WO2015046999A1 - Polarizing plate and image display apparatus comprising same - Google Patents
Polarizing plate and image display apparatus comprising same Download PDFInfo
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- WO2015046999A1 WO2015046999A1 PCT/KR2014/009130 KR2014009130W WO2015046999A1 WO 2015046999 A1 WO2015046999 A1 WO 2015046999A1 KR 2014009130 W KR2014009130 W KR 2014009130W WO 2015046999 A1 WO2015046999 A1 WO 2015046999A1
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- 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
-
- 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
Definitions
- the present invention relates to a polarizing plate and an image display device including the same, and more particularly, to a polarizing plate excellent in adhesion between a polarizer and a protective layer, excellent in water resistance, and thinly manufactured, and an image display device including the same. will be.
- the polarizing plate has been commonly used in a structure in which a protective film is laminated on both sides of a polarizer made of a polyvinyl alcohol (hereinafter referred to as 'PVA')-based resin dyed with a dichroic dye or iodine.
- 'PVA' polyvinyl alcohol
- the triacetyl cellulose (TAC, triacetyl cellulose) -based film has been used a lot of films in terms of excellent optical transparency and moisture permeability.
- the active energy ray-curable composition proposed to date can be divided into a radical curable composition and a cationic curable composition according to the curing method.
- the transparent thin film layer is formed using the cation-curable composition, there is an advantage of having excellent adhesion with the polarizer, but has a number of disadvantages in the manufacturing process due to the slow curing rate and low curing degree.
- the new polarizing plate which is excellent in the adhesiveness of a polarizer and a protective layer, and excellent in water resistance is calculated
- the present invention is to solve the above problems, to provide a polarizing plate excellent in the adhesion between the polarizer and the protective layer, excellent in water resistance, and can be manufactured in a thin shape and an image display device including the same.
- the present invention is a polarizer; And a protective layer formed on at least one surface of the polarizer, wherein the protective layer comprises: (A) a radical polymerizable compound including at least one hydrophilic functional group in a molecule; (B) a polyfunctional (meth) acrylic compound; (C) phosphate compounds containing one or two (meth) acryl groups in a molecule; And (D) a polarizing plate which is a cured product of a radical curable composition containing a radical initiator.
- the radical curable composition is 30 parts by weight or more and 93 parts by weight or less with respect to 100 parts by weight of the radical curable composition, (A) a radically polymerizable compound including at least one hydrophilic functional group in a molecule; (B) 5 to 40 parts by weight of the multifunctional (meth) acrylic compound; (C) 1 to 40 parts by weight of a phosphate compound containing one or two (meth) acryl groups in the molecule; And (D) 0.5 to 20 parts by weight of a radical initiator.
- A a radically polymerizable compound including at least one hydrophilic functional group in a molecule
- B 5 to 40 parts by weight of the multifunctional (meth) acrylic compound
- C 1 to 40 parts by weight of a phosphate compound containing one or two (meth) acryl groups in the molecule
- D 0.5 to 20 parts by weight of a radical initiator.
- the total hydroxyl value of the radical curable composition is preferably 500 to 900 mg ⁇ KOH / g.
- the hydrophilic functional group of the said (A) radically polymerizable compound is a hydroxyl group.
- the (A) radically polymerizable compound uses a mixture of a radically polymerizable compound having one hydroxy group in the molecule (a-1) and a radically polymerizable compound having at least two hydroxy groups in the molecule (a-2) It is more preferable.
- the (b) radically polymerizable compound preferably has an acid value of 100 to 1000 mg ⁇ KOH / g.
- the (B) polyfunctional (meth) acrylic compound preferably includes one or more selected from the group consisting of compounds represented by the following [Formula I] to [Formula III].
- R 1 and R 2 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group.
- R 3 , R 4 and R 5 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group
- R 6 is a (meth) acryloyloxy group, (meth ) Acryloyloxyalkyl group, a hydroxy group, or a substituted or unsubstituted C 1-10 alkyl group.
- R 7 is substituted or unsubstituted C 1-10 alkylene
- R 8 and R 9 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group.
- the (C) phosphate compound preferably includes a compound represented by the following [Formula IV].
- R 10 is a substituted or unsubstituted C 1 ⁇ 10 alkyl group, a substituted or unsubstituted C 4 ⁇ 14 cycloalkyl group, a substituted or unsubstituted C 6 ⁇ 14 aryl group, or their Combination;
- R 11 is hydrogen or a methyl group;
- the protective layer preferably has a thickness of 0.5 to 20 ⁇ m.
- the polarizing plate of the present invention may be further attached to the protective film via the adhesive layer on the opposite side of the surface on which the protective layer of the polarizer is formed.
- the polarizing plate of the present invention may further include an adhesive layer on the protective layer.
- the present invention provides an image display device including the polarizing plate.
- the polarizing plate of this invention is excellent in the adhesiveness of a polarizer and a protective layer, and is excellent in water resistance, such as being able to prevent the discoloration of the iodine ion in a polarizer even in a high humidity environment.
- the polarizing plate of the present invention has a thin protective layer compared to the polarizing plate having a conventional transparent protective film, it can be manufactured in a thin shape.
- the present inventors have conducted extensive research and used a mixture of a polyfunctional (meth) acrylic compound and a phosphate compound having one or two (meth) acryl groups in a molecule to a radical curable composition having a hydrophilic functional group for forming a protective layer. In this case, it was found that the adhesion and water resistance is excellent, and completed the present invention.
- the radical curable composition of this invention is a polarizer; And a protective layer formed on at least one surface of the polarizer, wherein the protective layer comprises: (A) a radical polymerizable compound including at least one hydrophilic functional group in a molecule; (B) a polyfunctional (meth) acrylic compound; (C) phosphate compounds containing one or two (meth) acryl groups in a molecule; And (D) hardened
- the polarizer of the present invention may use a film made of polyvinyl alcohol (PVA) containing a polarizer well known in the art, for example, iodine or dichroic dye.
- PVA polyvinyl alcohol
- the polarizer may be prepared by dyeing iodine or dichroic dye on a polyvinyl alcohol film, but a method of manufacturing the same is not particularly limited.
- the polarizer means a state not including a protective layer (or protective film), and the polarizing plate means a state including a polarizer and a protective layer (or protective film).
- the polyvinyl alcohol-based film can be used without particular limitation as long as it contains a polyvinyl alcohol resin or a derivative thereof.
- examples of the derivative of the polyvinyl alcohol resin include, but are not limited to, polyvinyl formal resin, polyvinyl acetal resin, and the like.
- the polyvinyl alcohol-based film may be a commercially available polyvinyl alcohol-based film commonly used in the manufacture of polarizers in the art, for example, P30, PE30, PE60 manufactured by Gurere, M3000 M6000 manufactured by Japan Synthetic, and the like. .
- the polyvinyl alcohol-based film is not limited to this, but the degree of polymerization is preferably about 1,000 to 10,000, preferably 1,500 to 5,000. This is because when the degree of polymerization satisfies the above range, the molecular motion is free and can be mixed flexibly with iodine or dichroic dye.
- the protective layer of the present invention is formed using the radical curable composition to support and protect the polarizer, it may be formed by a method well known in the art.
- the radical curable composition is applied to one surface of the polarizer by a coating method well known in the art such as spin coating, bar coating, roll coating, gravure coating, blade coating, and the like to form a protective layer. It may be carried out by a method of curing through active energy ray irradiation.
- the active energy ray irradiation method is not particularly limited, and for example, may be performed by irradiating an ultraviolet ray of about 10 to 2500 mJ / cm 2 using an ultraviolet ray irradiation apparatus (fusion lamp, D bulb).
- the radical curable composition of the present invention as described above (A) a radically polymerizable compound containing at least one hydrophilic functional group in the molecule; (B) a polyfunctional (meth) acrylic compound; (C) phosphate compounds containing one or two (meth) acryl groups in a molecule; And (D) a radical initiator.
