CN113917577B - High-water-resistance and bending-resistance optical protective film, polarizer and liquid crystal display device - Google Patents

High-water-resistance and bending-resistance optical protective film, polarizer and liquid crystal display device Download PDF

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CN113917577B
CN113917577B CN202111514492.2A CN202111514492A CN113917577B CN 113917577 B CN113917577 B CN 113917577B CN 202111514492 A CN202111514492 A CN 202111514492A CN 113917577 B CN113917577 B CN 113917577B
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film
protective film
acrylate
resistance
optical protective
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CN113917577A (en
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马春霞
严兵华
施明志
张良宝
黄源
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Hengmei Optoelectronics Co ltd
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Hengmei Optoelectronics Co ltd
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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
    • 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
    • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)

Abstract

The invention relates to an optical protective film with high water resistance and bending resistance, a polarizer and liquid crystal display equipment thereof. The high water-resistant bending-resistant optical protective film comprises an acrylate film and a functional coating formed on at least one surface of the acrylate film; the acrylate film comprises polymeric core-shell particles; the coating composition of the functional coating comprises a water dispersible resin and a trifunctional or higher epoxy compound; the coating composition of the functional coating provided by the invention has the advantages that the trifunctional or more than trifunctional epoxy compound in the coating composition forms a cross-linked structure with high cross-linking density after polymerization, so that the adhesion of the optical protective film is improved, meanwhile, moisture is difficult to permeate into the functional coating, and the water resistance of the optical protective film is enhanced; and polymer core-shell particles are added in the optical protective film to serve as stress concentration points, impact energy is absorbed to reduce creep, and the optical protective film is endowed with excellent impact resistance, so that the optical protective film has excellent toughness and bending resistance, and meets the requirement of flexible display.

Description

High-water-resistance and bending-resistance optical protective film, polarizer and liquid crystal display device
Technical Field
The present invention relates to an optical protective film. More particularly, the present invention relates to an optical protective film having high water resistance and bending resistance, a method of preparing the same, and a polarizer and a liquid crystal display device including the same.
Background
The polarizer is one of the indispensable structural members of the lcd, and functions to convert natural light with non-polarized polarity into polarized light with a certain polarization direction, so that the lcd panel has the possibility of displaying images. The polarizer has a basic structure of an optical composite laminated body formed by laminating a plurality of film materials, wherein a polarizer PVA (polyvinyl alcohol) film mainly playing a role of polarization is produced by washing, dyeing, stretching and other links, and a protective film is laminated on the upper surface and the lower surface or two surfaces of the polarizer by using an adhesive. Triacetyl cellulose (TAC) -based films are widely used as polarizer protective films, however, since TAC films have weak surface hardness and are easily subjected to moisture, are easily shrunk and deformed under high temperature and high humidity environments, and suffer warpage, peeling, light leakage, and the like, thereby decreasing durability thereof, development of protective films prepared from various materials capable of replacing TAC films, such as polyethylene terephthalate (PET), cycloolefin polymer films (COP), polycarbonate films (PC), acrylate films, and the like, has been recently studied. In particular, an acrylate film has been receiving particular attention because it has excellent optical properties, durability, and low price. However, the acrylate film has poor mechanical properties compared to other materials, resulting in high brittleness and easy breakage due to impact, thereby limiting its wide application in polarizers. In order to meet the requirements of large-size flexible displays in the future, the polarizer needs to have certain flexibility and pliability, so that it is important to further improve the toughness and bending resistance of the acrylate film.
However, when an acrylate film is used as a protective film for a polarizer and is bonded to a PVA polarizer film using only a general adhesive, peeling and peeling are easily generated due to insufficient adhesive strength in general, a functional coating is generally applied to the acrylate film to improve the adhesive strength, but when the polymer is rearranged in a stretching process to obtain good optical properties, the functional coating is also stretched, and there is a problem that the adhesion of the adhesive to the acrylate stretch protective film is reduced. In addition, a water-dispersible resin is generally used to form the functional coating layer for environmental reasons, and when the polarizer is exposed to a high-temperature and high-humidity environment for a long time, the water-dispersible resin of the functional coating layer is easily hydrolyzed, resulting in a problem of a decrease in adhesive strength.
Therefore, it is required to develop a polarizer protective film and a polarizer having excellent adhesion and bending resistance, and simultaneously having excellent durability, not only satisfying the severe use environment of high temperature and high humidity, but also realizing the bending and foldability of a flexible display.
Disclosure of Invention
The main object of the present invention is to provide a highly water-resistant and bending-resistant optical protective film having excellent adhesion even under a high-temperature and high-humidity environment and excellent bending resistance, which satisfies the need for flexible display, and a method for producing the same.
Another object of the present invention is to provide a polarizer and a liquid crystal display device based on the above optical protective film.
In order to achieve the above object, the present invention provides an optical protective film having high water resistance and bending resistance, characterized by comprising an acrylate film and a functional coating layer formed on at least one surface of the acrylate film; the acrylate film comprises polymeric core-shell particles; the coating composition of the functional coating comprises a water-dispersible resin and a trifunctional or higher epoxy compound.
As a further improvement of the invention, the acrylate film comprises the following components in parts by weight:
68.5-98.8 parts of acrylate copolymer resin
1-30 parts of polymer core-shell particles
0.1 to 0.5 part of ultraviolet absorber
0.1 to 1 portion of other components
The polymeric core shell microparticles are selected from hard shell polymers having a high glass transition temperature, clad with soft core polymers having a low glass transition temperature;
the other components are at least one of lubricant, flexibilizer, antioxidant, flatting agent, antifouling agent, antistatic agent and preservative.
As a further improvement of the invention, the diameter of the polymer core-shell particles is 10-500 nm.
As a further improvement of the invention, the diameter of the polymer core-shell particles is 50-200 nm.
As a further improvement of the invention, the coating composition of the functional coating comprises the following components in parts by weight:
1-30 parts of water-dispersible resin
0.01-10 parts of epoxy compound with three or more functional groups
0.1-10 parts of nano dispersed particles
0.01-5 parts of cross-linking agent
45-98.88 parts of water.
As a further improvement of the present invention, the trifunctional or higher epoxy compound is selected from one or more of 4, 5-epoxytetrahydrophthalic acid diglycidyl ester, 1, 3-bis (N, N-diglycidyl ester) diiminomethylcyclohexane, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, 4- (2, 3-epoxypropoxy) -N, N-bis (2, 3-epoxypropyl) aniline, or tetraglycidyl-m-xylylenediamine.
As a further improvement of the present invention, the trifunctional or higher epoxy compound includes an aliphatic hydrocarbon ring, and at least one or more epoxy functional groups are formed between two adjacent carbon atoms constituting the aliphatic hydrocarbon ring.
As a further improvement of the present invention, the water-dispersible resin includes a water-dispersible polyurethane-based resin, a water-dispersible acrylic resin, a water-dispersible polyester-based resin, or a combination thereof.
As a further development of the invention, the crosslinking agent is selected from one or more of dihydrazide systems, imidazole systems, melamine systems, amine systems, anhydride systems, isocyanate systems, thiol systems, carboxylic acid systems, polyol systems, polythiol systems or phenol systems.
As a further improvement of the invention, the cross-linking agent is selected from one or more of adipic acid dihydrazide, oxazoline, carbodiimide and isophthalic acid dihydrazide.
As a further improvement of the invention, the hard shell polymer in the polymer core-shell particles is selected from copolymers with a glass transition temperature higher than 80 ℃, and the monomer of the copolymer with the glass transition temperature higher than 80 ℃ is selected from one or more of styrene, acrylamide, methacrylamide, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate.
