WO2016018103A1 - Composition de résine pour film protecteur de polariseur, film protecteur de polariseur, et plaque polarisante le comprenant - Google Patents

Composition de résine pour film protecteur de polariseur, film protecteur de polariseur, et plaque polarisante le comprenant Download PDF

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Publication number
WO2016018103A1
WO2016018103A1 PCT/KR2015/008001 KR2015008001W WO2016018103A1 WO 2016018103 A1 WO2016018103 A1 WO 2016018103A1 KR 2015008001 W KR2015008001 W KR 2015008001W WO 2016018103 A1 WO2016018103 A1 WO 2016018103A1
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WO
WIPO (PCT)
Prior art keywords
protective film
curable monomer
resin composition
polarizer protective
polarizer
Prior art date
Application number
PCT/KR2015/008001
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English (en)
Korean (ko)
Inventor
이한나
장영래
박준욱
허은수
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020150107552A external-priority patent/KR101748409B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US15/329,563 priority Critical patent/US20170210915A1/en
Priority to CN201580038438.1A priority patent/CN106536573B/zh
Priority to JP2017503570A priority patent/JP6638157B2/ja
Priority to EP15828000.8A priority patent/EP3144327A4/fr
Publication of WO2016018103A1 publication Critical patent/WO2016018103A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the present invention relates to a resin composition for a polarizer protective film, a polarizer protective film, and a polarizing plate including the same. More specifically, the superior physical, resin composition, a polarizer protective film for a polarizer protective film having the optical characteristics: relates to a polarizing plate and it comprises.
  • LCDs are one of the most widely used flat panel displays at present.
  • liquid crystal displays are TFT (Thin)
  • a liquid crystal layer is enclosed between the array substrate and the color filter substrate.
  • an electric field is applied to the electrodes on the array substrate and the color filter substrate, the arrangement of the liquid crystal molecules of the liquid crystal charge enclosed therebetween changes, and an image is displayed using the array.
  • the polarizing plate is provided outside the array substrate and the color filter substrate.
  • the polarizer may control polarization by selectively transmitting light in a specific direction among light incident from the backlight and light passing through the liquid crystal layer.
  • the polarizing plate generally has a structure in which a protective film for supporting and protecting the polarizer is adhered to a polarizer capable of polarizing light in a specific direction.
  • the film which consists of triacetyl cellulose (TAC) is used widely.
  • TAC triacetyl cellulose
  • a protective film has been proposed for coating a hard coat layer to achieve a film having high strength and wear resistance properties.
  • these days the use of liquid crystal devices has become widespread, and they have been used in devices of various fields, and interest in improving the strength and thinning of polarizing plates is increasing.
  • the present invention exhibits high strength and high transparency, and the overall polarizing plate can be thinned, and at the same time curl characteristics : resin composition for polarizer protective film, polarizer protective film, excellent coating workability and crack resistance, And it provides a polarizing plate comprising the same.
  • the present invention is a cation-curable monomer; Cationic photopolymerization initiator; Radically curable monomers; And it provides a resin composition comprising a radical photopolymerization initiator.
  • the present invention In addition, the present invention; And a coating layer provided on at least one side of the substrate, wherein the coating layer comprises a cured resin of a cation-curable monomer; And it provides a polarizer protective film comprising a cured resin of a radical curable monomer.
  • a polarizer In addition, the present invention, a polarizer; Adhesive layer; And it provides a polarizing plate comprising the polarizer protective film.
  • the resin composition for polarizer protective film of the present invention is excellent in curl characteristics, surface hardness, film strength, coating workability and crack resistance, and according to the protective film manufactured using the same, high strength, high hardness, scratch resistance, high transparency The occurrence of curls or cracks is reduced and can be usefully applied for the polarizer protective film.
  • a protective film is required on both the upper and lower sides of the polarizer to secure a constant strength and modulus, but according to the polarizing plate of the present invention, the lower protective film may be omitted. To achieve strength and modulus equivalent to or higher than conventional Can be.
  • the polarizer protective film of the present invention is applied only to the upper part of the polarizer, there is no drop in overall strength or modulus, and thus a structure in which the lower protective film having a large retardation value is omitted is possible.
  • the polarizing plate of the structure in which the lower protective film is omitted can be thinned because the overall thickness can be reduced while showing a high strength.
  • FIG. 1 is a view showing the structure of a general polarizing plate.
  • FIG. 2 is a view showing the structure of a polarizing plate according to an embodiment of the present invention.
  • the resin composition of this invention is a cation curable monomer; Cationic photopolymerization initiator; Radically curable monomers; And radical photopolymerization initiators.
  • the polarizer protective film of this invention is a base material; And a coating layer provided on at least one side of the substrate, wherein the coating layer comprises a cured resin of a cation-curable monomer; And cured resins of radically curable monomers.