- the radical curable composition of the present invention in 100 parts by weight of the radical curable composition, (A) more than 30 parts by weight and 93 parts by weight or less of the radically polymerizable compound containing at least one hydrophilic functional group in a molecule; (B) 5 to 40 parts by weight of the multifunctional (meth) acrylic compound; (C) 1 to 40 parts by weight of a phosphate compound containing one or two (meth) acryl groups in the molecule; And (D) 0.5 to 20 parts by weight of radical initiator.
- the radically polymerizable compound included in the radical curable composition according to the present invention is a component for implementing adhesion between the polarizer and the protective layer, and has at least one hydrophilic functional group in the molecule to realize adhesion through hydrogen bonding.
- the radical polymerizable compound is capable of radical polymerization by the presence of an unsaturated double bond between carbons in the molecule, it can be used without particular limitation.
- the hydrophilic functional group is not particularly limited as long as it is possible to hydrogen bond such as hydroxy group, carboxyl group, urethane group, amine group, amide group, etc. Among them, the hydroxy group is particularly preferable for the implementation of excellent adhesion.
- the radically polymerizable compound is not limited thereto, and may be, for example, a compound represented by the following [Formula 1] to [Formula 24]. These can be used individually or in mixture.
- the radically polymerizable compound is not limited thereto, and in particular, the radically polymerizable compound having one hydroxyl group in the molecule (a-1) (for example, the above [Formula 1] to [Formula 6], etc.) ) And a mixture of (a-2) radically polymerizable compounds having at least two hydroxy groups in the molecule (for example, [Formula 7] to [Formula 24], etc.) in terms of excellent adhesion and heat resistance desirable.
- a-1 for example, the above [Formula 1] to [Formula 6], etc.
- a mixture of (a-2) radically polymerizable compounds having at least two hydroxy groups in the molecule for example, [Formula 7] to [Formula 24], etc.
- the content of the radically polymerizable compound of the present invention is more than 30 parts by weight and 93 parts by weight or less, preferably 35 to 90 parts by weight, and more preferably 45 to 90 parts by weight based on 100 parts by weight of the radical curable composition. It may be part by weight. If it is included in such a content because it is possible to implement excellent adhesion.
- the polyfunctional (meth) acrylic compound included in the radical curable composition according to the present invention is a component for improving the water resistance by increasing the degree of crosslinking in the protective layer and showing stable physical properties even in a high humidity environment.
- Various well-known polyfunctional (meth) acrylic compounds can be used without particular limitation.
- the compounds corresponding to the above-mentioned (A) compounds and the (C) compounds described later are excluded from the polyfunctional (meth) acrylic compounds.
- examples of the polyfunctional (meth) acrylic compound include ethylene glycol di (meth) acrylate, 1,3-butanedioldi (meth) acrylate, and 1,4-butanedioldi (meth).
- the present invention is not limited thereto, but the polyfunctional (meth) acrylic compound is more preferably one or more selected from the group consisting of compounds represented by the following [Formula I] to [Formula III]. This is because the water resistance improvement effect is more excellent.
- R 1 and R 2 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group.
- the alkyl of the (meth) acryloyloxyalkyl group is a linear or branched hydrocarbon site of 1 to 10, or 1 to 8, or 1 to 4 carbon atoms Meaning, the (meth) acryloyloxy group may be substituted at any position of the alkyl group. The remaining one or more hydrogen atoms included in the alkyl may be substituted with any substituent.
- R 3 , R 4 and R 5 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group
- R 6 is a (meth) acryloyloxy group, (meth ) Acryloyloxyalkyl group, a hydroxy group, or a substituted or unsubstituted C 1-10 alkyl group.
- the alkyl of the (meth) acryloyloxyalkyl group is 1 to 10, or 1 to 8, or a straight chain of 1 to 4 carbon atoms or A branched hydrocarbon moiety, wherein the (meth) acryloyloxy group can be substituted at any position of the alkyl group.
- the remaining one or more hydrogen atoms included in the alkyl may be substituted with any substituent.
- the alkyl group means a straight or branched chain hydrocarbon site of 1 to 10, or 1 to 8, or 1 to 4 carbon atoms, and at least one hydrogen contained in the alkyl group.
- the atom may be substituted with any substituent.
- R 7 substituted or unsubstituted C 1-10 alkylene, and R 8 and R 9 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group.
- the alkylene refers to a straight or branched chain divalent hydrocarbon moiety of 1 to 10, or 1 to 8, or 1 to 6 carbon atoms, in the present specification
- the group may comprise at least one unsaturated bond in the molecule.
- the alkylene group includes, but is not limited to, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, nonamethylene, decamethylene and the like.
- One or more hydrogen atoms included in the alkylene may be substituted with any substituent.
- the alkyl of the (meth) acryloyloxyalkyl group is a straight or branched chain hydrocarbon site of 1 to 10, or 1 to 8, or 1 to 4 carbon atoms. Meaning, the (meth) acryloyloxy group may be substituted at any position of the alkyl group. The remaining one or more hydrogen atoms included in the alkyl may be substituted with any substituent.
- the (B) polyfunctional (meth) acrylic compound is particularly preferably one or more selected from the group consisting of compounds represented by the following [Formula 25] to [Formula 28].
- the content of the multifunctional (meth) acrylic compound of the present invention is about 5 to 40 parts by weight, preferably about 5 to 35 parts by weight, and more preferably 5 to 30 parts by weight based on 100 parts by weight of the radical curable composition. It can be negation. If the content of the polyfunctional (meth) acrylic compound is included in more than the above range may not be sufficient adhesion, if less than the above range may be weak in water resistance.
- the phosphate compound included in the radical curable composition according to the present invention is a component for further improving the adhesion and water resistance of the protective layer, and various phosphate compounds including one or two (meth) acryl groups in a molecule may be used. have.
- the phosphate compound is more preferably a compound represented by the following [formula V]. This is because the adhesiveness and the water resistance improving effect are particularly excellent.
- R 10 is a substituted or unsubstituted C 1 ⁇ 10 alkyl group, a substituted or unsubstituted C 4 ⁇ 14 cycloalkyl group, a substituted or unsubstituted C 6 ⁇ 14 aryl group, or their Combination;
- R 11 is hydrogen or a methyl group;
- the alkylene group refers to a straight or branched chain divalent hydrocarbon moiety of 1 to 10, or 1 to 8, or 1 to 4 carbon atoms, in the present specification
- the group may comprise at least one unsaturated bond in the molecule.
- the alkylene group includes, but is not limited to, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, nonamethylene, decamethylene and the like.
- One or more hydrogen atoms included in the alkylene group may be substituted with any substituent.
- the cycloalkylene group may be selected from 4 to 14, or 4 to 10, or 4 to 6 non-aromatic divalent monocyclic, bicyclic or tricyclic hydrocarbon moieties.
- the alkylene group may include at least one unsaturated bond in the molecule.
- a bivalent cyclopentane ring, a cyclohexane ring, etc. are mentioned as an example.
- One or more hydrogen atoms included in the cycloalkylene group may be substituted with any substituent.
- the arylene group means a divalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having 6 to 14, or 6 to 12 ring atoms, but is not limited thereto. And divalent, benzene ring, naphthalene ring, anthracene ring, biphenyl ring and the like. One or more hydrogen atoms included in the arylene group may be substituted with any substituent.
- the R 10 include, but are not limited to this, it is preferable that among a substituted or unsubstituted C 1 ⁇ 10 alkylene group, and more preferably substituted or unsubstituted C 1 ⁇ 8 alkylene group, a substituted or unsubstituted C 1 ⁇ 4 alkylene group is more preferable.