As a further improvement of the present invention, the soft core polymer in the polymer core-shell particles is selected from copolymers with a glass transition temperature below 40 ℃, and the copolymers with a glass transition temperature below 40 ℃ are selected from one or more of silicone rubber, polystyrene butadiene copolymer, 1, 4-polyisoprene copolymer, 1, 4-polybutadiene copolymer, chloroprene copolymer, ethylene-propylene-non-conjugated diene copolymer, isobutylene copolymer, polyamide elastomer, polyolefin elastomer, polyurethane elastomer, styrene thermoplastic elastomer, polyethylene octene elastomer, and ethylene-vinyl acetate elastomer; or the monomer of the copolymer with the glass transition temperature lower than 40 ℃ is selected from one or more of methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethyl acrylate, isooctyl acrylate, hydroxypropyl acrylate and hydroxyethyl acrylate.
As a further development of the invention, the uv absorber is selected from the group consisting of 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3, 3-tetramethylbutyl) phenol, 2' - (2' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' bis (a, a-dimethylbenzyl) phenyl) benzotriazole, 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxy-phenol, 2- (2' -hydroxy-3 ',5 '-di-tert-phenyl) -5-chlorobenzotriazole, 2,4, 6-tris (2' -n-butoxyphenyl) -1,3, 5-triazine.
In order to achieve the above object, the present invention further provides a method for preparing an optical protective film with high water resistance and bending resistance, comprising the following steps:
(1) preparing a coating composition of the functional coating: weighing and uniformly mixing all components of the coating composition of the functional coating to obtain the coating composition of the functional coating;
(2) preparing an acrylate film: uniformly mixing all components of the acrylate film through a mixer, extruding and granulating by using an extruder to obtain acrylate particles, and preparing the acrylate film through a film forming method;
(3) applying the coating composition of step (1) to at least one surface of the acrylate film of step (2) to form the functional coating; and then sequentially stretching, drying and thermally curing the acrylate film coated with the functional coating at high temperature to obtain the high-water-resistance and bending-resistance optical protective film.
As a further improvement of the present invention, the step (2) of preparing the acrylate film by the film forming method further comprises a stretching process to obtain a stretched film, and the stretching ratio is 1.1 to 5 times the length based on the stretching direction. The acrylic film stretched film obtained in the step (2) is one of a uniaxially stretched film and a biaxially stretched film.
As a further improvement of the invention, the stretching temperature of the acrylate film coated with the functional coating in the step (3) is 80-200 ℃.
As a further improvement of the present invention, the stretch ratio of the acrylate film coated with the functional coating in the step (3) is 1.05 to 10 times the length based on the stretching direction.
In order to achieve the above object, the present invention further provides a polarizer with high water resistance and bending resistance, which comprises a polarizer film, an adhesive, and the optical protection film with high water resistance and bending resistance or the optical protection film with high water resistance and bending resistance prepared by the above preparation method, wherein the optical protection film is adhered to at least one surface of the polarizer film through the adhesive.
As a further improvement of the invention, the polarizer further comprises a universal protective film and a release film, wherein the universal protective film is selected from one or more of a cellulose triacetate film, a polyethylene terephthalate film, a polycarbonate film, a polymethyl methacrylate film, a cycloolefin polymer film and a cycloolefine polymer-like film, one surface of the universal protective film is attached to the polarizer film through an adhesive, and the other surface of the universal protective film is attached to the release film through a pressure-sensitive adhesive.
As a further improvement of the present invention, the upper surface of the high water-resistant and bending-resistant optical protective film is provided with a surface treatment layer, and the surface treatment layer is selected from one or a combination of multiple layers of an anti-glare layer, a low reflection layer, a high hardening layer, an anti-reflection layer, an antistatic layer and an anti-fouling layer.
In order to achieve the above object, the present invention further provides a liquid crystal display device including the polarizer having high water resistance and bending resistance as described above.
The invention has the beneficial effects that:
(1) the invention provides a high-water-resistance bending-resistance optical protective film, wherein a trifunctional or more epoxy compound in a coating composition of a functional coating forms a cross-linked structure through a cross-linking reaction with a water-dispersible resin, so that the interface bonding strength between the functional coating and an adjacent film layer is enhanced, and the adhesion of the optical protective film is effectively improved; in addition, three or more epoxy groups form a high crosslinking density after polymerization, making it difficult for moisture to penetrate into the functional coating layer, effectively improving the water resistance of the optical protective film, so that the optical protective film has excellent adhesion even in a high-temperature and high-humidity environment.
(2) The polymer core-shell particles are added in the high-water-resistant and bending-resistant optical protective film, are of a structure that a soft core is coated by a hard shell, can be used as a stress concentration point and absorb impact energy to reduce creep, so that the high-water-resistant and bending-resistant optical protective film is endowed with excellent impact resistance, meanwhile, the brittleness of a traditional acrylic film can be improved, the high-water-resistant and bending-resistant optical protective film has excellent toughness and bending resistance, the bending resistance times can reach more than 1000 times, and the requirement of flexible display can be met.
(3) The coating composition of the functional coating of the optical protective film with high water resistance and bending resistance also comprises a cross-linking agent, so that the cross-linking strength of the epoxy compound with more than three functional groups after polymerization is further enhanced, and the water resistance of the optical protective film is further improved.
(4) The ultraviolet absorbent is added into the high-water-resistance and bending-resistance optical protective film, so that the transmittance of the optical protective film at 380nm is less than 10%, and the transmittance of the polarizer at 380nm is less than 3%, and the requirement of the protective film for the polarizer on long-term use under the action of ultraviolet rays is met.
(5) The functional coating of the high-water-resistance and bending-resistance optical protective film is integrated with the acrylate film and stretched, so that the functional coating is thinner and is more beneficial to improving the adhesiveness of the optical film protective film.
Drawings
FIG. 1 is a schematic structural view of a high water-resistant and bending-resistant optical protective film according to the present invention;
FIG. 2 is a schematic representation of the polymeric core-shell particle structure of the present invention;
FIG. 3 is a schematic view of a polarizer with high water resistance and bending resistance according to an embodiment of the present invention;
FIG. 4 is a schematic view of a polarizer with high water resistance and bending resistance according to another embodiment of the present invention;
FIG. 5 is a schematic view of a polarizer with high water resistance and bending resistance according to another embodiment of the present invention;
FIG. 6 is a schematic diagram of an adhesion test for an optical protective film of the present invention;
FIG. 7 is a schematic diagram of the polarizer adhesion test of the present invention.
Description of reference numerals: 1. core-shell polymer microparticles; 11. a hard shell polymer; 12. a soft core polymer; 2. an acrylate film; 3. a functional coating; 4. an optical protective film; 5. a polarizing film; 6. a binder; 7. a general protective film; 8. a pressure sensitive adhesive; 9. a release film; 10. a polarizer; 11. and (5) a surface treatment layer.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings.
As shown in fig. 1, the present application provides a high water-resistant bending-resistant optical protective film 4 comprising an acrylate film 2 and a functional coating layer 3 formed on at least one surface of the acrylate film 2; the acrylate film 2 comprises polymeric core-shell particles 1; the coating composition of the functional coating layer 3 includes a water-dispersible resin and a trifunctional or higher epoxy compound. The optical protection film 4 with high water resistance and bending resistance has a total light transmittance of more than 90%, a transmittance of 380nm wavelength of less than 10% and a haze of less than 3%.
The acrylate film 2 comprises the following components in parts by weight:
68.5-98.8 parts of acrylate copolymer resin
11-30 parts of polymer core-shell particles
0.1 to 0.5 part of ultraviolet absorber
0.1-1 part of other components.
The acrylate copolymer resin comprises a copolymer of alkyl methacrylate units, a copolymer of alkyl (meth) acrylate units and styrene units, a copolymer resin of 3-6 membered heterocyclic units substituted by at least one carbonyl group and vinyl cyanide units substituted by at least one carbonyl group; or may be a methacrylate copolymer resin having a lactone structure. However, the present invention is not limited thereto.
The other components of the acrylate film 2 include at least one of a lubricant, a toughening agent, an antioxidant, a leveling agent, an antifouling agent, an antistatic agent, and a preservative. Additives generally used in the art to which the present invention pertains may be further included. The functional coating layer 3 of the present invention is not particularly limited, since various adjustments can be made within a range that does not deteriorate the physical properties of the coating composition.
The diameter of the polymer core-shell particle 1 is 10 to 500nm, and more preferably 50 to 200 nm.