  • Polarizing plate of the present invention a polarizer; Adhesive layer; And the polarizer protective film.
  • the term 'top surface' refers to a surface that is disposed to face the viewer when the polarizer is mounted on the device.
  • the "upper” means the direction toward the viewer when the polarizer is mounted on the device.
  • 'lower' or 'lower' means the opposite side of the viewer when the polarizer is mounted on the device. Means a face or direction disposed to face.
  • Resin composition according to an aspect of the present invention, a cation-curable monomer; Cationic photopolymerization initiator; Radically curable monomers; And radical photopolymerization initiators.
  • the resin composition of the present invention is a coating composition used to form a polarizer protective film used for protecting the polarizer from the outside.
  • polarizer protective films include polyesters such as polyethylene terephthalate (PET), cyclic olefin copolymers (COC), polyacrylates (polyacrylates, PACs), and polycarbonates ( polycarbonate, PC), polyethylene (PE), polymethylmethacrylate (PMMA), polyetheretherketon (PEEK), polyethylenenaphthalate (PEN), polyetherimide (PEI) And substrates made of polyimide (PI) or triacetylcellulose (TAC).
  • PET polyethylene terephthalate
  • COC cyclic olefin copolymers
  • PES polyacrylates
  • PACs polycarbonates
  • PC polycarbonate
  • PE polyethylene
  • PMMA polymethylmethacrylate
  • PEEK polyetheretherketon
  • PEN polyethylenenaphthalate
  • PEI polyetherimide
  • triacetyl cellulose (TAC) films are particularly used because of their excellent optical properties.
  • TAC triacetyl cellulose
  • the surface hardness is weak and vulnerable to humidity, so it is necessary to add a functional coating layer such as hard coating using an ultraviolet curable resin.
  • a method of improving the surface hardness of the coating layer a method of increasing the thickness of the hard coating layer may be considered.
  • the surface hardness may be increased, but the curl may increase due to curing shrinkage and cracking or peeling of the coating layer may occur. Since it becomes easy, it is not easy to apply practically.
  • such curing shrinkage is a problem when curing the acrylate-based binder do.
  • Acrylate-based binders which are frequently used as UV-curable resins, are used for the purpose of forming a coating layer of high hardness by showing a high film strength after curing, but in a manner in which double bonds of the acrylate-based binder are crosslinked and cured, Is short, hardening shrinkage phenomenon occurs, resulting in a decrease in adhesion between the substrate and the curling or cracking of the coating layer.
  • the present invention provides a protective film having a layered film strength and surface hardness and less curing shrinkage and no problem of curling or cracking, a resin composition used in the preparation thereof, a polarizer protective film and the polarizing plate including the protective film. do. Furthermore, the protective film of this invention can exhibit the outstanding optical characteristic calculated
  • a protective film under the polarizer may be omitted and a protective film of the present invention may be provided only on the upper part in order to realize a clear image quality. That is, when applying the polarizer protective film of the present invention to the polarizing plate, it is possible to omit the lower polarizer protective film included in the prior art to ensure a constant modulus, so that the thickness of the polarizing plate is reduced without a decrease in the overall strength of the polarizer, the phase difference value Low low phase difference polarizers and displays can be provided.
  • the resin composition of the present invention for realizing the above properties includes a bivalent curable monomer, a bivalent photopolymerization initiator, a radical curable monomer, and a radical photopolymerization initiator.
  • the cationically curable monomer is a monomer in which curing is initiated by a cation generated from a different photopolymerization initiator by ultraviolet irradiation, for example, an epoxy group, an oxetane group, a vinyl ether group, or It may be a monomer including a functional group such as a siloxane group.
  • the bivalent curable monomer may be a compound including at least one epoxy group.
  • the cationically curable monomer has one or more cationically curable functional groups in the molecule, preferably may comprise two or more cationically curable functional groups in the molecule. It may also be desirable to include one or more cycloalkyl groups in the molecule.
  • a cation-curable monomer having a structure containing a cycloalkyl group in the molecule as described above a certain distance between the molecules is ensured even after curing due to the void occupied by the cycloalkyl group can reduce the curing shrinkage of the coating layer. Accordingly, it is possible to improve the curl characteristics of the coating layer generated by the curing shrinkage of the radical curable monomer such as an acrylate binder.
  • the cycloalkyl group may include one or two or more ring compounds, and the two or more rings may be simply connected to each other or connected by another linking group. Or the two or more rings may be present in a condensed (f sed) form sharing one or more carbon atoms.
  • the cycloalkyl group is not limited thereto, and may be, for example, a compound having 3 to 90 carbon atoms.
  • the cationically curable monomer including a cycloalkyl group is cured by a cation generated from a cationic photopolymerization initiator to form a crosslinked structure, and the formed crosslinked structure is excellent in flexibility and elasticity. Therefore, the protective film formed by using the resin composition comprising the same, while securing the mechanical properties can be secured high elasticity or flexibility, the coating workability is good and can also minimize the occurrence of curl or stack.
