent display quality at a wide viewing angle. If the glossiness at 60 degrees is more than 50%, the antiglare property of the antiglare film is lowered, the external light source cannot be effectively scattered, the display device is affected by the light reflection of the external light source, and the display quality is lowered, and if the glossiness at 60 degrees is less than 30%, the antiglare property of the antiglare film is too high, and the display image of the display device is easily blurred.
The anti-dazzle film disclosed by the invention adopts the PET film as a base material, and has favorable adhesion between an anti-dazzle layer and the base material besides satisfactory anti-dazzle property and surface fineness.
In one embodiment of the present invention, the PET substrate of the antiglare film has a light transmittance of 80% or more, preferably 90% or more, and the PET substrate has a thickness of about 10 μm to 250 μm, preferably 20 μm to 100 μm.
In one embodiment of the present invention, the thickness of the cured antiglare hard coat layer of the antiglare film is preferably 3 μm to 9 μm, more preferably 4 μm to 7 μm.
In the antiglare film of the present invention, the acrylic binder resin is used in an amount of 75 to 90 parts by weight, preferably 80 to 90 parts by weight.
In the antiglare film disclosed in the present invention, the cured antiglare hard coat layer comprises organic microparticles and silica nanoparticles, wherein the organic microparticles are used to provide light diffusion of the cured antiglare hard coat layer, providing an appropriate internal haze to homogenize the light emitted from the inside of the display. The internal haze of the antiglare film of the present invention can be adjusted according to the refractive index, particle diameter and addition amount of the selected organic microparticles. The refractive index of the organic fine particles suitable for use in the present invention is 1.40 to 1.60, and the average particle diameter is 2 μm to 6. Mu.m, preferably 2 μm to 5. Mu.m. The organic fine particles are preferably used in an amount of 5 to 20 parts by weight, more preferably 7 to 15 parts by weight. If the amount of the organic fine particles is too low, a sufficient light scattering effect cannot be provided, so that the antiglare property of the antiglare film is insufficient, and the display is easily affected by light reflection of an external light source, thereby causing a problem of deterioration in display quality. If the amount of the organic fine particles is too large, the light scattering effect of the antiglare film becomes too high, and the display image of the display tends to be whitened and the contrast tends to be lowered.
Suitable organic microparticles are polymethyl methacrylate resin microparticles, polystyrene resin microparticles, styrene-methyl methacrylate copolymer microparticles, polyethylene resin microparticles, epoxy resin microparticles, silicone resin microparticles, polyvinylidene fluoride resin or polyvinyl fluoride resin microparticles, which are surface-treated with hydrophobic or hydrophilic treatment. The organic particles may be resin fine particles containing a styrene group, or organic particles whose surfaces are hydrophilized with, for example, 2-hydroxyethyl (meth) acrylate (2-HE (M) A) or (meth) acrylonitrile (meth) acrylate).
In an antiglare film of the present invention, the cured antiglare hard coat layer contains silica nanoparticles that promote the anti-settling of organic particles and increase the surface definition of the cured antiglare hard coat layer. The silica nanoparticles suitable for use in the present invention have an average primary particle diameter (d 50) of about 5nm to 30nm and an average secondary particle diameter (d 50) of about 50nm to 120nm, and the silica nanoparticles are preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.05 to 7 parts by weight. If the amount of silica nanoparticles used is too low, sedimentation of the organic fine particles cannot be effectively prevented, and surface irregularities on the antiglare film cannot be appropriately provided to increase the fineness. If the amount of silica nanoparticles used is too high, the dispersibility of the silica nanoparticles tends to decrease, which tends to increase the haze of the antiglare film, and cause problems such as whitening and contrast reduction in the display.
The antiglare film of the present invention, wherein the leveling agent is used in an amount of 0.1 to 1 part by weight.