As shown in fig. 2, the polymer core-shell particles 1 are selected from a high glass transition temperature hard shell polymer 11 encapsulating a low glass transition temperature soft core polymer 12.
The high glass transition temperature hard shell polymer 11 is selected from copolymers with a glass transition temperature higher than 80 ℃, and the monomers of the copolymers with the glass transition temperature higher than 80 ℃ are selected from one or more of styrene, acrylamide, methacrylamide, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate.
The low glass transition temperature soft core polymer 12 is selected from copolymers with a glass transition temperature below 40 ℃, and the copolymers with a glass transition temperature below 40 ℃ are selected from one or more of silicone rubber, polystyrene butadiene copolymers, 1, 4-polyisoprene copolymers, 1, 4-polybutadiene copolymers, chloroprene copolymers, ethylene-propylene-non-conjugated diene copolymers, isobutylene copolymers, polyamide elastomers, polyolefin elastomers and polyurethane elastomers, styrenic thermoplastic elastomers, polyethylene octene elastomers, ethylene-vinyl acetate elastomers; or the monomer of the copolymer with the glass transition temperature lower than 40 ℃ is selected from one or more of methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethyl acrylate, isooctyl acrylate, hydroxypropyl acrylate and hydroxyethyl acrylate.
The ultraviolet absorber is selected from the group consisting of 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3, 3-tetramethylbutyl) phenol, 2' - (2' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' bis (a, a-dimethylbenzyl) phenyl) benzotriazole, 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxy-phenol, 2- (2' -hydroxy-3 ',5' -di-tert-phenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole, 2-methyl-1-phenylethyl) phenol, 2' - (2' -hydroxy-3 ',5' -di-tert-methylbenzyl) phenyl, 2' -methyl-1-methyl-phenyl) benzotriazole, 2' -methyl-5-chlorobenzotriazole, 2' -methyl-butyl-phenyl-5-benzotriazol, 2,4, 6-tri (2' -n-butoxyphenyl) -1,3, 5-triazine.
The acrylate film 2 may be an unstretched film or a stretched film, and the stretched film may be a uniaxially stretched film or a biaxially stretched film.
The thickness of the acrylate film 2 is selected from the range of 10 to 200 μm, and more preferably 20 to 100 μm after stretching.
The coating composition of the functional coating 3 comprises the following components in parts by weight:
1-30 parts of water-dispersible resin
0.01-10 parts of epoxy compound with three or more functional groups
0.1-10 parts of nano dispersed particles
0.01-5 parts of cross-linking agent
45-98.88 parts of water.
The water-dispersible resin is a polymer resin having water dispersibility, and any resin having a minimum glass transition temperature lower than the stretching temperature in the stretching step described later may be used without limitation; may be selected from water dispersible polyurethane based resins, water dispersible acrylic resins, water dispersible polyester based resins or combinations thereof.
The trifunctional or higher epoxy compound is selected from the group consisting of epoxy compounds having 3 to 4 epoxy groups and epoxy compounds having alicyclic groups, and the epoxy compounds having 3 or more epoxy groups form a high crosslinking density after polymerization, so that moisture hardly penetrates into the coating layer. Meanwhile, the trifunctional or higher epoxy compound may be polymerized on the surface of the acrylic substrate, so that the interfacial adhesion between the acrylate film 2 and the functional coating layer 3 is enhanced, and thus the water resistance of the adhesion may be improved. In addition, when a monomer containing less than 3 epoxy groups is used, it is difficult to obtain sufficient crosslinking density and water resistance; when the number of epoxy functional groups exceeds 4, compatibility with the water-dispersible resin is very low, and it is difficult to use the epoxy resin in a coating composition based on the water-dispersible resin.
The epoxy compound with more than three functional groups is selected from one or more of 4, 5-epoxy tetrahydrophthalic acid diglycidyl ester, 1, 3-bis (N, N-diglycidyl ester) diiminomethylcyclohexane, 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane, 4- (2, 3-epoxy propoxy) -N, N-bis (2, 3-epoxy propyl) aniline or tetraglycidyl-m-xylene diamine.
The trifunctional or higher epoxy compound is more preferably an alicyclic epoxy compound, and among the trifunctional or higher epoxy monomers, 3 or more epoxy monomers are used, and at least one epoxy group of 3 or more epoxy groups is adjacent to 2 carbon atoms constituting the aliphatic hydrocarbon ring, and an alicyclic epoxy monomer formed between 2 carbon atoms can be used. These trifunctional or more alicyclic epoxy compounds have an alicyclic structure and therefore have better water resistance, and 4, 5-epoxytetrahydrophthalic acid diglycidyl ester can be used as the trifunctional or more alicyclic epoxy compound.
The content of the trifunctional or higher epoxy compound in the coating composition is further preferably 3 to 7 parts, when the content of the epoxy monomer is too much, the solubility is lowered and it is difficult to use in an aqueous system, and when the content of the epoxy monomer is too little, the improvement of the water resistance is insignificant.
The epoxy equivalent of the trifunctional or higher epoxy compound is about 80 to 140 g/eq, more preferably 90 to 130 g/eq, still more preferably 100 to 120 g/eq, and if the epoxy equivalent is too large, the crosslinking density of the water-resistant adhesive may be insufficient; if the epoxy equivalent is too small, the crosslinking density is too high, and film stretching may not be performed. Therefore, the epoxy equivalent of the epoxy compound is preferably within the above range.
The weight average molecular weight of the trifunctional or higher epoxy compound may be 200 to 500g/mol, and more preferably about 300 to 400 g/mol. If the weight average molecular weight is too large, it may be difficult to dissolve, and if it is too small, it may evaporate at high temperature to be cured, and therefore, the weight average molecular weight of the epoxy compound is preferably within the above range.
The crosslinking agent is selected from one or more of dihydrazide system, imidazole system, melamine system, amine system, acid anhydride system, isocyanate system, thiol system, carboxylic acid system, polyol system, polythiol system or phenol system, and further preferably one or more of adipic acid dihydrazide, oxazoline, carbodiimide and isophthalic acid dihydrazide.
The crosslinking agent may further enhance a crosslinking structure between epoxy compounds, and the content of the crosslinking agent is 0.1 to 7 parts, preferably 0.3 to 6 parts, and more preferably 0.5 to 5 parts, based on 100 parts by weight of the water-dispersible resin. When the content of the crosslinking agent is too large, stretching may be difficult, and when the content of the crosslinking agent is too large, the effect of adding the crosslinking agent is not remarkable.
The coating composition of the functional coating layer 3 of the present invention can be formed into an aqueous dispersion or an aqueous solution by dissolving or dispersing the water-dispersible resin, the trifunctional or higher epoxy compound and the crosslinking agent in water, and the amount of water at this time is coatability, and can be appropriately adjusted depending on the efficiency in the subsequent heat curing process.
The nano-dispersed particles are selected from inorganic nano-particles, organic nano-particles or a mixture of organic and inorganic nano-particles, the inorganic nano-particles comprise inorganic oxide selected from silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide and antimony oxide; the organic nano-particles are selected from silicon resin, fluororesin, methacrylic resin, cross-linked polyvinyl alcohol and melamine resin. The average particle size of the nano-dispersed particles is 10-300 nm, preferably 50-100 nm, or is selected from a mixture of nano-dispersed particles with an average particle size of 20-50 nm and nano-dispersed particles with an average particle size of 80-150 nm.
The coating composition of the functional coating layer 3 may further include a slip agent, a curing aid, a surfactant, a coupling agent, an antioxidant, a leveling agent, an antifouling agent, an antistatic agent, an antifoaming agent, an antiseptic agent, and the like. It may further include additives commonly used in the art to which the present invention pertains. The coating composition of the present invention may be adjusted in various ways within a range not deteriorating the physical properties thereof, and is not particularly limited.