  • the cationically curable monomers may be used alone or in combination with one another.
  • the weight average molecular weight of the cationically curable monomer is not particularly limited, but may have a range of, for example, about 1,000 to less than about 1,500 g / mol. If the weight average molecular weight is too large, compatibility with the protective film to be produced may be reduced or the film strength of the coating film may be lowered. From this point of view, the weight average molecular weight of the cationically curable monomer is preferably less than about 1,500 g / mol.
  • the total weight of the resin composition is 100 parts by weight, about 20 to about 90 parts by weight, or about 30 to about 85 parts by weight, or about 40 to about 85 parts by weight of the cationically curable monomer It may be included in parts by weight.
  • Particular implementation and coating of mechanical properties including the film strength of the coating layer In view of workability, the above-described weight range may be preferable.
  • the resin composition of this invention contains the cationic photoinitiator which starts hardening of the said cationically curable monomer by generating a cation by ultraviolet irradiation.
  • cationic photopolymerization initiator for example, an onium salt, an organometallic salt, or the like may be used, but the present invention is not limited thereto. Specifically, a diarylodonium salt, a triarylsulfonium salt, an aryldiazonium salt, an iron-arene complex, etc.
  • an aryl sulfonium nucleofluorofluoromonium salt an aryl sulfony Um nucleus fluorophosphate salts, diphenyldiodonium nucleus fluorophosphate salts, diphenyldiodonium nucleus antimony salts, ditoryliodonium nucleus fluorophosphate salts, 9- (4-hydroxyethoxyphenyl) cysteine It may include, but is not limited to, one or more selected from the group consisting of nium nucleophosphate salts and the like.
  • the cationic photopolymerization initiator when the total weight of the resin composition is 100 parts by weight, may include about 0.01 to about 5 parts by weight or about 0.1 to about 1 part by weight. When the cationic photopolymerization initiator is included in the above-described range, proper cation initiated photopolymerization may occur without deteriorating the physical properties of the composition.
  • the resin composition of this invention contains a radical photoinitiator for starting hardening of a radical curable monomer and the said radical curable monomer in addition to the said cation curable monomer as a binder.
  • the radical curable monomer is a monomer in which curing is initiated by free radicals generated from a radical photopolymerization initiator by ultraviolet irradiation.
  • the radical curable monomer may be a polyfunctional acrylate monomer.
  • the multifunctional acrylate monomer may include two or more acrylate functional groups, for example, 2 to 6 and a molecular weight of less than l, 000 g / mol. More specifically, for example, nucleic acid diol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), ethylene glycol Diacrylate (EGDA), trimethylolpropane triacrylate (TMPTA), trimethyl to propaneethoxy triacrylate (TMPEOTA), glycerin propoxylated triacrylate (GPTA), pentaerythritol tri (tetra) acrylate (PETA) or dipentaerythrane may include nuxaacrylate (DPHA) and the like, but the present invention is not limited thereto.
  • the polyfunctional acrylate monomer serves to further impart a constant pencil hardness and wear resistance to the protective film together with the above-described cation-curable monomer.
  • the total weight of the resin composition is 100 parts by weight, about 5 to about 70 parts by weight, or about 10 to about 60 parts by weight, about 15 to about 50 parts by weight of the radical curable monomer It can be included as a wealth. If the content of the radically curable monomer is too large than the above-mentioned range, there may be curl generation due to curing shrinkage, and when the radically curable monomer is included too little, the effect of improving the mechanical properties of the protective film may not be improved.
  • the weight ratio of the cationically curable monomer and the radical curable monomer is about 2: 8 to about 9: 1, preferably about 3: 7 to about 9: 9. 1, more preferably about 4: 6 to about 9: 1.
  • the protective film of the present invention may have a film strength improving effect and good curl characteristics without deterioration of other mechanical properties.
  • the protective film obtained by using the resin composition having a weight ratio of the cationically curable monomer and the radical curable monomer in the range of about 4: 6 to about 9: 1 may have excellent balance between curl and strength.
  • the resin composition of this invention also contains the radical photoinitiator which starts hardening of the said radical curable monomer by generating a radical by ultraviolet irradiation.
  • radical photopolymerization initiator examples include 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone,
  • Diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide or bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.
  • Commercially available products include Irgacure 184, Irgacure 500, Irgacure 651, Irgacure 369, Irgacure 907, Darocur 1173, Darocur MBF, Irgacure 819, Darocur TPO, Irgacure 907, and Esacure KIP 100F.
  • These radical photoinitiators can be used individually or in mixture of 2 or more types different from each other.