In an antiglare film of the present invention, the leveling agent is contained in the cured antiglare hard coat layer to give a good coating surface, and has surface lubricity, antifouling property, scratch resistance, etc. The leveling agent that can be used for the antiglare film of the present invention may be a fluorine-based or silicone-based leveling agent, such as silicone oil, fluorine-based surfactant, or the like. The leveling agent suitable for use in the cured antiglare hard coat layer of the antiglare film of the present invention may be, for example, polyether-modified polysiloxane, and is used in an amount of 0.05 to 2 parts by weight, preferably 0.2 to 1 part by weight. If the amount of the leveling agent used is too low, the leveling agent may be insufficient in the surface of the antiglare film, and drying defects may be easily generated during coating. If the amount of the leveling agent used is too high, excessive microcells are generated in the antiglare film by the leveling agent, and physical properties of the antiglare film are lowered.
In the antiglare film of the present invention, the acrylic binder resin of the cured antiglare hard coat layer comprises a (meth) acrylate composition and an initiator, wherein the (meth) acrylate composition comprises 35 to 50 parts by weight of a urethane (meth) acrylate oligomer having a functionality of 6 to 15, 12 to 20 parts by weight of a (meth) acrylate monomer having a functionality of 3 to 6, and 1.5 to 12 parts by weight of a (meth) acrylate monomer having a functionality of less than 3, wherein the urethane (meth) acrylate oligomer has a molecular weight of 1,000 to 4,500. The acrylic binder resin used in the present invention can provide a cured antiglare hard coat layer having good adhesion to a PET substrate, and having good weather resistance, sufficient surface hardness, and scratch resistance.
In one embodiment of the present invention, the polyurethane (meth) acrylate oligomer having a functionality of 6 to 15 has a molecular weight of 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 invention, the (meth) acrylate monomer having a functionality of 3 to 6 has a molecular weight of less than 1,000, preferably a molecular weight of less than 800. Suitable (meth) acrylate monomers for use in the present invention having a functionality of 3 to 6 may be, for example, one of pentaerythritol tetra (meth) acrylate (pentaerythritol tetra (meth) acrylate), dipentaerythritol penta (meth) acrylate (dipentaerythritol penta (meth) acrylate, DPP (M) a), dipentaerythritol hexa (meth) acrylate (dipentaerythritol hexa (meth) acrylate, DPH (M) a), trimethylolpropane tri (meth) acrylate (trimethylolpropane tri (meth) acrylate, TMPT (M) a), ditrimethylolpropane tetra (ditrimethylolpropane tetra (meth) acrylate, DTMPT (M) a), pentaerythritol tri (meth) acrylate (pentaerythritol tri (meth) acrylate, PET (M) a), or a combination thereof, but are not limited thereto. The (meth) acrylate monomer having a functionality of 3 to 6 is preferably one of pentaerythritol triacrylate (pentaerythritol triacrylate, PETA), dipentaerythritol hexaacrylate (dipentaerythritol hexaacrylate, DPHA), dipentaerythritol pentaacrylate (dipentaerythritol pentaacrylate, DPPA) or a combination thereof.
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. (meth) acrylate monomers having a functionality of less than 3 suitable for use in the present invention may be, for example, 2-ethylhexyl (meth) acrylate (2-ethylhexyl (meth) acrylate,2-EH (M) A), 2-hydroxyethyl (meth) acrylate (2-hydroxyethyl (meth) acrylate,2-HE (M) A), 3-hydroxypropyl (meth) acrylate (3-hydroxypropyl (meth) acrylate,3-HP (M) A), 4-hydroxybutyl (meth) acrylate (4-hydroxybutyl (meth) acrylate,4-HB (M) A), 2-butoxyethyl (meth) acrylate (2-butoxyethyl (meth) acrylate), 1,6-hexanediol di (meth) acrylate, HDD (M) A), ditrimethylolpropane methylal (meth) acrylate (cyclic trimethylolpropane formal (meth) acrylate, CTF (M) A), 2-phenoxyethyl (meth) acrylate (2-phenoxyethyl (meth) acrylate, E (M), tetrahydrofuran (meth) acrylate (35A), tetrahydrofuran (meth) acrylate (35 methacrylate) and methyl methacrylate (35A), l (M) a), diethylene glycol di (meth) acrylate (diethylene glycol di (meth) acrylate, DEGD (M) a), dipropylene glycol di (meth) acrylate (dipropylene glycol di (meth) acrylate, DPGD (M) a), tripropylene glycol di (meth) acrylate (tripropylene glycol di (meth) acrylate, TPGD (M) a), isobornyl (meth) acrylate (isobornyl (meth) acrylate), or combinations thereof. The (meth) acrylate monomer having a functionality of less than 3 is preferably one of 1,6-hexanediol diacrylate (HDDA), cyclotrimethylol propane methylacrylate (CTFA), 2-phenoxyethyl acrylate (PHEA) or a combination thereof.