- the phosphate compound is particularly preferably one or more selected from the group consisting of compounds represented by the following [Formula 29] to [Formula 32].
- the content of the phosphate compound of the present invention may be about 1 to 40 parts by weight, preferably about 1 to 35 parts by weight, and more preferably about 1 to 30 parts by weight based on 100 parts by weight of the radical curable composition.
- the amount of the phosphate compound is included in more than the above range, the adhesion and glass transition temperature may decrease, and when less than the above range, the water resistance may be weak.
- radical initiators contained in the radical curable composition according to the present invention is for promoting radical polymerizability and improving the curing rate.
- radical initiators generally used in the art may be used without limitation, for example, 1-hydroxy-cyclohexyl-phenyl-ketone (1-Hydroxy-cyclohexyl-phenyl-ketone) , 2-hydroxy-2-methyl-1-phenyl-1-propanone (2-Hydroxy-2-methyl-1-phenyl-1-propanone), 2-hydroxy-1- [4- (2-hydroxy Hydroxyethoxy) phenyl] -2-methyl-1-propanone (2-Hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propanone), methylbenzoylformate, Oxy-phenyl-acetic acid-2- [2 oxo-2phenyl-acetoxy-ethoxy] -ethyl ester (oxy-phenyl)
- the content of the radical initiator is preferably about 0.5 to 20 parts by weight, 0.5 to 15 parts by weight or 0.5 to 10 parts by weight with respect to 100 parts by weight of the radical curable composition. This is because when the content of the radical initiator satisfies the numerical range, the protective layer may be smoothly cured.
- the radical curable composition of the present invention has a total hydroxyl value (hydroxyl value) of 500 to 900 mg KOH / g, more preferably 500 to 850 mg KOH / g, more preferably 500 to 800 mg It is about KOH / g.
- hydroxyl value of the radical curable composition satisfies the numerical range
- the protective layer formed by using the radical curable composition can stably maintain high adhesion with the polarizer even under relatively high humidity. Since the bonding force inside the cured protective layer is strong and may have a high glass transition temperature, there is an advantage that the thermal stability can be secured.
- the hydroxyl value means the number of mg of potassium hydroxide (KOH) required to neutralize the acetic acid bound to the hydroxyl group when acetylating the sample 1g
- the measurement method is not particularly limited.
- the hydroxyl value in the sample can be calculated through the following equation (1).
- the radical curable composition may have a glass transition temperature of 50 ° C. or higher after curing, for example, 80 ° C. to 300 ° C. or 90 ° C. to 200 ° C.
- the glass transition temperature in the numerical range as described above may have a good heat resistance and water resistance.
- the radical curable composition preferably has a viscosity of about 10 to 300 cP or about 20 to 100 cP.
- the thickness of the protective layer may be thinly formed, and since the composition has a low viscosity, there is an excellent workability.
- the thickness of the protective layer formed using the radical curable composition is preferably 0.5 to 20 ⁇ m, for example, may be 0.5 to 15 ⁇ m or 0.5 to 10 ⁇ m. This is because when the thickness of the protective layer satisfies the above range, the thickness of the polarizing plate produced can be reduced. If it is less than 0.5 ⁇ m, the thermal shock stability and curl characteristics of the polarizer are weak, and if it is 20 ⁇ m or more, the thickness of the polarizing plate is difficult.
- the polarizing plate of the present invention may further include a protective film on one surface of the polarizer as needed. More specifically, in the polarizing plate of the present invention, when the protective layer is formed on one surface of the polarizer, a separate protective film may be attached through the adhesive layer to support and protect the polarizer on the opposite side of the surface on which the protective layer is formed. have.
- the protective film is for supporting and protecting the polarizer
- protective films of various materials generally known in the art for example, cellulose-based film, polyethylene terephthalate (PET) film, cyclo An olefin polymer (COP, cycloolefin polymer) film, acrylic film, or the like can be used without limitation.
- PET polyethylene terephthalate
- COP cycloolefin polymer
- acrylic film or the like
- the acrylic film usable in the present invention can be obtained by molding a molding material containing (meth) acrylate-based resin as a main component by extrusion molding.
- the (meth) acrylate-based resin is a resin containing a (meth) acrylate-based unit as a main component, as well as a homopolymer resin consisting of (meth) acrylate-based units, as well as (meth) acrylate-based units
- the concept also includes a blend resin blended with other resin.
- the (meth) acrylate-based unit may be, for example, an alkyl (meth) acrylate-based unit.
- the alkyl (meth) acrylate-based unit means both an alkyl acrylate-based unit and an alkyl methacrylate-based unit
- the alkyl group of the alkyl (meth) acrylate-based unit is preferably 1 to 10 carbon atoms, It is more preferable that it is C1-C4.
- a styrene type unit, a maleic anhydride type unit, a maleimide type unit, etc. are mentioned as a monomeric unit copolymerizable with the said (meth) acrylate type unit.
- the styrene-based unit is not limited thereto, and examples thereof include styrene, ⁇ -methylstyrene, and the like;
- the maleic anhydride monomer include, but are not limited to, maleic anhydride, methyl maleic anhydride, cyclohexyl maleic anhydride, phenyl maleic anhydride, and the like;
- the maleimide monomers include, but are not limited to, maleimide, N-methyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, and the like. These may be used alone or in combination.
- the acrylic film may be a film containing a (meth) acrylate resin having a lactone ring structure.
- (meth) acrylate type resin which has a lactone ring structure it is the lactone described, for example in Unexamined-Japanese-Patent No. 2000-230016, Unexamined-Japanese-Patent No. 2001-151814, 2002-120326, etc.
- (Meth) acrylate type resin which has a ring structure is mentioned.
- the method for producing the acrylic film is not particularly limited, and for example, (meth) acrylate-based resin and other polymers, additives, and the like are sufficiently mixed by any suitable mixing method to prepare a thermoplastic resin composition, which is then film-molded. Or (meth) acrylate-based resin and other polymers, additives and the like may be prepared in a separate solution and then mixed to form a uniform mixed solution and then film-molded.
- the acrylic film may be any of an unstretched film or a stretched film. In the case of a stretched film, it may be a uniaxial stretched film or a biaxially stretched film, and in the case of a biaxially stretched film, it may be either a simultaneous biaxially stretched film or a successive biaxially stretched film.
- the polarizing plate of the present invention may further include a primer layer between the adhesive layer and the protective film in order to further improve the adhesive force.
- the primer layer may be formed by coating and drying a coating solution containing a water dispersible polymer resin, water dispersible fine particles and water on a protective film using a bar coating method, a gravure coating method, or the like.
- the water-dispersible polymer resin may be, for example, a water-based polyurethane resin, a water-based acrylic resin, a water-based polyester resin, or a combination thereof, and the water-dispersible microparticles may be inorganic fine particles such as silica, titania, alumina, zirconia, or the like.
- organic fine particles made of silicone resin, fluorine resin, (meth) acrylic resin, crosslinked polyvinyl alcohol and melamine resin, or a combination thereof may be used, but are not limited thereto.
- the polarizer and the protective film is attached to the surface of the polarizer or the protective film using a roll coater, gravure coater, bar coater, knife coater or capillary coater, etc., and then heat lamination with a lamination roll, It may be carried out by a method of pressing at room temperature and laminating or a method of UV irradiation after lamination.
- the adhesive various polarizing plate adhesives used in the art, for example, polyvinyl alcohol-based adhesives, polyurethane-based adhesives, acrylic adhesives, cationic or radical-based adhesives and the like can be used without limitation.
- the polarizing plate of the present invention may include an adhesive layer on an upper portion of the protective layer, if necessary, for attachment to an optical film such as a display panel or a retardation film.
- the pressure-sensitive adhesive layer may be formed using various pressure-sensitive adhesives well known in the art, and the kind thereof is not particularly limited.