  • the radical photopolymerization initiator when the total weight of the resin composition is 100 parts by weight, may include about 0.01 to about 5 parts by weight or about 0.1 to about 1 part by weight. When the radical photopolymerization initiator is included in the above-described range, appropriate radical initiation photopolymerization may occur without deteriorating the physical properties of the composition.
  • the resin composition may further include inorganic fine particles to improve the surface hardness of the protective film.
  • the inorganic fine particles may be included in the resin composition in a form dispersed in the cationic curable monomer, the radical curable monomer, or a solvent.
  • the inorganic fine particles may be nanoscale inorganic particles having a particle size of nanoscale, for example, particles having a particle diameter of about loOnm or less, or about 10 to about 100 nm, or about 10 to about 50 nm.
  • the inorganic fine particles may include, for example, silica fine particles, aluminum oxide particles, titanium oxide particles, or zinc oxide particles.
  • the hardness of a protective film can be improved further.
  • the inorganic fine particles when the total weight of the resin composition is 100 parts by weight, may include about 10 to about 80 parts by weight or about 20 to about 70 parts by weight. By including the said inorganic fine particle in the said range, the protective film excellent in both high hardness and a curl characteristic can be formed.
  • the resin composition of the present invention may be used in the form of a solvent-free solvent containing a solvent when the formulation of each component is uniform and has an appropriate viscosity and there is no problem in the coating process.
  • the resin composition of the present invention may further include an organic solvent for uniform blending and coating properties of each component.
  • organic solvent examples include methane, ethane, isopropyl alcohol, alcohol solvents such as butanol, 2-methoxyethane, 2-ethoxyethanol, alkoxy alcohol solvents such as 1-methoxy-2-propanol, Ketone solvents, such as acetone, methyl ethyl ketone, methyl isobutyl ke methyl propyl ketone, cyclonucleanone propylene glycol monopropyl ether, propylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol monopropyl ether ethylene glycol monobutyl ether, di Ether solvents such as ethylene glycol monomethyl ether diethyl glycol monoethyl ether, diethyl glycol monopropyl ether diethyl glycol monobutyl ether, diethylene glycol -2-ethyl nucleosil ether, aromatics such as benzene, toluene and x
  • the content of the organic solvent is not particularly limited because it can be variously adjusted within a range that does not lower the physical properties of the resin composition.
  • the resin composition in addition to the aforementioned cationic curable monomer, radical curable monomer, cationic photopolymerization initiator, radical photopolymerization initiator, inorganic fine particles, organic solvent, UV absorber, surfactant, anti-yellowing agent, leveling agent, antifouling agent, etc. It may further include additives commonly used in the art. In addition, since the content can be variously adjusted within a range that does not lower the physical properties of the protective film of the present invention, it is not particularly limited. According to one embodiment of the present invention, for example, the resin composition may include a surfactant as an additive, and the surfactant may be a 1 to 2 functional fluorine acrylate, a fluorine surfactant or a silicone surfactant.
  • the additive may include a yellowing inhibitor, the yellowing Examples of the inhibitor include benzophenone compounds, benzotriazole compounds, and the like.
  • a polarizer protective film can be formed by photocuring the resin composition of this invention containing a radical curable monomer, a bivalent photoinitiator, a radical photoinitiator, and optionally an inorganic fine particle, an organic solvent, and other additives.
  • the substrate ; And a coating layer provided on at least one side of the substrate, wherein the coating layer provides a polarizer protective film including a cured resin of a cation-curable monomer and a cured resin of a radical curable monomer.
  • the coating layer contains a cured resin of the cationic curable monomer and a cured resin of a radical curable monomer.
  • the protective film of the present invention includes a cured resin in which a cationic curable monomer is cured and a cured resin of a radical curable monomer to secure high strength, high hardness and excellent curl characteristics without deterioration of optical properties. can do.
  • the polarizer protective film of the present invention when applying the polarizer protective film of the present invention to the polarizing plate to omit a protective film of the lower polarizer, which is essentially included in order to secure a film strength of a predetermined level or more, even if the protective film of the present invention is applied only to the upper portion of the polarizer It is possible to realize thinning, high hardness, high strength, low phase difference, and clearer image quality since it is not degraded and can be used in display devices requiring low phase difference values.
  • the coating layer is a cured resin of the bivalent curable monomer, the cation curable monomer and radical curable monomer It may contain a cured resin of, a cured resin of the radical curable monomer, or a mixture thereof.
  • an increase ratio of the cured resin of the cationic curable monomer and the cured resin of the radical curable monomer is about 2: 8 to about 9: 1, preferably about 3: 7 to about 9: 1, More preferably about 4: 6 to about 9 : may be one.
  • the protective film of the present invention may have sufficient curl characteristics without deterioration of mechanical properties.
  • the coating layer contains a cured resin of a cationic curable monomer and a curable resin of a radical curable monomer at about 4: 6 to about 9: 1, curling hardly occurs, and thus, very good curl characteristics can be exhibited.