A preparation method of an optical protective film with high water resistance and bending resistance comprises the following steps:
(1) preparing a coating composition of the functional coating: weighing the components of the coating composition of the functional coating 3, mixing and stirring to obtain the coating composition of the functional coating 3;
(2) preparation of acrylate film: uniformly mixing the components of the acrylate film 2 through a mixer, extruding and granulating through extruders such as a single-screw extruder, a double-screw extruder or a pressure kneader to obtain acrylate particles, and preparing the acrylate film 2 through a film forming method;
(3) applying the coating composition of the functional coating 3 of the step (1) to at least one surface of the acrylate film 2 of the step (2) to form a functional coating 3; and then stretching, drying and thermosetting the acrylate film 2 coated with the functional coating 3 at high temperature in sequence to obtain the high-water-resistance and bending-resistance optical protective film 4.
The forming method of the acrylate film 2 in the step (2) may be selected from forming methods such as a solution casting method, a melt extrusion method, a calendering method, and an extrusion film method. The present invention is not limited thereto.
The acrylate film 2 prepared in the step (2) may further include a stretching process to obtain a stretched film, and the stretching direction of the stretched film is not particularly limited, and the stretching ratio may be 1.1 to 5 times, and more preferably 1.5 to 3 times, the length based on the stretching direction.
The acrylic film stretched film obtained in the step (2) is one of a uniaxially stretched film and a biaxially stretched film. The method of applying the coating composition of the functional coating layer 3 to the acrylate film 2 in the step (3) may be selected from bar coating, blade coating, roll coating, blade coating, die coating, and specifically, a micro gravure coating method, a slot die coating method, a lip coating method, or a solution casting method may be used, but the present invention is not limited thereto.
The step (3) is to stretch the acrylic film 2 of the coating composition coated with the functional coating layer 3 at a high temperature, preferably at a stretching temperature of 80 to 200 ℃, more preferably 100 to 160 ℃, and if the stretching temperature is too low, the acrylic base film may not be sufficiently cured with respect to the coating composition, and if the stretching temperature is too high, the acrylic base film may be thermally deformed, and therefore, the above temperature range is preferable from the viewpoint of the above.
The step (3) is to stretch the acrylic film 2 of the coating composition coated with the functional coating layer 3 at a high temperature at a stretch ratio of 1.05 to 10 times, more preferably 1.5 to 3 times, the length in the stretching direction, and if the stretch ratio is less than 1.05 times, the stretching effect may not be sufficiently exhibited, and if it exceeds 10 times, the coating layer may be broken, and therefore, it is preferable to perform stretching at the stretch ratio.
The step (3) stretches the acrylate film 2 of the coating composition coated with the functional coating layer 3 at a high temperature, preferably in a direction perpendicular to the stretching direction of the stretched film of acrylate prepared in the step (2). That is, if the acrylate film 2 is stretched in the length (MD) direction before the coating composition is applied, it may be stretched in the width (TD) direction after the coating composition of the functional coating layer 3 is applied.
The stretching direction after the step (3) of applying the coating composition of the functional coating layer 3 is preferably simultaneously biaxially stretched, for example, simultaneously in the length (MD) direction and in the width (TD) direction.
The stretching process in the step (2) or (3) has a total stretching ratio of 1.1 to 25 times, more preferably 1.2 to 10 times, and still more preferably 1.5 to 7 times, based on the total stretching area of the acrylate film 2. If the stretching ratio is less than 1.1 times, the stretching effect may not be sufficiently exhibited, and if it exceeds 25 times, the coating layer may be broken, and therefore, it is preferable to perform stretching at the above stretching ratio.
The final thickness of the functional coating 3 obtained in the step (3) after stretching and thermosetting is about 50-2000 nm, more preferably 100-1500 nm, and still more preferably 150-300 nm.
The functional coating layer 3 of the step (3) may be formed only on one side of the acrylate film 2, or may be formed on both sides of the acrylate film 2.
When the functional coating 3 of the step (3) is coated on only one side of the acrylate film 2, the other side of the acrylate film 2 may further include one or more other coatings or other films, and the method and the step of forming the bending-resistant optical protective film for a polarizer are not limited. For example, a method of applying another coating layer before stretching the optical protective film 4 and curing after stretching, or a method of applying another coating layer after stretching the optical protective film 4 and curing, or a film separately formed on the optical protective film 4 using the adhesive 6. Another film or film may be laminated on the other side of the acrylate film 2 by various methods known in the art, such as a lamination method.
The invention also provides a high-water-resistance and bending-resistance polarizer 10 which comprises a polarizer film 5, an adhesive 6 and the high-water-resistance and bending-resistance optical protection film 4 bonded with at least one surface of the polarizer film 5 through the adhesive 6.
The polarizing film 5 is a polyvinyl alcohol (PVA) polarizing film and is prepared by the following steps: a polyvinyl alcohol (PVA) film is immersed in an aqueous solution to swell, dyed with a dichroic material that imparts polarization to the polyvinyl alcohol (PVA) film, and the dyed polyvinyl alcohol (PVA) film is stretched to swell. The polyvinyl alcohol (PVA) polarizer film is formed through a stretching step of aligning dichroic dye materials side by side in a stretching direction and a complementary color step of correcting a color of the polyvinyl alcohol (PVA) film after the stretching step. However, the polyvinyl alcohol (PVA) polarizing film of the present invention is not limited thereto.
The adhesive 6 is selected from a water-based adhesive, a polyvinyl alcohol (PVA) -based adhesive, a polyurethane-based adhesive, an epoxy-based adhesive, an acrylic-based adhesive, a styrene butadiene rubber-based (SBR-based) adhesive, or a hot melt adhesive, as long as it is known in the art, but the present invention is not limited to these examples.
The high water-resistant and bending-resistant polarizer 10 may be bonded to the high water-resistant and bending-resistant optical protective film 4 only on one surface of the polarizer film 5 by an adhesive 6, and may be attached to a general protective film 7, which is generally used for protection of the polarizer 10, on the other surface of the polarizer film 5 by the adhesive 6. The general protective film 7 is selected from one or more of a triacetate fiber (TAC) film, a polyethylene terephthalate (PET) film, a Polycarbonate (PC) film, a polymethyl methacrylate (PMMA) film, a Cyclic Olefin Polymer (COP) film, and a cyclic olefin polymer (SANUQI) like film. The other surface of the general protection film 7 is attached to a release film 9 through a pressure sensitive adhesive 8. The general protective film 7 can also be a functional film with compensation, brightness enhancement and wide viewing angle.
The upper surface of the high-water-resistance and bending-resistance optical protection film 4 can be further provided with a surface treatment layer 11, and the surface treatment layer 11 is selected from one or more layers of an anti-glare layer, a low-reflection layer, a high-hardening layer, an anti-reflection layer, an antistatic layer and an anti-fouling layer.
The present invention also provides a liquid crystal display device including the above polarizer 10 having high water resistance and bending resistance.
Example 1
A. Preparation of optical protective film
Preparing a coating composition of the functional coating: the coating composition of the functional coating 3 was prepared by weighing 11 parts of a polyester acrylic resin (30% solid content dispersion), 4 parts of a polyurethane resin (25% solid content dispersion), 3 parts of 4, 5-epoxy tetrahydrophthalic acid diglycidyl ester, 2 parts of colloidal silica (solid content 40% dispersion) nano-dispersed particles, 0.3 part of a crosslinking agent carbodiimide (solid content 4% aqueous solution), 0.7 part of a coupling agent γ -methacryloxypropyl trimethoxysilane, and 79 parts of pure water according to the formulation, and mixing and stirring the above components.
Preparing an acrylate film: according to the formula of the acrylate film 2, 84 parts of polymethyl methacrylate resin, 15.5 parts of styrene-methyl methacrylate copolymer coated silicon rubber polymer core-shell particles 1, 0.2 part of 2- (2H-benzotriazole-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3, 3-tetramethylbutyl) phenol ultraviolet absorbent and 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester antioxidant are mixed by a high-speed mixer and then extruded and granulated at 230-260 ℃ by using a single-screw extruder to obtain acrylate particles.
Using the acrylic ester particles obtained in the above procedure, an unstretched film having a width of 920mm and a thickness of 200 μm was produced at 250 ℃ using a T-die film forming machine. The unstretched film was stretched 1.8 times in the length (MD) direction at a temperature of 135 ℃ to produce a uniaxially stretched acrylate film 2.