- the pressure-sensitive adhesive layer may be a rubber pressure sensitive adhesive, an acrylic pressure sensitive adhesive, a silicone pressure sensitive adhesive, a urethane pressure sensitive adhesive, a polyvinyl alcohol pressure sensitive adhesive, a polyvinylpyrrolidone pressure sensitive adhesive, a polyacrylamide pressure sensitive adhesive, a cellulose pressure sensitive adhesive, a vinyl alkyl ether pressure sensitive adhesive, or the like. It can be formed using. Among these, in consideration of transparency, heat resistance and the like, it is particularly preferable to use an acrylic pressure-sensitive adhesive.
- the pressure-sensitive adhesive layer may be formed by applying a pressure-sensitive adhesive on the protective layer, or may be formed by a method of attaching the pressure-sensitive adhesive sheet prepared by applying the pressure-sensitive adhesive on the release sheet and dried on the protective layer.
- the polarizing plate of the present invention as described above can be usefully applied to an image display device such as a liquid crystal display device.
- the image display apparatus may be, for example, a liquid crystal display including a liquid crystal panel and polarizing plates provided on both surfaces of the liquid crystal panel, wherein at least one of the polarizing plates may be a polarizing plate according to the present invention.
- the type of liquid crystal panel included in the liquid crystal display device is not particularly limited.
- a panel of a passive matrix type such as, but not limited to, a twisted nematic (TN) type, a super twisted nematic (STN) type, a ferrolectic (F) type, or a polymer dispersed (PD) type; Active matrix panels such as two-terminal or three-terminal; All known panels, such as an In Plane Switching (IPS) panel and a Vertical Alignment (VA) panel, can be applied.
- IPS In Plane Switching
- VA Vertical Alignment
- other configurations constituting the liquid crystal display device for example, types of upper and lower substrates (eg, color filter substrates or array substrates) are not particularly limited, and configurations known in the art may be employed without limitation. Can be.
- the raw material hopper is a resin composition obtained by uniformly mixing poly (N-cyclohexylmaleimide-co-methylmethacrylate), styrene-maleic anhydride copolymer resin and phenoxy resin in a weight ratio of 100: 2.5: 5. From the extruder to a nitrogen-substituted 24 ⁇ extruder and melted at 250 ° C. to prepare a raw material pellet.
- the poly (N-cyclohexylmaleimide-co-methylmethacrylate) resin was used in which the content of N-cyclohexylmaleimide was 6.5% by weight as a result of NMR analysis.
- the obtained raw material pellets were vacuum-dried and melted with an extruder at 260 degreeC, passed through the T-die of a coat hanger type, and the film of 150 micrometers in thickness was produced through the chrome plating casting roll, a drying roll, etc.
- the film was stretched at a rate of 170% using a speed difference of the roll in the MD direction at 125 ° C. using a pilot stretching equipment to produce an acrylic film.
- Radical initiator was added to 100 parts by weight of the resin composition prepared by adding 64.5% by weight of GLA (glyceryl monoacrylate), 16.1% by weight of HEA (hydroxyethyl acrylate), 16.1% by weight of dimethylol tricyclodecane diacrylate (DCPDA), and 3.3% by weight of di- (methacryloyloxy ethyl) phosphate. 3 parts by weight of phosphorus irgacure-819 (Ciba) was added to prepare a radical curable composition A for polarizing plates.
- GLA glycol monoacrylate
- HEA hydroxyethyl acrylate
- DCPDA dimethylol tricyclodecane diacrylate
- Siba phosphorus irgacure-819
- Radical initiator was added to 100 parts by weight of the resin composition prepared by adding 56.5% by weight of GLA (glyceryl monoacrylate), 24.2% by weight of HEA (hydroxyethyl acrylate), 16.1% by weight of dimethylol tricyclodecane diacrylate (DCPDA), and 3.2% by weight of di- (methacryloyloxy ethyl) phosphate. 3 parts by weight of phosphorus irgacure-819 (Ciba) was added to prepare a radical curable composition B for a polarizing plate.
- GLA glycol monoacrylate
- HEA hydroxyethyl acrylate
- DCPDA dimethylol tricyclodecane diacrylate
- Ciba phosphorus irgacure-819
- Radical initiator was added to 100 parts by weight of the resin composition prepared by adding 55.5% by weight of GLA (glyceryl monoacrylate), 13.9% by weight of HEA (hydroxyethyl acrylate), 27.8% by weight of dimethylol tricyclodecane diacrylate (DCPDA), and 2.8% by weight of di- (methacryloyloxy ethyl) phosphate. 3 parts by weight of phosphorus irgacure-819 (Ciba) was added to prepare a radical curable composition E for polarizing plates.
- GLA glycol monoacrylate
- HEA hydroxyethyl acrylate
- DCPDA dimethylol tricyclodecane diacrylate
- Siba phosphorus irgacure-819
- a radical initiator was added to 100 parts by weight of a resin composition prepared by adding 72.6% by weight of GLA (glyceryl monoacrylate), 8.1% by weight of HEA (hydroxyethyl acrylate), 16.1% by weight of dimethylol tricyclodecane diacrylate (DCPDA), and 3.2% by weight of di- (methacryloyloxy ethyl) phosphate. 3 parts by weight of phosphorus irgacure-819 (Ciba) was added to prepare a radical curable composition F for polarizing plates.
- GLA glycol monoacrylate
- HEA hydroxyethyl acrylate
- DCPDA dimethylol tricyclodecane diacrylate
- Ciba phosphorus irgacure-819
- a radical initiator irgacure-819 (Ciba) in 100 parts by weight of 66.7% by weight of GLA (glyceryl monoacrylate), 16.65% by weight of HEA (hydroxyethyl acrylate) and 16.65% by weight of dimethylol tricyclodecane diacrylate (DCPDA). It added and produced the radical curable composition O for polarizing plates.
- GLA glycol monoacrylate
- HEA hydroxyethyl acrylate
- DCPDA dimethylol tricyclodecane diacrylate
- Radical curable composition A was applied to the primer layer of the acrylic film-based protective film prepared in Preparation Example 1 with a dropper, laminated on one surface of a polarizer (PVA device), and then the conditions were such that the thickness of the final adhesive layer was 1 to 2 ⁇ m. After setting, passed the laminator (5m / min). Then, the surface of the acrylic film is laminated using a UV irradiation device (metal halide lamp), by irradiating ultraviolet light of 1000mJ / cm 2 , to prepare a polarizing plate having a protective film on one surface of the polarizer.
- a UV irradiation device metal halide lamp
- the radical curable composition A is applied to the other surface of the surface on which the protective film of the polarizer of the prepared polarizer is laminated, the PET film having a releasing force is laminated, and the final protective layer thickness is 4 to 5 ⁇ m.
- the laminator 5m / min.
- the surface on which the release PET is laminated is irradiated with ultraviolet light of 1000 mJ / cm 2 using a ultraviolet halide lamp, and the PET film is removed, and a protective film is provided on one side of the polarizer, and on the other side.
- the polarizing plate provided with a protective layer was manufactured.
- a polarizing plate was manufactured in the same manner as in Example 1, except that B was used as the radical curable composition.
- a polarizing plate was manufactured in the same manner as in Example 1 except that C was used as the radical curable composition.
- a polarizing plate was manufactured in the same manner as in Example 1 except that D was used as the radical curable composition.
- a polarizing plate was manufactured in the same manner as in Example 1 except that E was used as the radical curable composition.
- a polarizing plate was manufactured in the same manner as in Example 1, except that F was used as the radical curable composition.
- a polarizing plate was manufactured in the same manner as in Example 1, except that G was used as the radical curable composition.
- a polarizing plate was manufactured in the same manner as in Example 1 except that H was used as the radical curable composition.
- a polarizing plate was manufactured in the same manner as in Example 1 except that I was used as the radical curable composition.