  • the coating layer may further include inorganic fine particles.
  • the inorganic fine particles may be included in a form dispersed in the cured resin.
  • the inorganic fine particles may be inorganic fine particles having a nanoscale particle diameter, for example, nanoparticles having a particle diameter of about 100 nm or less, or about 10 to about 100 nm, or about 10 to about 50 nm.
  • the inorganic fine particles may include, for example, silica fine particles, aluminum oxide particles, titanium oxide particles, zinc oxide particles, and the like.
  • the hardness of a protective film can be improved further.
  • the inorganic fine particles when the total weight of the coating layer is 100 parts by weight, may be included in an amount of about 10 to about 80 parts by weight, or about 20 to about 70 parts by weight.
  • the inorganic fine particles By including the inorganic fine particles in the above range, it is possible to provide a protective film excellent in both hardness and curl properties.
  • the coating layer is a range that satisfies both sufficient film strength and curl characteristics, for example about 2 or more, for example about 2 to about 50 zm, or about 5 to about 40 / ⁇ , or about It may have a thickness of 10 to about 30 / im, or about 20 to about 30.
  • the coating layer of the present invention can exhibit a good curling property even when coating a thick film of 20 an or more by simultaneously comprising a cured resin of a bi-curable monomer and a cured resin of a radical curable monomer.
  • the protective film of the present invention may have a thickness of about 30 or more, for example, about 30 to about 100 / m, or about 30 to about 70, or about 35 to about 60 ⁇ .
  • the polarizer protective film of the present invention as described above is a resin composition comprising a cationic curable monomer, a cationic photopolymerization initiator, a radical curable monomer, a radical photopolymerization initiator, and optionally inorganic fine particles, an organic solvent, and other additives as described above on a substrate. It can be formed by coating and photocuring.
  • the polarizer protective film of this invention can be manufactured by apply
  • polyester such as polyethyleneterephtalate (PET), polyethylene such as ethylene vinyl acetate (EVA), cyclic olefin Polymer (cyclic olefin polymer, COP), cyclic olefin copolymer (COC), polyacrylate (polyacrylate, PAC), polycarbonate (PC), polyethylene (PE, PE), polymethylmethacryl Polymethylmethacrylate (PMMA), polyetheretherketon (PEEK), polyethylenenaphthalate (PEN), polyetherimide (PEI), polyimide (PI), triacetylcellulose , TAC), MMA (methyl methacrylate), or a film containing a fluorine-based resin, etc., preferably using a TAC film There.
  • PET polyethyleneterephtalate
  • EVA ethylene vinyl acetate
  • COP cyclic olefin Polymer
  • COC cyclic olefin copolymer
  • PC polyacrylate
  • PE PE
  • PE
  • the substrate may be a single layer or a multilayer structure including two or more substrates made of the same or different materials as necessary, but is not particularly limited.
  • the thickness of the substrate is not particularly limited, and a film having a thickness of about 20 to about 200 / ⁇ , or about 20 to about 100 / m, or about 20 to about 50 may be mainly used.
  • the protective film of the present invention is generally high even when using a thin film substrate having a thickness of less than or equal to the high strength characteristic of the coating layer. Strength and modulus can be shown.
  • the method of applying the resin composition is not particularly limited as long as it can be used in the technical field to which the present technology belongs, and for example, a bar coating method, a knife coating method, a coating method, a blade coating method, a die coating method, and a microgravure coating method. Method, comma coating method, slot die coating method, lip coating method, or solution casting method.
  • the protective D film can be formed by irradiating the applied resin composition with ultraviolet rays to perform photocuring reaction. Before irradiating the ultraviolet rays, a process of flattening the coated surface of the resin composition and drying to volatilize the solvent included in the composition may be further performed.
  • the irradiation amount of ultraviolet rays may be, for example, about 20 to about 600 mJ / cm 2 .
  • the light source for ultraviolet irradiation is not particularly limited as long as it can be used in the art to which the present technology belongs, and for example, a high pressure mercury lamp, a metal halide lamp, a black light fluorescent lamp, or the like can be used.
  • the protective film of the present invention exhibits high strength, high strength, excellent curl properties, scratch resistance, high transparency, and excellent optical properties, and thus can be used as a polarizer protective film and can be usefully used in various polarizing plates.
  • the coating layer may be formed only on one side of the substrate, or both sides of the substrate.
  • the polarizer It provides a polarizing plate comprising an adhesive layer and the polarizer protective film.
  • Base materials for the protective film And a coating layer provided on at least one side of the substrate, wherein the coating layer includes a cured resin of a cationic curable monomer and a curable resin of a radical curable monomer, and a detailed description thereof is as described in the polarizer protective film. .