Suitable initiators for the acrylic binder resin of the present invention may be any of those known to the art and may be used, and are not particularly limited, and examples thereof include acetophenone type initiators, diphenyl ketone type initiators, propiophenone type initiators, dibenzoyl type initiators, bifunctional α -hydroxy ketone type initiators, and acylphosphine oxide type initiators. The aforementioned initiators may be used alone or in combination.
In other embodiments of the present invention, additives such as antistatic agents, colorants, flame retardants, antibacterial agents, ultraviolet absorbers, antioxidants, surface modifiers, and the like may be added to the acrylic adhesive resin as required.
Other optical functional layers, such as a low refractive layer, may also be optionally coated on the antiglare film of the present invention to provide antireflection.
The method for producing an antiglare film of the present invention comprises uniformly mixing a urethane (meth) acrylate oligomer having a functionality of 6 to 15, a (meth) acrylate monomer having a functionality of not less than 3, a (meth) acrylate monomer having a functionality of less than 3, and an initiator with a suitable solvent to form a solution of an acrylic binder resin; adding organic microparticles, silicon dioxide nanoparticles, a leveling agent, an additive, an organic solvent and the like into the solution of the acrylic adhesive resin, and uniformly mixing to form an anti-dazzle solution; the anti-dazzle solution is coated on a transparent substrate, and after the anti-dazzle solution coated on the transparent substrate is dried, a cured anti-dazzle hard coating is formed on the transparent substrate after radiation curing or electron beam curing so as 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 as the solution of the binder resin, and suitable solvents may be, for example, acetone, butanone, cyclohexanone, methyl isobutyl ketone, hexane, cyclohexane, methylene chloride, dichloroethane, toluene, xylene, propylene glycol methyl ether, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isopropyl alcohol, n-butanol, isobutyl alcohol, cyclohexanol, diacetone alcohol, propylene glycol methyl ether acetate, tetrahydrofuran, or the like, but are not limited thereto.
The method for applying the antiglare solution may be, for example, a roll coating method, a doctor blade coating method, a dip coating method, a roll coating method, a spin coating method, a slit coating method, or any other coating method 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 cured antiglare hard coat layer.
According to the antiglare film disclosed in the above embodiment of the present invention, in another embodiment, the present invention further provides a polarizing plate including a polarizing element, wherein the polarizing plate has the antiglare film disclosed in the above embodiment of the present invention on a surface of the polarizing element.
The following examples are provided to further illustrate the invention, but the invention is not limited thereto.
Examples
Preparation example 1: preparation of acrylic adhesive resin I
42 g of urethane acrylate (functionality 6, molecular weight about 1200, viscosity about 30,000cps (25 ℃ C.), purchased from IGM, taiwan, china), 4.5 g of pentaerythritol triacrylate (PETA), 12 g of dipentaerythritol hexaacrylate (DPHA), 3 g of cyclotrimethylolpropane formal acrylate (CTFA), 4 g of polymerization initiator (Chemcure-481, purchased from Hengqiao industry, taiwan, china), 24.5 g of Ethyl Acetate (EAC) and 10 g of n-butyl acetate (nBAC) were mixed and stirred for 1 hour to form a solution of the acrylic binder resin I having a solid content of 65.5%.