- the adhesiveness of the protective layer of the polarizing plates manufactured by the said Example and the comparative example was measured, and is shown in following [Table 1]. Specifically, the radical curable composition used in the above Examples and Comparative Examples on the polarizer (PVA device) is applied to 4 ⁇ 5 ⁇ m, laminated on the polarizer (PVA device) and passed through the laminator, and then UV irradiation device (Metal halide) UV) was irradiated at 1000 mJ / cm 2 using a lamp) to prepare a peel force sample consisting of a polarizer / protective layer / polarizer. The sample was left for 4 days at a temperature of 20 ° C.
- peeling force was measured. At this time, when peeling force was 1.0N / 2cm-2.0N / 2cm, it was excellent, 0.5N / 2cm or more and less than 1.0N / 2cm, and it displayed as bad if it was less than 0.5N / 2cm.
- the water resistance of the polarizing plates prepared in Examples and Comparative Examples was measured and shown in the following [Table 1]. Specifically, after laminating the polarizing plates of the above Examples and Comparative Examples on a glass substrate (glass lamination), the polarizing plate was immersed in a 60 ° C thermostat, and after 8 hours, the water resistance was judged by the discoloration of the ends of the polarizing plate, and the case of no deformation was excellent. , The case where discoloration occurred was marked as bad.
- Comparative Example 1 which does not contain the compound (B), is vulnerable to water resistance
- Comparative Example 2 which does not include the compound (C), is also vulnerable to water resistance
- the adhesive layer and the protective layer were manufactured using the same radical curable composition for convenience, but the present invention is not necessarily limited thereto.
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Abstract
The present invention relates to a polarizing plate and an image display apparatus comprising same, the polarizing plate comprising: a polarizer; and a protection layer formed on at least one side of the polarizer, wherein the protection layer is a cured product of a radical curable composition that comprises: (A) a radical polymerizable compound of which a molecule comprises at least one hydrophilic functional group; (B) a multifunctional (meth)acrylic compound; (C) a phosphate compound of which a molecule comprises one or two (meth)acrylic groups; and (D) a radical initiator.
Description
본 발명은 편광판 및 이를 포함하는 화상표시장치에 관한 것으로, 보다 구체적으로는, 편광자 및 보호층의 밀착성이 우수하고, 내수성이 우수하며, 박형으로 제조가 가능한 편광판 및 이를 포함하는 화상표시장치에 관한 것이다.The present invention relates to a polarizing plate and an image display device including the same, and more particularly, to a polarizing plate excellent in adhesion between a polarizer and a protective layer, excellent in water resistance, and thinly manufactured, and an image display device including the same. will be.
편광판은 통상 이색성 염료 또는 요오드로 염색된 폴리비닐알코올(Polyvinyl alcohol, 이하 'PVA'라 함)계 수지로 이루어진 편광자의 양면에 보호 필름을 적층한 구조로 사용되어 왔다. 이때, 상기 보호 필름으로는 광학적 투명성이나 투습성이 우수하다는 점에서 트리아세틸셀룰로오스(TAC, triacetyl cellulose)계 필름이 필름이 많이 사용되고 있다.The polarizing plate has been commonly used in a structure in which a protective film is laminated on both sides of a polarizer made of a polyvinyl alcohol (hereinafter referred to as 'PVA')-based resin dyed with a dichroic dye or iodine. At this time, the triacetyl cellulose (TAC, triacetyl cellulose) -based film has been used a lot of films in terms of excellent optical transparency and moisture permeability.
한편, 최근 액정표시장치의 노트북형 개인용 컴퓨터, 휴대 전화, 카 내비게이션 등의 모바일 기기로의 전개에 따라, 액정표시장치를 구성하는 편광판에는 박형 경량화가 요구되게 되고 있다. 그러나, 상기와 같이 보호 필름으로 TAC 필름 등을 적층한 편광판에서는, 작업시의 취급성이나 내구 성능의 관점에서 보호 필름의 두께를 20 ㎛ 이하로 하는 것이 곤란하여, 박형 경량화에 한계가 있었다.On the other hand, with the development of a liquid crystal display device into a mobile device such as a notebook personal computer, a mobile phone, a car navigation system, and the like, a thin and light weight is required for the polarizing plate constituting the liquid crystal display device. However, in the polarizing plate which laminated | stacked TAC film etc. with the protective film as mentioned above, it was difficult to make the thickness of a protective film 20 micrometers or less from a viewpoint of the handling property and durability at the time of work, and there existed a limit in thin weight reduction.
상기와 같은 문제점을 해결하기 위하여, 편광자의 한쪽 면에만 보호 필름을 구비하고, 반대 면에는 활성 에너지선 경화성 조성물을 도공하여, 투명 박막층을 형성하는 기술이 제안되고 있다. 한편, 현재까지 제안된 상기 활성 에너지선 경화성 조성물로는 경화방식에 따라 라디칼 경화형 조성물과 양이온 경화형 조성물로 나눌 수 있다. 이때, 양이온 경화형 조성물을 이용하여 투명 박막층을 형성하는 경우 편광자와의 우수한 밀착성을 가지는 장점이 있으나, 느린 경화속도 및 낮은 경화도로 인해 제조 공정상 많은 단점을 갖는다.In order to solve the above problems, a technique for forming a transparent thin film layer by providing a protective film on only one side of the polarizer and coating an active energy ray-curable composition on the opposite side is proposed. On the other hand, the active energy ray-curable composition proposed to date can be divided into a radical curable composition and a cationic curable composition according to the curing method. In this case, when the transparent thin film layer is formed using the cation-curable composition, there is an advantage of having excellent adhesion with the polarizer, but has a number of disadvantages in the manufacturing process due to the slow curing rate and low curing degree.
이러한 양이온 경화형 조성물의 문제점을 해결하기 위해 아크릴계 또는 아크릴 아마이드계 화합물을 주성분으로 하는 라디칼 경화형 조성물을 이용하여 투명 박막층을 형성하는 기술이 제안되었다. 그러나, 아크릴계 또는 아크릴 아마이드계 화합물을 주 성분으로 하는 라디칼 경화형 조성물의 경우, 양이온 경화형 조성물에 비해 경화 속도가 빠르기는 하나, 고습 분위기에서는 경화 속도가 느려지고, 이를 이용하여 형성된 투명 보호층이 편광자와 충분한 밀착성을 가지지 못하며, 또한 편광자 내의 요오드 이온에 영향을 주는 등 내수성이 좋지 못하다는 문제점이 있다.In order to solve the problem of such a cation-curable composition, a technique of forming a transparent thin film layer using a radical curable composition containing an acrylic or acrylamide-based compound as a main component has been proposed. However, in the case of a radically curable composition containing an acrylic or acrylamide compound as a main component, although the curing speed is faster than that of the cationic curable composition, the curing speed is slow in a high humidity atmosphere, and the transparent protective layer formed by using the polarizer is sufficient There is a problem in that the adhesiveness is not good and the water resistance is poor, such as affecting iodine ions in the polarizer.
따라서, 라디칼 경화로 형성이 가능한 박형의 보호층을 가지면서도, 편광자 및 보호층의 밀착성이 우수하고, 내수성이 우수한 새로운 편광판이 요구되고 있다.Therefore, while having the thin protective layer which can be formed by radical hardening, the new polarizing plate which is excellent in the adhesiveness of a polarizer and a protective layer, and excellent in water resistance is calculated | required.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로, 편광자 및 보호층의 밀착성이 우수하고, 내수성이 우수하며, 박형으로 제조가 가능한 편광판 및 이를 포함하는 화상표시장치를 제공하고자 한다.The present invention is to solve the above problems, to provide a polarizing plate excellent in the adhesion between the polarizer and the protective layer, excellent in water resistance, and can be manufactured in a thin shape and an image display device including the same.