  • the polarizer exhibits a property of extracting only light vibrating in one direction from incident light while vibrating in various directions. This property can be achieved by stretching polyvinyl alcohol (PVA) absorbing iodine with strong tension. For example, more specifically, swelling by swelling the PVA film in an aqueous solution to swell, wherein the swelled PVA film has a polarization property. Dyeing with a dichroic substance to be imparted, stretching the dyed PVA film to arrange the dichroic dye materials side by side in the stretching direction, and correcting the color of the PVA film subjected to the stretching step
  • the polarizer may be formed through a complementary color step.
  • the polarizing plate of the present invention is not limited thereto.
  • the polarizing plate of the present invention includes a protective film provided on at least one surface of the polarizer.
  • the polarizing plate of this invention contains an adhesive bond layer between the said polarizer and a polarizer protective film.
  • the adhesive layer may include a polarizer adhesive, which may have transparency and maintain polarization characteristics of the polarizer.
  • a polarizer adhesive which may have transparency and maintain polarization characteristics of the polarizer.
  • Usable adhesives are not particularly limited as long as they are known in the art. For example, there are one-component or two-component polyvinyl alcohol (PVA) adhesives, acrylic adhesives, polyurethane adhesives, epoxy adhesives, styrene butadiene rubber (SBR) adhesives, or hot melt adhesives. It is not limited only to an example.
  • PVA polyvinyl alcohol
  • SBR styrene butadiene rubber
  • the thickness of the adhesive layer may be about 0.1 to about 10, or about ⁇ to about 5, but the present invention is not limited only to these examples.
  • the polarizing plate of the present invention can be obtained by laminating and bonding the polarizer protective film to the polarizer using an adhesive.
  • the protective film may be attached to both sides of the polarizer.
  • the protective film may be attached only to one surface of the polarizer, and the other surface may be attached to another general protective film such as TAC.
  • the protective film of the present invention may be attached only to one surface of the polarizer, and the protective film may be omitted on the other surface. That is, the polarizing plate according to the embodiment of the present invention includes a polarizer, an adhesive layer provided on the polarizer, and a polarizer protective film provided on the adhesive layer, and the lower surface of the polarizer does not include a polarizer protective film. You may not. As described above, even if the protective film of the lower polarizer is omitted and the protective film of the present invention is applied only to the upper part of the polarizer, the film strength is not lowered and thus thinning is possible.
  • the film strength or modulus does not decrease, it is possible to provide a high strength polarizing plate of low phase difference. Accordingly, a clearer image quality can be realized and can be used in a display device requiring a low phase difference value.
  • Figure 1 is a view showing the structure of a general polarizing plate
  • Figure 2 is a view showing the structure of a polarizing plate according to an embodiment of the present invention.
  • the conventional general polarizing plate 100 protects the upper polarizer 5 to protect the polarizer 5, respectively, with respect to the polarizer 5 and the adhesive layers 6 and 4 on the upper and lower surfaces of the polarizer 5. It has a structure in which the film 7 and the lower protective film 3 are laminated.
  • the lower surface of the lower protective film 3 is provided with a pressure-sensitive adhesive layer 2 for adhering the polarizing plate 100 to an adherend such as another layer or a film, and additionally a release film for protecting the pressure-sensitive adhesive layer 2 ( 1) may be provided.
  • the release film 1 is peeled later.
  • FIG. 2 the structure of the polarizing plate according to the exemplary embodiment of the present invention is illustrated in FIG. 2.
  • the polarizing plate 200 is a protective film for protecting the polarizer 30, and an upper protective film 50 having an upper adhesive layer 40 on the upper surface of the polarizer 30.
  • Only the lower adhesive layer and the lower protective film as shown in Figure 1 may have a structure to omit. Therefore, only the release film 10 for protecting the pressure-sensitive adhesive 20 and the pressure-sensitive adhesive layer 20 for attaching the polarizing plate 200 to the lower surface of the polarizer 30 may be provided without the lower protective film.
  • a lower protective film is essential to compensate for the low modulus of the pressure-sensitive adhesive layer 2, that is, to improve the polarizing plate pressing phenomenon caused by the pressure-sensitive adhesive layer having a low modulus.
  • a method of increasing the thickness of the coating layer may be considered as a method of improving the strength of the coating layer. have.
  • it is necessary to realize a high thickness of the coating layer but as the thickness of the coating layer is increased, the strength may be increased, but wrinkles or curls increase due to curing shrinkage, and cracking or peeling of the coating layer may occur.
  • the polarizing plate according to an embodiment of the present invention has a protective film having a sufficient strength and less curing shrinkage and thus does not have a problem of curl or crack, and applies such a protective film only to the polarizer at the top and omits the lower protective film. Even if it prevents the pressing phenomenon by the pressure-sensitive adhesive layer can exhibit high strength and high modulus.
  • the polarizer protective film of the present invention and the polarizing plate including the same may exhibit high strength and low phase difference characteristics and may be used without limitation in various display devices.