Preparation example 2: preparation of acrylic adhesive resin II
40.5 grams of a urethane acrylate oligomer (functionality 9, molecular weight about 2,000, viscosity about 86,000cps (25 ℃), purchased from Allnex, usa), 4.5 grams of pentaerythritol triacrylate (PETA), 10.5 grams of dipentaerythritol hexaacrylate (DPHA), 4.5 grams of hexanediol diacrylate (HDDA), 1.5 grams of 2-phenoxyethyl acrylate (PHEA), 3.5 grams of a polymerization initiator (Chemcure-481, purchased from the constant bridge industry, taiwan), 0.5 grams of a polymerization initiator (TR-PPI-One, purchased from the strong new material, hong gang), 24.5 grams of Ethyl Acetate (EAC), and 10 weight percent of n-butyl acetate (nBAC) were mixed and stirred for 1 hour to form a solution of an acrylic binder resin II having a solids content of 65.5%.
Example 1
199 g of binder resin I, 7.4 g of hydrophobically modified silica nanoparticle dispersion sol (NanoBYK-3650, average primary particle diameter of 20nm, solid content of 31%, solvent of propylene glycol methyl ether acetate/propylene glycol monomethyl ether solution, from BYK, germany), 5.3 g of polyether modified polydimethylsiloxane leveling agent (BYK-333, solid content of 10%, solvent of ethyl acetate, from BYK, germany), 19.6 g of polystyrene particles (SSX-303 ABE, average particle diameter of 3.0 μm, refractive index of 1.59, from water-logging finished product, japan), 48.3 g of propylene glycol methyl ether acetate (PMA) and 100 g of n-propyl acetate (nPAC) were mixed and stirred for 1 hour to form an antiglare solution.
The antiglare solution was coated on one of the surfaces of a polyethylene terephthalate (PET) substrate having a thickness of 80 μm, and after drying, photocuring was performed under a nitrogen atmosphere with a UV lamp having a radiation dose of 80mJ/cm2 to form a cured antiglare hard coat layer having a thickness of 4.2 μm on one of the surfaces of the PET substrate, and an antiglare 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 scratch resistance measurement, hardness measurement, and adhesion to a substrate were performed, and the test results are shown in table 2.
Example 2
199 g of binder resin II, 0.5 g of hydrophobically modified silica nanoparticle dispersion sol (NanoBYK-3650, average primary particle diameter of 20nm, solid content of 31% in propylene glycol methyl ether acetate/propylene glycol monomethyl ether solution, from BYK, germany), 5.2 g of polyether modified polydimethylsiloxane leveling agent (BYK-333, solid content of 10% in ethyl acetate, from BYK, germany), 16.3 g of polystyrene particles (XX-35 IK, average particle diameter of 3.8 μm, refractive index of 1.59, from hydrorefining product, japan), 37.4 g of Ethyl Acetate (EAC) and 112 parts by weight of methyl isobutyl ketone (MIBK) were mixed and stirred for 1 hour to form an antiglare solution.
The antiglare solution was coated on one surface of a polyethylene terephthalate (PET) substrate having a thickness of 80 μm, dried, and then light-cured under a nitrogen atmosphere with a UV lamp having a radiation dose of 80mJ/cm2 to form a cured antiglare hard coat layer having a thickness of 5.0 μm on one surface of the PET substrate, and an antiglare film was obtained.
The antiglare film obtained was subjected to the test as in example 1, and the results are shown in tables 1 and 2.
Example 3
212 grams of binder resin II, 21.6 grams of silica nanoparticle dispersion sol (MEK-9130X, average primary particle diameter of 12nm, average secondary particle diameter of 90 to 100nm, solids content of 30%, solvent of butanone, available from the national silica industry, taiwan, china), 5.4 grams of polyether modified polydimethylsiloxane leveling agent (BYK-307, solids content of 10%, solvent of ethyl acetate, available from BYK, germany), 16.2 grams of polystyrene particles (XX-29 IK, average particle diameter of 3.5 μm, refractive index of 1.59, available from watered end product, japan), 39.45 grams of n-butyl acetate (nBAC), 39.45 grams of n-propyl acetate (nPAC), and 72.5 grams of methyl isobutyl ketone (MIBK) were mixed and stirred for 1 hour to form an antiglare solution.