일 측면에서, 본 발명은 편광자; 및 상기 편광자의 적어도 일면에 형성되는 보호층을 포함하는 편광판이며, 상기 보호층은 (A) 분자 내에 적어도 하나의 친수성 관능기를 포함하는 라디칼 중합성 화합물; (B) 다관능성 (메트)아크릴계 화합물; (C) 분자 내에 하나 또는 두 개의 (메트)아크릴기를 포함하는 포스페이트 화합물; 및 (D) 라디칼 개시제를 포함하는 라디칼 경화형 조성물의 경화물인 편광판을 제공한다.In one aspect, the present invention is a polarizer; And a protective layer formed on at least one surface of the polarizer, wherein the protective layer comprises: (A) a radical polymerizable compound including at least one hydrophilic functional group in a molecule; (B) a polyfunctional (meth) acrylic compound; (C) phosphate compounds containing one or two (meth) acryl groups in a molecule; And (D) a polarizing plate which is a cured product of a radical curable composition containing a radical initiator.
이때, 상기 라디칼 경화형 조성물은 라디칼 경화형 조성물 100 중량부에 대하여, (A) 분자 내에 적어도 하나의 친수성 관능기를 포함하는 라디칼 중합성 화합물 30 중량부 초과 93 중량부 이하; (B) 다관능성 (메트)아크릴계 화합물 5 내지 40 중량부; (C) 분자 내에 하나 또는 두 개의 (메트)아크릴기를 포함하는 포스페이트 화합물 1 내지 40 중량부; 및 (D) 라디칼 개시제 0.5 내지 20 중량부를 포함하는 것이 바람직하다.At this time, the radical curable composition is 30 parts by weight or more and 93 parts by weight or less with respect to 100 parts by weight of the radical curable composition, (A) a radically polymerizable compound including at least one hydrophilic functional group in a molecule; (B) 5 to 40 parts by weight of the multifunctional (meth) acrylic compound; (C) 1 to 40 parts by weight of a phosphate compound containing one or two (meth) acryl groups in the molecule; And (D) 0.5 to 20 parts by weight of a radical initiator.
또한, 상기 라디칼 경화형 조성물의 전체 수산기값(hydroxyl value)는 500 내지 900 mg·KOH/g인 것이 바람직하다.In addition, the total hydroxyl value of the radical curable composition is preferably 500 to 900 mg · KOH / g.
한편, 상기 (A) 라디칼 중합성 화합물의 친수성 관능기는 히드록시기인 것이 바람직하다.On the other hand, it is preferable that the hydrophilic functional group of the said (A) radically polymerizable compound is a hydroxyl group.
한편, 상기 (A) 라디칼 중합성 화합물은 (a-1) 분자 내에 하나의 히드록시기를 갖는 라디칼 중합성 화합물과 (a-2) 분자 내에 적어도 두 개의 히드록시기를 갖는 라디칼 중합성 화합물의 혼합물을 사용하는 것이 보다 바람직하다.On the other hand, the (A) radically polymerizable compound uses a mixture of a radically polymerizable compound having one hydroxy group in the molecule (a-1) and a radically polymerizable compound having at least two hydroxy groups in the molecule (a-2) It is more preferable.
또한, 상기 (b) 라디칼 중합성 화합물은 산가(acid value)가 100 내지 1000 mg·KOH/g 인 것이 바람직하다.In addition, the (b) radically polymerizable compound preferably has an acid value of 100 to 1000 mg · KOH / g.
한편, 상기 (B) 다관능성 (메트)아크릴계 화합물은 하기 [화학식 I] 내지 [화학식 Ⅲ]로 표시되는 화합물들로 이루어진 군으로 선택된 1종 이상을 포함하는 것이 바람직하다.Meanwhile, the (B) polyfunctional (meth) acrylic compound preferably includes one or more selected from the group consisting of compounds represented by the following [Formula I] to [Formula III].
[화학식 I][Formula I]
상기 [화학식 I]에서, R1 및 R2는 각각 독립적으로 (메트)아크릴로일옥시기 또는 (메트)아크릴로일옥시알킬기임.In [Formula I], R 1 and R 2 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group.
[화학식 Ⅱ][Formula II]
상기 [화학식 Ⅱ]에서, R3, R4 및 R5는 각각 독립적으로 (메트)아크릴로일옥시기 또는 (메트)아크릴로일옥시알킬기이고, R6는 (메트)아크릴로일옥시기, (메트)아크릴로일옥시알킬기, 히드록시기, 또는 치환 또는 비치환된 C1~10 알킬기임.In [Formula II], R 3 , R 4 and R 5 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group, and R 6 is a (meth) acryloyloxy group, (meth ) Acryloyloxyalkyl group, a hydroxy group, or a substituted or unsubstituted C 1-10 alkyl group.
[화학식 Ⅲ][Formula III]
상기 [화학식 Ⅲ]에서, R7은 치환 또는 비치환된 C1~10 알킬렌이고, R8 및 R9는 각각 독립적으로 (메트)아크릴로일옥시기 또는 (메트)아크릴로일옥시알킬기임.In [Chemical Formula III], R 7 is substituted or unsubstituted C 1-10 alkylene, and R 8 and R 9 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group.
한편, 상기 (C) 포스페이트 화합물은 하기 [화학식 Ⅳ]로 표시되는 화합물을 포함하는 것이 바람직하다.On the other hand, the (C) phosphate compound preferably includes a compound represented by the following [Formula IV].
[화학식 Ⅳ][Formula IV]
상기 [화학식 Ⅳ]에서, R10은 치환 또는 비치환된 C1~10 알킬렌기, 치환 또는 비치환된 C4~14 시클로알킬렌기, 치환 또는 비치환된 C6~14 아릴렌기, 또는 이들의 조합이고; R11는 수소 또는 메틸기이고; n 은 1 내지 2의 정수이고, m은 1 내지 2의 정수이고, n+m=3임.The Formula Ⅳ] in, R 10 is a substituted or unsubstituted C 1 ~ 10 alkyl group, a substituted or unsubstituted C 4 ~ 14 cycloalkyl group, a substituted or unsubstituted C 6 ~ 14 aryl group, or their Combination; R 11 is hydrogen or a methyl group; n is an integer of 1-2, m is an integer of 1-2, and n + m = 3.
한편, 상기 보호층은 두께가 0.5 내지 20㎛인 것이 바람직하다.On the other hand, the protective layer preferably has a thickness of 0.5 to 20㎛.
한편, 본 발명의 상기 편광판은 상기 편광자의 보호층이 형성된 면의 반대면에 접착제층을 매개로 보호 필름을 더 부착될 수 있다.On the other hand, the polarizing plate of the present invention may be further attached to the protective film via the adhesive layer on the opposite side of the surface on which the protective layer of the polarizer is formed.
또한, 본 발명의 상기 편광판은 상기 보호층 상부에 점착층을 더 포함할 수 있다.In addition, the polarizing plate of the present invention may further include an adhesive layer on the protective layer.
다른 측면에서, 본 발명은 상기 편광판을 포함하는 화상표시장치를 제공한다.In another aspect, the present invention provides an image display device including the polarizing plate.
본 발명의 편광판은 편광자 및 보호층의 밀착성이 우수하며, 고습 환경에서도 편광자 내의 요오드 이온의 탈색을 방지할 수 있는 등 내수성이 우수하다. 또한, 본 발명의 편광판은 종래의 투명 보호 필름을 갖는 편광판에 비해 두께가 얇은 보호층을 갖는바, 박형으로 제조가 가능하다.The polarizing plate of this invention is excellent in the adhesiveness of a polarizer and a protective layer, and is excellent in water resistance, such as being able to prevent the discoloration of the iodine ion in a polarizer even in a high humidity environment. In addition, the polarizing plate of the present invention has a thin protective layer compared to the polarizing plate having a conventional transparent protective film, it can be manufactured in a thin shape.