  • the polarizer protective film of the present invention when stored in a cut-on to 10cm X 10cm for 24 hours and placed in a plane, each corner or one side of the distance spaced from the plane
  • the average value may represent 50 mm or less, or 30 mm or less, or about 20 mm or less.
  • the pencil hardness measured at 500g load according to ASTM D3363 may be H or more, or 3H or more, or 4H or more.
  • the polarizer protective film of the present invention may have a light transmittance of 90% or more, or 91% or more, and a haze of 2% or less, or 1% or less, or 5% or less.
  • the polarizing plate according to an embodiment of the present invention nano indentation (Nano at least about 4 GPa, or at least about 5 GPa, or at least about 6 GPa, as measured by an indentation method; And modulus of about 9 GPa or less, or about 8 GPa or less, or about 7 GPa or less.
  • the polarizing plate according to an embodiment of the present invention when measured by the nanoindentation method, about 0.4GPa or more, or about 0.5GPa or more, or about 0.6GPa or more; And a hardness of about l.OGPa or less, or about 0.9 GPa or less, or about 0.8 GPa or less.
  • the polarizing plate may be a twisted nematic (TN), a super twisted nematic (STN) liquid crystal, an in-plane switching (IPS), a super-IPS, a fringe field switching (FFS), or the like. May be a polarizing plate for horizontal alignment mode, or may be a polarizing plate for vertical alignment mode.
  • TN twisted nematic
  • STN super twisted nematic
  • IPS in-plane switching
  • FFS fringe field switching
  • the resin composition was applied to one side of a TAC film having a thickness of 25. After drying for 2 minutes at 60 ° C., about 200 mJ / cm 2 was irradiated with a metal halide lamp to obtain a protective film. After curing was completed, the thickness of the coating layer was 20 zm.
  • the protective film was laminated by laminating with a PVA film so that the thickness of the adhesive layer was approximately 2 using an acrylic adhesive.
  • a polarizing plate was prepared by laminating a 12i ⁇ m thick adhesive film on glass without a protective film.
  • Example 3 The rest of the process was the same as in Example 1 to prepare a protective film and a polarizing plate.
  • Example 3 The rest of the process was the same as in Example 1 to prepare a protective film and a polarizing plate.
  • Yi is 5 g of celloxide 8000 (manufactured by Daicel) as a curable monomer, 7 g of pentaerythritol tri (tetra) acrylate (PETA) as a radical curable monomer, cationic photopolymerization initiator (trade name UVI-6976, Dow chemical) 0.05 g, radical A resin composition was prepared by mixing 0.1 g of a photopolymerization initiator (trade name Irgacure 184), 30 g of surface modified colloidal silica MEK-AC-2140Z (manufactured by Nissan chemical, 30% solids), and 5 g of MEK.
  • a photopolymerization initiator trade name Irgacure 184
  • surface modified colloidal silica MEK-AC-2140Z manufactured by Nissan chemical, 30% solids
  • Example 4 The rest of the process was the same as in Example 1 to prepare a protective film and a polarizing plate.
  • Example 4 The rest of the process was the same as in Example 1 to prepare a protective film and a polarizing plate.
  • Example 1 The rest of the process was the same as in Example 1 to prepare a protective film and a polarizing plate. Comparative Example 1
  • a resin composition was prepared by mixing pentaerythritol with 10 g of tri (tetra) acrylate (PETA), 0.1 g of a radical photopolymerization initiator (trade name Irgacure 184), and 5 g of MEK as a radical curable monomer.
  • Example 2 The rest of the process was the same as in Example 1 to prepare a protective film and a polarizing plate. Comparative Example 2
  • a protective film was prepared in the same manner as in Comparative Example 1 except that 30 g of surface-modified colloidal silica MEK-AC-2140Z (manufactured by Nissan chemical, 30% solids) was further mixed.
  • Example 3 The rest of the process was the same as in Example 1 to prepare a protective film and a polarizing plate. Comparative Example 3
  • Example 2 The rest of the process was the same as in Example 1 to prepare a protective film and a polarizing plate.
  • Each polarizer protective film was cut into 10 cm and 10 cm, and stored at room temperature for 24 hours, and then, when placed on a plane, the average value of the distance from one side of each corner to the plane was measured.
  • the distance which a protective film curled and separated from a plane cannot be measured, it described as NG.
  • the polarizer protective films of Examples and Comparative Examples were laminated by laminating the PVA film and one side using an acrylic adhesive so that the thickness of the adhesive layer was approximately 2 ⁇ 2 ⁇ m thick adhesive without the protective film on the other side of the PVA film. Only the film was attached and the polarizing plate with the adhesive film attached thereto was measured under the following measurement conditions using a Nanoindenter XP instrument of MTS.