The antiglare solution was coated on one of the surfaces of a polyethylene terephthalate (PET) substrate having a thickness of 80 μm, dried, and then photocured under a nitrogen atmosphere with a UV lamp having a radiation dose of 80mJ/cm2 to form a cured antiglare hard coat layer having a thickness of 4.4 μm on one of the surfaces of the substrate, and an antiglare film was obtained.
The antiglare film obtained 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 binder resin II, 3.6 g of a hydrophobically modified silica nanoparticle dispersion sol (NanoBYK-3650, average primary particle diameter of 20nm, solid content of 31% in propylene glycol methyl ether acetate/propylene glycol monomethyl ether solution, available from BYK, germany), 5.3 g of a polyether modified polydimethylsiloxane leveling agent (BYK-333, solid content of 10% in ethyl acetate, available from BYK, germany), 16.3 g of polystyrene particles (SSX-303 ABE), 36.8 g of Ethyl Acetate (EAC) and 112 g of methyl isobutyl ketone (MIBK) were mixed and stirred for 1 hour to uniformly disperse them, thereby forming an antiglare solution.
The antiglare solution was coated on one of surfaces of a polyethylene terephthalate (PET) substrate having a thickness of 80 μm, dried, and then photocured under a nitrogen atmosphere with a UV lamp having a radiation dose of 80mJ/cm2, to form a cured antiglare hard coat layer having a thickness of 4.3 μm on one of the surfaces of the PET substrate, and an antiglare film was obtained.
The antiglare film obtained was subjected to the test as in example 1, and the results are shown in tables 1 and 2.
Example 5
212 grams of binder resin II, 32.4 grams of silica nanoparticle dispersion sol (MEK-9130X, average primary particle diameter of 12nm, average secondary particle diameter of 90 to 100nm, solid content of 30%, solvent of butanone, available from national silica industry, taiwan), 5.4 grams of polyether modified polydimethylsiloxane leveling agent (BYK-307, solid content of 10%, solvent of ethyl acetate, available from BYK, germany), 13 grams of polystyrene particles (XX-31 IK, average particle diameter of 3.8 μm, refractive index of 1.59, available from hydrosulfite finished product, japan), 39.45 grams of n-butyl acetate (nBAC), 39.45 grams of n-propyl acetate (nPAC) and 72.5 grams of methyl isobutyl ketone (MIBK) were mixed and stirred for 1 hour to uniformly disperse to form an antiglare solution.
The antiglare solution was coated on one of surfaces of a polyethylene terephthalate (PET) substrate having a thickness of 80 μm, dried, and then photocured under a nitrogen atmosphere with a UV lamp having a radiation dose of 80mJ/cm2, to form a cured antiglare hard coat layer having a thickness of 4.6 μm on one of the surfaces of the PET substrate, and an antiglare film was obtained.
The antiglare film obtained was subjected to the test as in example 1, and the results are shown in tables 1 and 2.
Optical measuring method
The antiglare film obtained in the foregoing examples was optically measured according to the measurement method of Japanese Industrial Standard (JIS).
Light transmittance measurement: the measurement was performed by using an NDH-2000 haze meter (manufactured by Nippon Denshoku industries Co., ltd.) according to the measurement method of JIS K7361.
Measurement of haze: haze was evaluated according to the description of JIS K7136 using NDH-2000 (manufactured by Nippon electric color industry Co., ltd.).
Measurement of internal haze and surface haze: a triacetyl cellulose base material (T40 UZ, thickness 40 μm, fuji film Co.) was stuck to the surface of the antiglare film by using a transparent optical adhesive, whereby the uneven surface of the antiglare film was flattened, and in this state, the haze was evaluated by using an NDH-2000 haze meter (manufactured by Japanese electric color industry Co., ltd.) in accordance with the description of JIS K7136 to obtain a total haze value and 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 glued on a black acrylic plate, and the Gloss values at viewing angles of 20, 60 and 85 degrees were selected using a BYK Micro-Gloss meter, measured according to the description of JIS Z8741.