이하, 본 발명의 바람직한 실시 형태들을 설명한다. 그러나, 본 발명의 실시형태는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 이하 설명하는 실시 형태로 한정되는 것은 아니다. 또한, 본 발명의 실시형태는 당해 기술분야에서 평균적인 지식을 가진 자에게 본 발명을 더욱 완전하게 설명하기 위해서 제공되는 것이다. Hereinafter, preferred embodiments of the present invention will be described. However, embodiments of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below. In addition, the embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.
1. 편광판1. Polarizer
본 발명자들은 연구를 거듭한 결과, 보호층을 형성하기 위한 친수성 관능기를 갖는 라디칼 경화형 조성물에 다관능성 (메트)아크릴계 화합물과 분자 내에 하나 또는 두개의 (메트)아크릴기를 갖는 포스페이트 화합물을 혼합하여 사용하는 경우, 밀착성 및 내수성이 우수하다는 것을 알아내고 본 발명을 완성하였다.The present inventors have conducted extensive research and used a mixture of a polyfunctional (meth) acrylic compound and a phosphate compound having one or two (meth) acryl groups in a molecule to a radical curable composition having a hydrophilic functional group for forming a protective layer. In this case, it was found that the adhesion and water resistance is excellent, and completed the present invention.
보다 구체적으로는, 본 발명의 라디칼 경화형 조성물은, 편광자; 및 상기 편광자의 적어도 일면에 형성되는 보호층을 포함하는 편광판이며, 상기 보호층은 (A) 분자 내에 적어도 하나의 친수성 관능기를 포함하는 라디칼 중합성 화합물; (B) 다관능성 (메트)아크릴계 화합물; (C) 분자 내에 하나 또는 두 개의 (메트)아크릴기를 포함하는 포스페이트 화합물; 및 (D) 라디칼 개시제를 포함하는 라디칼 경화형 조성물의 경화물이다.More specifically, the radical curable composition of this invention is a polarizer; And a protective layer formed on at least one surface of the polarizer, wherein the protective layer comprises: (A) a radical polymerizable compound including at least one hydrophilic functional group in a molecule; (B) a polyfunctional (meth) acrylic compound; (C) phosphate compounds containing one or two (meth) acryl groups in a molecule; And (D) hardened | cured material of the radical curable composition containing a radical initiator.
1-1. 편광자1-1. Polarizer
먼저, 본 발명의 상기 편광자는 당해 기술분야에 잘 알려진 편광자, 예를 들면 요오드 또는 이색성 염료를 포함하는 폴리비닐알콜(PVA)로 이루어진 필름을 사용할 수 있다. 상기 편광자는 폴리비닐알코올 필름에 요오드 또는 이색성 염료를 염착시켜서 제조될 수 있으나, 이의 제조방법은 특별히 한정되지 않는다. 본 명세서에 있어서, 편광자는 보호층(또는 보호 필름)을 포함하지 않는 상태를 의미하며, 편광판은 편광자와 보호층(또는 보호 필름)을 포함하는 상태를 의미한다.First, the polarizer of the present invention may use a film made of polyvinyl alcohol (PVA) containing a polarizer well known in the art, for example, iodine or dichroic dye. The polarizer may be prepared by dyeing iodine or dichroic dye on a polyvinyl alcohol film, but a method of manufacturing the same is not particularly limited. In the present specification, the polarizer means a state not including a protective layer (or protective film), and the polarizing plate means a state including a polarizer and a protective layer (or protective film).
한편, 상기 편광자가 폴리비닐알코올계 필름인 경우, 폴리비닐알코올계 필름은 폴리비닐알코올 수지 또는 그 유도체를 포함하는 것이면 특별한 제한 없이 사용이 가능하다. 이때, 상기 폴리비닐알코올 수지의 유도체로는, 이에 한정되는 것은 아니나, 폴리비닐포르말 수지, 폴리비닐아세탈 수지 등을 들 수 있다. 또는, 상기 폴리비닐알코올계 필름은 당해 기술분야에 있어서 편광자 제조에 일반적으로 사용되는 시판되는 폴리비닐알코올계 필름, 예컨대, 구라레 사의 P30, PE30, PE60, 일본합성사의 M3000 M6000 등을 사용할 수도 있다.On the other hand, when the polarizer is a polyvinyl alcohol-based film, the polyvinyl alcohol-based film can be used without particular limitation as long as it contains a polyvinyl alcohol resin or a derivative thereof. In this case, examples of the derivative of the polyvinyl alcohol resin include, but are not limited to, polyvinyl formal resin, polyvinyl acetal resin, and the like. Alternatively, the polyvinyl alcohol-based film may be a commercially available polyvinyl alcohol-based film commonly used in the manufacture of polarizers in the art, for example, P30, PE30, PE60 manufactured by Gurere, M3000 M6000 manufactured by Japan Synthetic, and the like. .
한편, 상기 폴리비닐알코올계 필름은, 이로써 한정되는 것은 아니나, 중합도가 1,000 내지 10,000 정도, 바람직하게는 1,500 내지 5,000 정도인 것이 좋다. 중합도가 상기 범위를 만족할 때, 분자 움직임이 자유롭고, 요오드 또는 이색성 염료 등과 유연하게 혼합될 수 있기 때문이다.On the other hand, the polyvinyl alcohol-based film is not limited to this, but the degree of polymerization is preferably about 1,000 to 10,000, preferably 1,500 to 5,000. This is because when the degree of polymerization satisfies the above range, the molecular motion is free and can be mixed flexibly with iodine or dichroic dye.
1-2. 보호층1-2. Protective layer
다음으로, 본 발명의 상기 보호층은 편광자를 지지 및 보호하기 위하여 상기 라디칼 경화형 조성물을 이용하여 형성된 것으로, 당해 기술 분야에 잘 알려진 방법에 의해 형성될 수 있다. 예를 들면, 편광자의 일면에 상기 라디칼 경화형 조성물을 당해 기술 분야에 잘 알려진 코팅 법, 예컨대 스핀 코팅, 바 코팅, 롤 코팅, 그라비아 코팅, 블레이드 코팅 등의 방법으로 도포하여 보호층을 형성한 다음, 활성 에너지선 조사를 통해 경화시키는 방법으로 수행될 수 있다. 활성 에너지선 조사 방법은 특별히 한정되지 않으며, 예를 들면, 자외선 조사장치(fusion lamp, D bulb)를 이용하여 10 내지 2500mJ/cm2 정도의 자외선을 조사하는 방법으로 수행할 수 있다.Next, the protective layer of the present invention is formed using the radical curable composition to support and protect the polarizer, it may be formed by a method well known in the art. For example, the radical curable composition is applied to one surface of the polarizer by a coating method well known in the art such as spin coating, bar coating, roll coating, gravure coating, blade coating, and the like to form a protective layer. It may be carried out by a method of curing through active energy ray irradiation. The active energy ray irradiation method is not particularly limited, and for example, may be performed by irradiating an ultraviolet ray of about 10 to 2500 mJ / cm 2 using an ultraviolet ray irradiation apparatus (fusion lamp, D bulb).
이때, 본 발명의 상기 라디칼 경화형 조성물은 상기한 바와 같이 (A) 분자 내에 적어도 하나의 친수성 관능기를 포함하는 라디칼 중합성 화합물; (B) 다관능성 (메트)아크릴계 화합물; (C) 분자 내에 하나 또는 두 개의 (메트)아크릴기를 포함하는 포스페이트 화합물; 및 (D) 라디칼 개시제를 포함한다.At this time, the radical curable composition of the present invention, as described above (A) a radically polymerizable compound containing at least one hydrophilic functional group in the molecule; (B) a polyfunctional (meth) acrylic compound; (C) phosphate compounds containing one or two (meth) acryl groups in a molecule; And (D) a radical initiator.