Preparing an optical protective film with high water resistance and bending resistance: on the uniaxially stretched acrylate film 2 obtained in the above step, after coating the coating composition of the functional coating layer 3 by a bar coating method, hot air-dried at a temperature of 100 ℃ for 30 seconds, then heated at a temperature of 135 ℃ for 1 minute, and then stretched 2.5 times in the width (TD) direction, and the width was adjusted by trimming, to prepare a highly water-resistant and bending-resistant optical protective film 4 having a coating layer thickness of about 280nm and a width of 2260 mm.
B. Preparation of polarizer
The functional coating 3 of the high-water-resistance and bending-resistance optical protection film 4 prepared in the above steps faces a polyvinyl alcohol (PVA) polarizer film 5, an ultraviolet-based adhesive 6 is coated between the polyvinyl alcohol (PVA) polarizer film 5 and the functional coating 3 to obtain an optical protection film 4 laminated on both sides of the polyvinyl alcohol (PVA) polarizer film 5, an original anti-polarizer in which the high-water-resistance and bending-resistance optical protection films 4 are laminated on both sides of the polyvinyl alcohol (PVA) polarizer film 5 is prepared after ultraviolet irradiation curing, and then a release film 9 is attached to the lower surface of the high-water-resistance and bending-resistance optical protection film 4 by using a pressure sensitive adhesive 8 to obtain a high-water-resistance and bending-resistance polarizer 10, as shown in fig. 3.
Example 2
A. Preparation of optical protective film
Preparing a coating composition of the functional coating: 15 parts of a urethane acrylic resin (30% solid content dispersion liquid), 15 parts of a polyurethane resin (25% solid content dispersion liquid), 10 parts of a 1, 3-bis (N, N-diglycidyl) diiminomethylcyclohexane epoxy compound, 3 parts of colloidal silica (40% solid content dispersion liquid), 0.5 part of adipic acid dihydrazide crosslinking agent (4% solid content aqueous solution), 0.5 part of an antioxidant tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 56 parts of pure water were weighed according to the formulation, and the above components were mixed and stirred to prepare a coating composition of the functional coating 3.
Preparing an acrylate film: according to the formula of the acrylate membrane 2, 68.5 parts of poly (methyl methacrylate-styrene) copolymer resin, 30 parts of poly (ethyl methacrylate) -coated polystyrene-butadiene copolymer polymer core-shell particles 1, 0.5 part of 2- (2' -hydroxy-3 ',5' -bis (a, a-dimethylbenzyl) phenyl) benzotriazole and 1 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester antioxidant are mixed by a high-speed mixer, and then extruded and granulated at 230-260 ℃ by using a double-screw extruder to obtain acrylate particles.
An unstretched acrylate film 2 having a width of 1300mm and a thickness of 150 μm was prepared at 250 ℃ using the acrylate particles obtained in the above procedure using a T-die film forming machine.
Preparing an optical protective film with high water resistance and bending resistance: after the coating composition of the functional coating layer 3 was applied on the unstretched acrylate film 2 obtained in the above step by a bar coating method, it was dried in hot air at a temperature of 100 ℃ for 30 seconds, then heated at a temperature of 135 ℃ for 1 minute, and then simultaneously biaxially stretched 3.8 times in the length (MD) and width (TD) directions, and the width was adjusted by trimming to prepare a highly water-resistant and bending-resistant optical protective film 4 having a coating layer thickness of about 250nm and a width of 2530 mm.
B. Preparation of polarizer
The high water-resistant and bending-resistant optical protection film 4 prepared in the above steps is prepared by facing the functional coating 3 to the upper surface of the polyvinyl alcohol (PVA) polarizer film 5, coating the ultraviolet-based adhesive 6 between the upper surface of the polyvinyl alcohol (PVA) polarizer film 5 and the functional coating 3, laminating, coating the ultraviolet-based adhesive 6 on the lower surface of the polyvinyl alcohol (PVA) polarizer film 5, laminating and bonding with the cycloolefin polymer (COP) general protection film 7, curing by ultraviolet irradiation to obtain the original reverse polarizer in which the high water-resistant and bending-resistant optical protection film 4 is laminated on the upper surface of the polyvinyl alcohol (PVA) polarizer film 5, and laminating the release film 9 on the lower surface of the olefin polymer (COP) general protection film 7 by using the pressure-sensitive adhesive 8 to obtain the high water-resistant and bending-resistant polarizer 10, as shown in fig. 4.
Example 3
A. Preparation of optical protective film
Preparing a coating composition of the functional coating: 0.5 part of urethane acrylic resin (30% solid content dispersion liquid), 0.5 part of urethane resin (25% solid content dispersion liquid), 0.01 part of 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane epoxy compound, 0.1 part of colloidal silica (solid content 40% dispersion liquid), 0.01 part of crosslinking agent oxazoline (solid content 25% aqueous solution) and 98.88 parts of pure water are weighed according to the formula, and the components are mixed and stirred to prepare the coating composition of the functional coating 3.
Preparing an acrylate film: according to the formula of an acrylate membrane 2, 98.8 parts of poly (cyclohexylmaleimide-methyl methacrylate) copolymer resin, 1 part of polycyclohexyl methacrylate-coated 1, 4-polyphenylbutadiene copolymer polymer core-shell particles 1, 0.1 part of 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole and 0.1 part of gamma-aminopropyltriethoxysilane coupling agent are mixed by a high-speed mixer, and then extruded and granulated by a double-screw extruder at 230-260 ℃ to obtain acrylate particles;
using the acrylic ester particles obtained in the above procedure, an unstretched film having a width of 800mm and a thickness of 200 μm was produced at 250 ℃ using a T-die film forming machine. The unstretched film was simultaneously stretched 1.5 times in the length (MD) direction and the width (TD) direction at a temperature of 135 ℃ to produce a biaxially stretched acrylate film 2.
Preparing an optical protective film with high water resistance and bending resistance: after the coating composition of the functional coating layer 3 was applied on the biaxially stretched acrylate film 2 obtained in the above step by the bar coating method, it was dried in hot air at a temperature of 100 ℃ for 30 seconds, then heated at a temperature of 135 ℃ for 1 minute, and then simultaneously biaxially stretched 3.5 times in the length (MD) and width (TD) directions, and the width was adjusted by trimming to prepare a highly water-resistant and bending-resistant optical protective film 4 having a coating layer thickness of about 150nm and a width of 1980 mm.
B. Preparation of polarizer
The highly water-resistant and bending-resistant optical protection film 4 prepared in the above steps is prepared by facing the functional coating layer to the upper side of the polyvinyl alcohol (PVA) polarizer film 5, coating a polyvinyl alcohol (PVA) -based adhesive 6 between the upper surface of the polyvinyl alcohol (PVA) polarizer film 5 and the functional coating layer 3 for lamination, coating the polyvinyl alcohol (PVA) -based adhesive 6 on the lower surface of the polyvinyl alcohol (PVA) polarizer film 5 for lamination and lamination with a triacetate fiber (TAC) universal protection film 7, drying and curing to obtain a proto-inverse polarizer in which the highly water-resistant and bending-resistant optical protection film 4 is laminated on the upper surface of the polyvinyl alcohol (PVA) polarizer film 5, and laminating a release film 9 on the lower surface of the triacetate fiber (TAC) universal protection film 7 by using a pressure-sensitive adhesive 8 to obtain a highly water-resistant and bending-resistant polarizer 10, as shown in fig. 4.
Example 4
A. Preparation of optical protective film
Preparing a coating composition of the functional coating: 20 parts of a polyurethane acrylic resin (30% solid content dispersion), 8 parts of a polyurethane resin (25% solid content dispersion), 10 parts of an epoxy compound 4- (2, 3-epoxypropoxy) -N, N-bis (2, 3-epoxypropyl) aniline, 10 parts of colloidal silica (40% solid content dispersion), 5 parts of a crosslinking agent isophthalic dihydrazide (25% solid content aqueous solution), 1.5 parts of a slip agent stearic acid, 0.5 part of a coupling agent gamma-methacryloxypropyltrimethoxysilane and 45 parts of pure water are weighed according to the formula, and the components are mixed and stirred to prepare the coating composition of the functional coating 3.