Definition measurement Using a SUGA ICM-IT image definition instrument, the values measured for the slits of 0.125mm, 0.25mm, 0.50mm, 1.00mm and 2.00mm were summed up, measured according to the description of JIS K7374.
Measurement of antiglare properties: the antiglare film was adhered to a black acrylic plate, and the surface of the antiglare film was exposed to 2 fluorescent lights, and the antiglare property of the antiglare film was evaluated on the following 5 scale by visually comparing the degree of blooming of the fluorescent lamp.
Lv.1: the separated 2 fluorescent tubes can be clearly seen, and the outline of the fluorescent tube can be clearly distinguished to be linear;
lv.2: the separated 2 fluorescent tubes can be clearly seen, but the outline is slightly blurred;
lv.3: 2 separated fluorescent tubes can be seen, the outline can be seen in a fuzzy manner, but the shape of the fluorescent tubes can be distinguished;
lv.4: 2 fluorescent tubes can be seen, but the shape cannot be distinguished;
lv.5: the separated 2 fluorescent tubes cannot be seen, and the shape of the fluorescent tubes cannot be distinguished.
Table 1 optical measurement results of antiglare films of examples 1 to 5:
method for measuring scratch resistance, hardness and adhesion between substrate
Scratch resistance measurement: on the surface of the antiglare film, a #0000 steel wool was used to rub back and forth 10 times under a rubbing load of 250gf/cm2, after which it was observed with eyes whether the surface of the antiglare layer remained scratched
Pencil hardness measurement: the surface of the antiglare layer was observed with eyes for scratch under five tests, measured with a mechanical pencil durometer in accordance with JIS K-5400 with a pencil with standard hardness of mitsubishi pencil of 2H. If no scratch is generated, the measurement result is marked with "0/5".
Measurement of adhesion: the adhesion was measured according to JIS K5600-5-6 using a hundred blade. The measurement method is that 10x 10 grids of 1mm x 1mm are firstly drawn on the surface of the anti-dazzle film by using a hundred-lattice knife, then the anti-dazzle film is stuck by using a standard test adhesive tape and then torn off, and the number of unpeeled grids is checked.
TABLE 2 scratch resistance, pencil hardness, adhesion measurement results of antiglare films of examples 1 to 5
As can be seen from tables 1 and 2, the antiglare films prepared in examples 1 to 5 of the present invention not only have good antiglare properties and the glossiness at 60 degrees can provide excellent display quality at a wide viewing angle, but also have good adhesion to polyethylene terephthalate (PET) substrate, and the antiglare film surface provides sufficient hardness and excellent scratch resistance.
In summary, the antiglare film and the polarizing plate having the antiglare film of the present invention can effectively reduce the flicker on the display surface and the appropriate internal haze damages the internal scattering of the antiglare layer to provide satisfactory antiglare properties and achieve high definition, high resolution, no flicker and good visibility. The antiglare film and the polarizing plate having the antiglare film disclosed by the invention also provide excellent display quality at a wide viewing angle, and antiglare property at a wide viewing angle is used to increase the visibility of the whole display. The antiglare film and the polarizing plate with the antiglare film have good adhesion between the antiglare layer and the base material.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (16)

1. An antiglare film, comprising:
a polyethylene terephthalate (PET) substrate; and
A cured antiglare hard coat layer formed on the surface of the substrate, wherein the cured antiglare hard coat layer comprises:
75 to 90 parts by weight of an acrylic binder resin;
0.05 to 10 parts by weight of silica nanoparticles;
5 to 20 parts by weight of organic fine particles; and
0.05 to 2 parts by weight of a leveling agent which is a polyether modified polysiloxane leveling agent;
the antiglare film has a total haze of 35% to 50% and a surface haze of 10% to 15%, a glossiness of 30% to 50% at a 60-degree viewing angle, the silica nanoparticle has a primary particle diameter (d 50) of 5nm to 30nm and a secondary particle diameter (d 50) of 50nm to 120nm, and the leveling agent is used in an amount of 0.1 part by weight to 1 part by weight.