  • Poissons Ratio (0.18), Surface Approach Velocity (10 nm / s), Depth Limit (1000 nm), Delta X For Finding Surface (-50 ⁇ ), Delta Y For Finding Surface (-50 ⁇ ), Strain Rate Target (0.05 / s), Allowable Drift Rate (0.3 nm / s), Harmonic Displacement Target ( 2 nm), Approach Distance to store (1000 nm), Frequency Target (45 Hz), Surface Approach Distance (1000 nm), Surface Approach Sensitivity (20%) The measurement results of the physical properties are shown in Tables 1 and 2 below.
  • the protective film of the embodiment of the present invention showed a good curl characteristics when evaluated by a method of measuring the distance the protective film is separated from the plane while showing a pencil hardness of 3H to 4H. It also showed high strength and modulus.
  • Table 2 in the case of Comparative Examples 1 to 2, the film curled in a cylinder due to curing shrinkage. The curl characteristics were very poor, and the strength and the modulus did not reach the present invention.
  • Comparative Example 3 the curl properties were relatively good, but pencil hardness, strength, modulus, scratch resistance, and other physical properties were found to be insufficient.

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  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

La présente invention concerne : une composition de résine pour un film protecteur de polariseur ; un film protecteur de polariseur ; et une plaque de polarisation le comprenant, et plus particulièrement : une composition de résine pour un film protecteur de polariseur, présentant une résistance élevée et d'excellentes caractéristiques ; un film protecteur de polariseur ; et une plaque de polarisation le comprenant. Selon la présente invention, la plaque de polarisation présente une résistance élevée, d'excellentes caractéristiques d'incurvation et propriétés optiques, et peut donc être utile dans divers domaines.
PCT/KR2015/008001 2014-07-30 2015-07-30 Composition de résine pour film protecteur de polariseur, film protecteur de polariseur, et plaque polarisante le comprenant WO2016018103A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US15/329,563 US20170210915A1 (en) 2014-07-30 2015-07-30 A resin composition for a polarizer protective film, a polarizer protective film, and a polarizing plate comprising the same
CN201580038438.1A CN106536573B (zh) 2014-07-30 2015-07-30 用于起偏器保护膜的树脂组合物、起偏器保护膜和包括其的偏光板
JP2017503570A JP6638157B2 (ja) 2014-07-30 2015-07-30 偏光子保護フィルム用樹脂組成物、偏光子保護フィルム、およびこれを含む偏光板
EP15828000.8A EP3144327A4 (fr) 2014-07-30 2015-07-30 Composition de résine pour film protecteur de polariseur, film protecteur de polariseur, et plaque polarisante le comprenant

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2014-0097314 2014-07-30
KR20140097314 2014-07-30
KR1020150107552A KR101748409B1 (ko) 2014-07-30 2015-07-29 편광자 보호 필름용 수지 조성물, 편광자 보호 필름, 및 이를 포함하는 편광판
KR10-2015-0107552 2015-07-29

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JP5291919B2 (ja) * 2007-11-20 2013-09-18 富士フイルム株式会社 ディスプレイ表面に用いる偏光板用保護フィルム又は画像表示装置前面板用フィルム
WO2014058042A1 (fr) * 2012-10-11 2014-04-17 東亞合成株式会社 Composition d'adhésif photodurcissable, polariseur et processus de production de celui-ci, élément optique et dispositif d'affichage à cristaux liquides

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JPH06123807A (ja) * 1992-10-12 1994-05-06 Konica Corp セルロースエステルフィルム
JP2007108765A (ja) * 1999-03-11 2007-04-26 Konica Minolta Holdings Inc 反射防止材、反射防止材の製造方法、偏光板保護フィルム、及び偏光板
JP5291919B2 (ja) * 2007-11-20 2013-09-18 富士フイルム株式会社 ディスプレイ表面に用いる偏光板用保護フィルム又は画像表示装置前面板用フィルム
JP2011052161A (ja) * 2009-09-04 2011-03-17 Toyo Ink Mfg Co Ltd 紫外線硬化性組成物、それを用いた偏光板及びその製造方法
WO2014058042A1 (fr) * 2012-10-11 2014-04-17 東亞合成株式会社 Composition d'adhésif photodurcissable, polariseur et processus de production de celui-ci, élément optique et dispositif d'affichage à cristaux liquides

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CN108780177A (zh) * 2016-03-28 2018-11-09 日东电工株式会社 偏振膜、带粘合剂层的偏振膜、偏振膜的制造方法及图像显示装置
CN108780177B (zh) * 2016-03-28 2021-02-05 日东电工株式会社 偏振膜、带粘合剂层的偏振膜、偏振膜的制造方法及图像显示装置
US11079526B2 (en) 2016-03-28 2021-08-03 Nitto Denko Corporation Polarizing film, pressure-sensitive-adhesive-layer-attached polarizing film, method for producing polarizing film, and image display device

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