Preparing an acrylate film: according to the formula of an acrylate film 2, 89 parts of poly (methyl methacrylate-styrene) copolymer resin, 10.2 parts of polymer core-shell particles of an ethylene-vinyl acetate copolymer coated with polyisobutyl methacrylate (1), 0.3 part of 2- (4, 6-diphenyl-1, 3, 5-triazine-2-yl) -5-hexyloxy-phenol and 0.5 part of silane coupling agent vinyl triethoxysilane are mixed by a high-speed mixer, and then a single-screw extruder is used for extrusion granulation at 230-260 ℃ to obtain acrylate particles;
using the acrylic ester particles obtained in the above procedure, an unstretched film having a width of 800mm and a thickness of 300 μm was produced at 250 ℃ using a T-die film forming machine. The unstretched film was stretched 2 times in the length (MD) direction at a temperature of 135 ℃ to produce a uniaxially stretched acrylate film 2.
Preparing an optical protective film with high water resistance and bending resistance: on the uniaxially stretched acrylate film 2 obtained in the above-mentioned step, after the coating composition of the functional coating layer 3 was applied by a bar coating method, it was dried in hot air at a temperature of 100 ℃ for 30 seconds, then heated at a temperature of 135 ℃ for 1 minute, and then stretched 3.5 times in the width (TD) direction, and the width was adjusted by trimming to prepare a highly water-resistant and bending-resistant optical protective film 4 having a coating layer thickness of about 300nm and a width of 2700 mm.
B. Preparation of polarizer
The highly water-resistant and bending-resistant optical protective film 4 prepared in the above steps is prepared by coating an acrylic-based adhesive 6 between the upper surface of the polyvinyl alcohol (PVA) polarizer film 5 and the functional coating layer so that the functional coating layer 3 faces the upper surface of the polyvinyl alcohol (PVA) polarizer film 5 for lamination, coating an acrylic-based adhesive 6 on the lower surface of the polyvinyl alcohol (PVA) polarizer film 5 for lamination with a cycloolefm-like polymer (SANUQI) universal protective film 7, performing ultraviolet irradiation curing, and preparing an original reverse polarizer in which the highly water-resistant and bending-resistant optical protective film 4 is laminated on the upper surface of the polyvinyl alcohol (PVA) polarizer film 5, and laminating a release film 9 on the lower surface of the cycloolefm-like polymer (SANUQI) universal protective film 7 by using a pressure-sensitive adhesive 8, so as to obtain a highly water-resistant and bending-resistant polarizer 10, as shown in fig. 4.
Example 5
A. Preparation of optical protective film
Preparing a coating composition of the functional coating: the coating composition of the functional coating 3 was prepared by weighing 10 parts of a polyester acrylic resin (30% solid content dispersion), 10 parts of a polyurethane resin (25% solid content dispersion), 4 parts of an epoxy compound tetraglycidyl-m-xylylenediamine, 1.5 parts of colloidal silica (solid content 40% dispersion), 1 part of a crosslinking agent isophthalic dihydrazide (solid content 25% aqueous solution), 1 part of a surfactant polyethylene glycol, 0.5 part of a coupling agent vinyltrimethoxysilane, and 72 parts of pure water according to the formulation, and mixing and stirring the above components.
Preparing an acrylate film: according to the formula of the acrylate film 2, 94 parts of polymethyl methacrylate resin, 5.3 parts of polymer core-shell particles 1 of poly-isobornyl methacrylate coated polyolefin elastomer, 0.4 part of 2,4, 6-tri (2' n-butoxyphenyl) -1,3, 5-triazine and 0.3 part of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate are mixed by a high-speed mixer, and then a single-screw extruder is used for extrusion granulation at 230-260 ℃ to obtain acrylate particles;
an unstretched acrylate film 2 having a width of 1200mm and a thickness of 200 μm was prepared using the acrylate particles obtained in the above step at 250 ℃ using a T-die film forming machine.
Preparing an optical protective film with high water resistance and bending resistance: after the coating composition of the functional coating layer 3 was applied to the acrylate film 2 obtained in the above step by a bar coating method, it was dried in hot air at a temperature of 100 ℃ for 30 seconds, then heated at a temperature of 135 ℃ for 1 minute, and then simultaneously stretched 5 times in the length (MD) and width (TD) directions, and the width was adjusted by trimming, to prepare a highly water-resistant and bending-resistant optical protective film 4 having a coating layer thickness of about 180nm and a width of 2560 mm.
B. Preparation of polarizer
The high water-resistant and bending-resistant optical protective film 4 prepared in the above steps is prepared by facing the functional coating 3 to the upper surface of a polyvinyl alcohol (PVA) polarizer film 5, coating an epoxy adhesive 6 between the upper surface of the PVA polarizer film 5 and the functional coating 3 for lamination and lamination, coating the epoxy adhesive 6 on the lower surface of the PVA polarizer film 5 and a polymethyl methacrylate (PMMA) general protective film 7 for lamination and lamination, irradiating and curing by ultraviolet rays to prepare an original polaroid with the high water-resistant and bending-resistant optical protective film 4 laminated on the upper surface of the PVA polarizer film 5, laminating a release film 9 on the lower surface of the polymethyl methacrylate (PMMA) general protective film 7 by using a pressure-sensitive adhesive 8, and then forming a surface treatment layer 11 with an anti-glare layer and a low reflection layer on the upper surface of the high water-resistant and bending-resistant optical protective film 4, the polarizer 10 having high water resistance and bending resistance was obtained as shown in FIG. 5.
Comparative example 1
A. Preparation of optical protective film
Preparing a coating composition of the functional coating: a coating composition for functional coating 3 was prepared by weighing 11 parts of a polyester acrylic resin (30% solid content dispersion), 4 parts of a polyurethane resin (25% solid content dispersion), 2 parts of colloidal silica (solid content 40% dispersion), and 83 parts of pure water, and mixing and stirring the above components.
Preparing an acrylate film: 99.7 parts of polymethyl methacrylate resin and 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are mixed by a high-speed mixer, and then extrusion granulation is performed at 230 to 260 ℃ by using a single-screw extruder and an extruder to obtain acrylate particles.
Using the acrylic ester particles obtained in the above procedure, an unstretched film having a width of 920mm and a thickness of 200 μm was produced at 250 ℃ using a T-die film forming machine. The unstretched film was stretched 1.8 times in the length (MD) direction at a temperature of 135 ℃ to produce a uniaxially stretched acrylate film 2.
Preparing an optical protective film: on the obtained uniaxially stretched acrylate film 2, after coating the coating composition of the functional coating layer 3 prepared in the above step by a bar coating method, hot air-dried at a temperature of 100 ℃ for 30 seconds, then heated at a temperature of 135 ℃ for 1 minute, and then stretched 2.5 times in the width (TD) direction, and the width was adjusted by trimming to prepare an optical protective film 4 having a coating layer thickness of about 280nm and a width of 2260 mm.
B. Preparation of polarizer
In the optical protective film 4 prepared in the above step, the functional coating 3 is made to face the polyvinyl alcohol (PVA) polarizer film 5, and the ultraviolet-based adhesive 6 is coated between the polyvinyl alcohol (PVA) polarizer film 5 and the functional coating 3 to obtain the laminated optical protective film 4 on both sides of the polyvinyl alcohol (PVA) polarizer film 5, the original inverse polarizer in which the optical protective films 4 are laminated on both sides of the PVA polarizer film 5 is prepared after ultraviolet irradiation curing, and the release film 9 is attached to the surface of the optical protective film 4 by using the pressure sensitive adhesive 8 to obtain the polarizer 10.