2. The antiglare film of claim 1, wherein the antiglare film has a total haze of from 40% to 50%, an internal haze of from 27% to 40%, and a surface haze of from 10% to 13%.
3. The antiglare film of claim 1, wherein the organic microparticles have an average particle size of 2 μm to 6 μm.
4. The antiglare film of claim 2, wherein the organic microparticles have an average particle size of 2 μm to 5 μm.
5. The antiglare film according to claim 1, wherein the acrylic binder resin is used in an amount of 80 to 90 parts by weight.
6. The antiglare film according to claim 1, wherein the organic fine particles are used in an amount of 7 parts by weight to 15 parts by weight.
7. The antiglare film of claim 1, wherein the silica nanoparticles are used in an amount of 0.05 to 7 parts by weight.
8. The antiglare film according to claim 1, wherein the 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 surfaces of which are subjected to a hydrophobic treatment or a hydrophilic treatment.
9. The antiglare film of claim 1, wherein the organic microparticle has a refractive index of from 1.40 to 1.60.
10. The antiglare film of claim 1, wherein the cured antiglare hard coat layer has a thickness of 3 μm to 9 μm.
11. The antiglare film according to claim 1, wherein the acrylic binder resin comprises a (meth) acrylate composition and an initiator, the (meth) acrylate composition comprising:
35 to 50 parts by weight of a polyurethane (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 polyurethane (meth) acrylate oligomer has a molecular weight of 1,000 to 4,500.
12. The antiglare film of claim 11, wherein the polyurethane (meth) acrylate oligomer having a functionality of 6 to 15 is an aliphatic polyurethane (meth) acrylate oligomer.
13. The antiglare film of claim 11, 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 (pentaerythritol tetra (meth) acrylate), dipentaerythritol penta (meth) acrylate (dipentaerythritol penta (meth) acrylate, DPP (M) a), dipentaerythritol hexa (meth) acrylate (dipentaerythritol hexa (meth) acrylate, DPH (M) a), trimethylolpropane tri (meth) acrylate (trimethylolpropane tri (meth) acrylate, TMPT (M) a), ditrimethylolpropane tetra (meth) acrylate (ditrimethylolpropane tetra (meth) acrylate, DTMPT (M) a), and pentaerythritol tri (meth) acrylate (pentaerythritol tri (meth) acrylate, PET (M) a), or a combination thereof.
14. The antiglare film of claim 11, 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-hydroxyethyl (meth) acrylate,2-HE (M) A), 3-hydroxypropyl (meth) acrylate (3-hydroxypropyl (meth) acrylate,3-HP (M) A), 4-hydroxybutyl (meth) acrylate (4-hydroxybutyl (meth) acrylate,4-HB (M) A), 2-butoxyethyl (meth) acrylate (2-butoxyethyl (meth) acrylate), 1,6-hexanediol di (meth) acrylate, HDD (M) A), cyclotrimethylol propane methylal (meth) acrylate (cyclic trimethylolpropane formal (meth) acrylate, CTF (M) A), 2-phenoxyethyl (meth) acrylate (2-35E) acrylate (35M), and tetrahydrofuran (meth) acrylate (35A), at least one of the group consisting of L (M) a), diethylene glycol di (meth) acrylate (diethylene glycol di (meth) acrylate, DEGD (M) a), dipropylene glycol di (meth) acrylate (dipropylene glycol di (meth) acrylate, DPGD (M) a), tripropylene glycol di (meth) acrylate (tripropylene glycol di (meth) acrylate, TPGD (M) a) and isobornyl (meth) acrylate (isobornyl (meth) acrylate), or a combination thereof.
15. The antiglare film of claim 11, wherein the initiator is at least one selected from the group consisting of acetophenone initiators, benzophenone initiators, propiophenone initiators, dibenzoyl initiators, difunctional α -hydroxy ketone initiators, and acylphosphine oxide initiators, or a combination thereof.
16. A polarizing plate comprising a polarizing element, wherein the polarizing plate has the antiglare film according to any one of claims 1 to 15 on at least one surface of the polarizing element.
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