Comparative example 2
A. Preparation of optical protective film
Preparing a coating composition of the functional coating: 15 parts of a urethane acrylic resin (30% solid content dispersion), 15 parts of a polyurethane resin (25% solid content dispersion), 3 parts of colloidal silica (40% solid content dispersion), 0.5 part of adipic acid dihydrazide crosslinking agent (4% solid content aqueous solution), 0.5 part of an antioxidant, and 66 parts of pure water were weighed, and the above components were mixed and stirred to prepare a coating composition for functional coating 3.
Preparing an acrylate film: 99.7 parts of polymethyl methacrylate resin and 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are mixed by a high-speed mixer, and then extrusion granulation is performed at 230 to 260 ℃ by using a single-screw extruder and an extruder to obtain acrylate particles.
Using the acrylic ester particles obtained in the above procedure, an unstretched film having a width of 920mm and a thickness of 200 μm was produced at 250 ℃ using a T-die film forming machine. The unstretched film was stretched 1.8 times in the length (MD) direction at a temperature of 135 ℃ to produce a uniaxially stretched acrylate film 2.
Preparing an optical protective film: on the uniaxially stretched acrylate film 2 obtained in the above step, after coating the coating composition of the functional coating layer 3 prepared in the above step by a bar coating method, hot air-dried at a temperature of 100 ℃ for 30 seconds, then heated at a temperature of 135 ℃ for 1 minute, and then stretched 2.5 times in the width (TD) direction, and the width was adjusted by trimming to prepare an optical protective film 4 having a coating layer thickness of about 280nm and a width of 2260 mm.
B. Preparation of polarizer
In the optical protection film 4 prepared in the above step, the functional coating 3 is made to face the polyvinyl alcohol (PVA) polarizer film 5, and the ultraviolet-based adhesive 6 is coated between the polyvinyl alcohol (PVA) polarizer film 5 and the functional coating 3 to obtain the laminated optical protection film 4 on both sides of the polyvinyl alcohol (PVA) polarizer film 5, the original inverse polarizer in which the optical protection films 4 are laminated on both sides of the polyvinyl alcohol (PVA) polarizer film 5 is prepared after ultraviolet irradiation curing, and the release film 9 is attached to the lower surface of the optical protection film 4 by using the pressure-sensitive adhesive 8 to obtain the polarizer 10.
Comparative example 3
A. Preparation of optical protective film
Preparing a coating composition of the functional coating: a coating composition for functional coating 3 was prepared by weighing 11 parts of a polyester acrylic resin (30% solid content dispersion), 4 parts of a polyurethane resin (25% solid content dispersion), 3 parts of 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexyl formate, 2 parts of colloidal silica (solid content 40% dispersion), and 83 parts of pure water, and mixing and stirring the above components.
Preparing an acrylate film: 99.7 parts of polymethyl methacrylate resin and 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are mixed by a high-speed mixer, and then extrusion granulation is performed at 230 to 260 ℃ by using a single-screw extruder and an extruder to obtain acrylate particles.
Using the acrylic ester particles obtained in the above procedure, an unstretched film having a width of 920mm and a thickness of 200 μm was prepared at 250 ℃ using a T-die film forming machine. The unstretched film was stretched 1.8 times in the length (MD) direction at a temperature of 135 ℃ to produce a uniaxially stretched acrylate film 2.
Preparation of the optical protective film 4: on the uniaxially stretched acrylate film 2 obtained in the above step, after coating the coating composition of the functional coating layer 3 prepared in the above step by a bar coating method, hot air-dried at a temperature of 100 ℃ for 30 seconds, then heated at a temperature of 135 ℃ for 1 minute, and then stretched 2.5 times in the width (TD) direction, and the width was adjusted by trimming to prepare an optical protective film 4 having a coating layer thickness of about 280nm and a width of 2260 mm.
B. Manufacture of polarizer
In the optical protection film 4 prepared in the above step, the functional coating 3 is made to face the polyvinyl alcohol (PVA) polarizer film 5, and the ultraviolet-based adhesive 6 is coated between the polyvinyl alcohol (PVA) polarizer film 5 and the functional coating 3 to obtain the laminated optical protection film 4 on both sides of the polyvinyl alcohol (PVA) polarizer film 5, and after ultraviolet irradiation curing, the original anti-polarizer in which the optical protection film 4 is laminated on both sides of the polyvinyl alcohol (PVA) polarizer film 5 is prepared, and the release film 9 can be attached to the lower surface of the optical protection film 4 by using the pressure sensitive adhesive 8 to obtain the polarizer 10.
The product-related tests are shown in tables 1, 2 and 3, and the test methods are as follows:
A. adhesion testing
(1) Adhesion of optical protective film
The polarizers 10 of the examples and comparative examples were cut to 120mm × 20mm, the release film 9 was peeled off, the pressure-sensitive adhesive 8 layer of the polarizer 10 was fixed on glass with a 3M double-sided tape, as shown in fig. 6, the adhesiveness between the acrylate film 2 and the functional coating 3 was evaluated, and a peel test was performed between the acrylate film 2 and the functional coating 3 of the polarizer 10 (i.e., the peel position a) at a speed of 300M/min and a 90 degree direction by testing the peel strength.
(2) Adhesion of polarizer
The adhesion between the functional coating 3 and the polarizer film 5 was evaluated, the release film 9 was peeled off, the outermost side of the optical protective film 4 of the polarizer 10 was fixed on glass with a 3M double-sided tape, the adhesion between the functional coating 3 and the polarizer film 5 was evaluated as shown in fig. 7, and a peel test was performed by testing the peel strength in the direction of 90 degrees at a speed of 300M/min at the functional coating 3 and the polarizer film 5 (i.e., the peel position B) of the optical protective film 4 of the polarizer 10.
(3) Water resistance
The polarizers 10 of the examples and comparative examples were cut into pieces of 120mm × 20mm, completely immersed in a water bath at 60 ℃, and left to stand for 24 hours. The polarizer 10 was taken out, the surface moisture was removed, and the adhesion of the optical protective film 4 and the polarizer 10 was evaluated in the same manner as described above, respectively, without additional drying.
B. Bending resistance test
The optical protective film 4 and the polarizer 10 of the examples and comparative examples were cut into 150mm × 15mm, placed on a bending strength tester, and the sample was bent back and forth in a vertical state with a load of 200g at a bending angle of 135 degrees to the left and right sides until the test piece was broken, and automatically counted.
C. Optical testing
(1) Optical characteristic test of optical protective film
Total light transmittance: the test was carried out using a haze meter (NDH 2000N).
Transmittance at 380 nm: the test was carried out using a spectrophotometer (V7100).
(2) Optical characteristic test of polarizer
Transmittance of monomer: the test was carried out using a spectrophotometer (V7100).
Transmittance at 380 nm: the test was carried out using a spectrophotometer (V7100).
Table 1 adhesion testing
Figure 875286DEST_PATH_IMAGE001
Note: the peel strength at a peel strength of not less than 2N/cm was judged as good (O), the peel strength at a peel strength of 1.5N/cm to 2N/cm was judged as moderate (. DELTA.), and the peel strength at a peel strength of less than 1.5N/cm was judged as not good (X).
TABLE 2 bending resistance test
Figure 220817DEST_PATH_IMAGE002
TABLE 3 optical testing
Figure 308859DEST_PATH_IMAGE003
Referring to table 1, the high water-resistant and bending-resistant optical protective film 4 obtained according to the example of the present invention showed excellent adhesion to both the acrylate film 2 and the polarizer 10, which was maintained even when immersed at high temperature (60 ℃) for a long time of 24 hours, and thus was excellent in water resistance; on the other hand, comparative example 1 in which the functional coating layer 3 was formed only of the water-dispersible resin was similar to comparative example 2 in which the functional coating layer 3 was formed of the water-dispersible resin and the crosslinking agent in initial adhesiveness, but adhesion after high-temperature immersion was poor, and thus the optical protective film 4 and the polarizer 10 provided by the present invention had excellent water resistance. In addition, comparative example 3 using a bifunctional epoxy compound in the functional coating layer 3 exhibited lower water resistance than the optical protective film 4 and the polarizer 10 in the embodiment of the present invention.
Referring to table 2, the high water-resistant and bending-resistant optical protective film 4 and the polarizer 10 obtained in the embodiment of the present invention have the bending-resistant times of more than 1000 times because the hard shell polymer 11 with the high glass transition temperature is added to coat the polymer core-shell particles 1 of the soft core polymer 12 with the low glass transition temperature, and the bending-resistant times of less than 200 times because the comparative example has no polymer core-shell particles, so the high water-resistant and bending-resistant optical protective film 4 and the polarizer 10 obtained in the present invention have excellent bending resistance and meet the requirement of flexible display.
Referring to table 3, the high water-resistant and bending-resistant optical protection film 4 and the polarizer 10 obtained according to the embodiments of the present invention both show excellent optical characteristics, and can effectively absorb ultraviolet rays due to the addition of an ultraviolet absorber, the transmittance of the high water-resistant and bending-resistant optical protection film 4 in the embodiments of the present invention at 380nm is less than 10%, the transmittance of the optical protection film 4 in the comparative examples at 380nm is greater than 10%, the transmittance of the polarizer 10 in the embodiments is less than 3%, and the transmittance of the polarizer 10 in the comparative examples at 380nm is greater than 3%.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (17)

1. An optical protective film having high water resistance and bending resistance, comprising an acrylate film and a functional coating layer formed on at least one surface of the acrylate film;
the acrylate film comprises polymeric core-shell particles;
the coating composition of the functional coating comprises a water-dispersible resin and a trifunctional or higher epoxy compound;
the polymeric core shell microparticles are selected from hard shell polymers having a high glass transition temperature, clad with soft core polymers having a low glass transition temperature; the hard shell polymer in the polymer core-shell particles is selected from a copolymer with a glass transition temperature higher than 80 ℃, and the soft core polymer in the polymer core-shell particles is selected from a copolymer with a glass transition temperature lower than 40 ℃;
the thickness of the functional coating is 150-300 nm;
the high-water-resistant and bending-resistant optical protective film is used for forming a high-water-resistant and bending-resistant polarizer;
the high-water-resistance and bending-resistance optical protective film is prepared by the following steps:
(1) preparing a coating composition of the functional coating: weighing and uniformly mixing all components of the coating composition of the functional coating to obtain the coating composition of the functional coating;
(2) preparing an acrylate film: uniformly mixing all components of the acrylate film through a mixer, extruding and granulating by using an extruder to obtain acrylate particles, and preparing the acrylate film through a film forming method;
(3) applying the coating composition of step (1) to at least one surface of the acrylate film of step (2) to form the functional coating; then sequentially stretching, drying and thermosetting the acrylate film coated with the functional coating at high temperature to obtain the high-water-resistance and bending-resistance optical protective film, wherein the stretching temperature is 80-200 ℃, and the stretching ratio is 1.05-10 times of the length based on the stretching direction;
the step (2) of preparing the acrylate film by the film forming method further includes a stretching process to obtain a stretched film, and a stretching ratio is 1.1 to 5 times a length based on a stretching direction.
2. The optical protective film with high water resistance and bending resistance according to claim 1, wherein the acrylate film comprises the following components in parts by weight:
68.5-98.8 parts of acrylate copolymer resin
1-30 parts of polymer core-shell particles
0.1 to 0.5 part of ultraviolet absorber
0.1 to 1 portion of other components
The other components are at least one of lubricant, flexibilizer, antioxidant, flatting agent, antifouling agent, antistatic agent and preservative.
3. The optical protective film with high water resistance and bending resistance according to claim 1, wherein the diameter of the polymer core-shell particles is 10-500 nm.
4. The optical protective film with high water resistance and bending resistance according to claim 3, wherein the diameter of the polymer core-shell particles is 50-200 nm.
5. The optical protective film with high water resistance and bending resistance according to claim 1, wherein the coating composition of the functional coating comprises the following components in parts by weight:
1-30 parts of water-dispersible resin
0.01-10 parts of epoxy compound with three or more functional groups
0.1-10 parts of nano dispersed particles
0.01-5 parts of cross-linking agent
45-98.88 parts of water.
6. The optical protective film with high water resistance and bending resistance according to claim 1, wherein the trifunctional or higher epoxy compound is one or more selected from 4, 5-epoxytetrahydrophthalic acid diglycidyl ester, 1, 3-bis (N, N-diglycidyl ester) diiminomethyl cyclohexane, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, 4- (2, 3-epoxypropoxy) -N, N-bis (2, 3-epoxypropyl) aniline, and tetraglycidyl-m-xylylenediamine.
7. The optical protective film having high water resistance and bending resistance according to claim 1, wherein the trifunctional or higher epoxy compound includes an aliphatic hydrocarbon ring, and at least one or more epoxy functional groups are formed between two adjacent carbon atoms constituting the aliphatic hydrocarbon ring.
8. The optical protective film with high water resistance and bending resistance according to claim 1, wherein the water-dispersible resin comprises one of a water-dispersible polyurethane resin, a water-dispersible acrylic resin, a water-dispersible polyester resin or a combination thereof.
9. The optical protective film according to claim 5, wherein the cross-linking agent is selected from one or more of dihydrazide system, imidazole system, melamine system, amine system, acid anhydride system, isocyanate system, thiol system, carboxylic acid system, polyol system, polythiol system, or phenol system.
10. The optical protective film with high water resistance and bending resistance according to claim 9, wherein the cross-linking agent is one or more selected from adipic acid dihydrazide, oxazoline, carbodiimide and isophthalic acid dihydrazide.
11. The optical protective film with high water resistance and bending resistance according to claim 2, wherein the monomer of the copolymer with the glass transition temperature higher than 80 ℃ is selected from one or more of styrene, acrylamide, methacrylamide, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate.
12. The optical protective film according to claim 2, wherein the copolymer having a glass transition temperature of less than 40 ℃ is selected from one or more of silicone rubber, polystyrene butadiene copolymer, 1, 4-polyisoprene copolymer, 1, 4-polybutadiene copolymer, chloroprene copolymer, ethylene-propylene-non-conjugated diene copolymer, isobutylene copolymer, polyamide elastomer, polyolefin elastomer, polyurethane elastomer, styrene thermoplastic elastomer, polyethylene octene elastomer, and ethylene-vinyl acetate elastomer; or the monomer of the copolymer with the glass transition temperature lower than 40 ℃ is selected from one or more of methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethyl acrylate, isooctyl acrylate, hydroxypropyl acrylate and hydroxyethyl acrylate.
13. The optical protective film according to claim 2, wherein the UV absorber is selected from the group consisting of 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3, 3-tetramethylbutyl) phenol, 2' - (2' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' bis (a, a-dimethylbenzyl) phenyl) benzotriazole, 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxy-phenol, and mixtures thereof, 2- (2 '-hydroxy-3', 5 '-di-tert-phenyl) -5-chlorobenzotriazole, 2,4, 6-tri (2' -n-butoxyphenyl) -1,3, 5-triazine.
14. A polarizer having high water resistance and bending resistance, comprising a polarizer film, an adhesive, and the optical protective film having high water resistance and bending resistance of any one of claims 1 to 13 bonded to at least one surface of the polarizer film via the adhesive.
15. The polarizer according to claim 14, further comprising a universal protective film and a release film, wherein the universal protective film is one or more selected from a group consisting of a triacetate film, a polyethylene terephthalate film, a polycarbonate film, a polymethyl methacrylate film, a cycloolefin polymer film, and a cyclic olefin-like polymer film, and one surface of the universal protective film is attached to the polarizer film by an adhesive and the other surface is attached to the release film by a pressure sensitive adhesive.
16. The polarizer having high water resistance and folding resistance according to claim 14 or 15, wherein the upper surface of the optical protective film having high water resistance and folding resistance is provided with a surface treatment layer selected from one or a combination of more than one layer of an anti-glare layer, a low reflection layer, a high hardening layer, an anti-reflection layer, an antistatic layer, and an anti-smudge layer.
17. A liquid crystal display device comprising the polarizer having high water resistance and bending resistance as claimed in any one of claims 14 to 16.
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