보다 바람직하게는, 본 발명의 상기 라디칼 경화형 조성물은, 라디칼 경화형 조성물 100 중량부에 있어서, (A) 분자 내에 적어도 하나의 친수성 관능기를 포함하는 라디칼 중합성 화합물 30 중량부 초과 93 중량부 이하; (B) 다관능성 (메트)아크릴계 화합물 5 내지 40 중량부; (C) 분자 내에 하나 또는 두 개의 (메트)아크릴기를 포함하는 포스페이트 화합물 1 내지 40 중량부; 및 (D) 라디칼 개시제 0.5 내지 20 중량부를 포함한다.More preferably, the radical curable composition of the present invention, in 100 parts by weight of the radical curable composition, (A) more than 30 parts by weight and 93 parts by weight or less of the radically polymerizable compound containing at least one hydrophilic functional group in a molecule; (B) 5 to 40 parts by weight of the multifunctional (meth) acrylic compound; (C) 1 to 40 parts by weight of a phosphate compound containing one or two (meth) acryl groups in the molecule; And (D) 0.5 to 20 parts by weight of radical initiator.
가. 라디칼 중합성 화합물 (A)end. Radical polymerizable compound (A)
먼저, 본 발명에 따른 라디칼 경화형 조성물에 포함되는 상기 라디칼 중합성 화합물은 편광자와 보호층 간의 밀착성을 구현하기 위한 성분으로, 분자 내에 적어도 하나의 친수성 관능기를 가짐으로써 수소 결합을 통한 밀착성 구현이 가능하고, 또한 라디칼 중합성 화합물로 분자 내에 탄소간 불포화 이중 결합이 존재함으로써 라디칼 중합이 가능한 것이면 특별한 제한 없이 사용이 가능하다. 이때, 상기 친수성 관능기는 히드록시기, 카르복시기, 우레탄기, 아민기, 아마이드기 등 수소 결합이 가능한 것이면 특별히 제한 되는 것은 아니나, 그 중에서도 특히 히드록시기인 것이 우수한 밀착성의 구현을 위하여 보다 바람직하다.First, the radically polymerizable compound included in the radical curable composition according to the present invention is a component for implementing adhesion between the polarizer and the protective layer, and has at least one hydrophilic functional group in the molecule to realize adhesion through hydrogen bonding. In addition, as long as the radical polymerizable compound is capable of radical polymerization by the presence of an unsaturated double bond between carbons in the molecule, it can be used without particular limitation. In this case, the hydrophilic functional group is not particularly limited as long as it is possible to hydrogen bond such as hydroxy group, carboxyl group, urethane group, amine group, amide group, etc. Among them, the hydroxy group is particularly preferable for the implementation of excellent adhesion.
보다 구체적으로, 상기 라디칼 중합성 화합물은, 이에 한정되는 것은 아니나, 예를 들면 하기 [화학식 1] 내지 [화학식 24]로 표시되는 화합물일 수 있다. 이들은 단독으로 또는 혼합하여 사용할 수 있다.More specifically, the radically polymerizable compound is not limited thereto, and may be, for example, a compound represented by the following [Formula 1] to [Formula 24]. These can be used individually or in mixture.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
[화학식 6][Formula 6]
[화학식 7][Formula 7]
[화학식 8][Formula 8]
[화학식 9][Formula 9]
[화학식 10][Formula 10]
[화학식 11][Formula 11]
[화학식 12][Formula 12]
[화학식 13][Formula 13]
[화학식 14][Formula 14]
[화학식 15][Formula 15]
[화학식 16][Formula 16]
[화학식 17][Formula 17]
[화학식 18][Formula 18]
[화학식 19][Formula 19]
[화학식 20][Formula 20]
[화학식 21][Formula 21]
[화학식 22][Formula 22]
[화학식 23][Formula 23]
[화학식 24][Formula 24]
한편, 상기 라디칼 중합성 화합물은, 이에 한정되는 것은 아니나, 그 중에서도 특히 (a-1) 분자 내에 하나의 히드록시기를 갖는 라디칼 중합성 화합물(예를 들면, 상기 [화학식 1] ~ [화학식 6] 등)과 (a-2) 분자 내에 적어도 두 개의 히드록시기를 갖는 라디칼 중합성 화합물(예를 들면, 상기 [화학식 7] ~ [화학식 24] 등)의 혼합물을 사용하는 것이 우수한 밀착성 구현 및 내열성 확보 측면에서 바람직하다.On the other hand, the radically polymerizable compound is not limited thereto, and in particular, the radically polymerizable compound having one hydroxyl group in the molecule (a-1) (for example, the above [Formula 1] to [Formula 6], etc.) ) And a mixture of (a-2) radically polymerizable compounds having at least two hydroxy groups in the molecule (for example, [Formula 7] to [Formula 24], etc.) in terms of excellent adhesion and heat resistance desirable.
한편, 본 발명의 상기 라디칼 중합성 화합물의 함량은, 라디칼 경화형 조성물 100 중량부에 대하여, 30 중량부 초과 93 중량부 이하정도, 바람직하게는 35 내지 90 중량부정도, 더욱 바람직하게는 45 내지 90 중량부정도일 수 있다. 이와 같은 함량으로 포함되는 경우 우수한 밀착성 구현이 가능하기 때문이다.On the other hand, the content of the radically polymerizable compound of the present invention is more than 30 parts by weight and 93 parts by weight or less, preferably 35 to 90 parts by weight, and more preferably 45 to 90 parts by weight based on 100 parts by weight of the radical curable composition. It may be part by weight. If it is included in such a content because it is possible to implement excellent adhesion.
나. 다관능성 (메트)아크릴계 화합물 (B)I. Polyfunctional (meth) acrylic compound (B)
다음으로, 본 발명에 따른 라디칼 경화형 조성물에 포함되는 상기 다관능성 (메트)아크릴계 화합물은 보호층 내에 가교도를 증가시켜 내수성을 개선하여 고습 환경에서도 안정한 물성을 나타내도록 하기 위한 성분으로, 당해 기술 분야에 널리 알려진 다양한 다관능성(메트)아크릴계 화합물을 특별한 제한 없이 사용할 수 있다. 다만, 본 명세서에서는 하기 예시로 나열한 다관능성 (메트)아크릴계 화합물을 제회하고는 상술한 (A) 화합물 및 후술할 (C) 화합물에 해당하는 화합물은 다관능성 (메트)아크릴계 화합물에서 제외한다.Next, the polyfunctional (meth) acrylic compound included in the radical curable composition according to the present invention is a component for improving the water resistance by increasing the degree of crosslinking in the protective layer and showing stable physical properties even in a high humidity environment. Various well-known polyfunctional (meth) acrylic compounds can be used without particular limitation. In the present specification, except for the polyfunctional (meth) acrylic compounds listed in the following examples, the compounds corresponding to the above-mentioned (A) compounds and the (C) compounds described later are excluded from the polyfunctional (meth) acrylic compounds.
예를 들어, 본 발명에 있어서, 상기 다관능성 (메트)아크릴계 화합물로는, 에틸렌글리콜디(메트)아크릴레이트, 1,3-부탄디올디(메트)아크릴레이트, 1,4-부탄디올디(메트)아크릴레이트, 1,6-헥산디올디(메트)아크릴레이트, 1,9-노난디올디(메트)아크릴레이트, 네오펜틸글리콜디(메트)아크릴레이트, 트리메틸올프로판디(메트)아크릴레이트, 펜타에리트리톨디(메트)아크릴레이트, 디트리메틸올프로판디(메트)아크릴레이트, 디에틸렌글리콜디(메트)아크릴레이트, 트리에틸렌글리콜디(메트)아크릴레이트, 디프로필렌글리콜디(메트)아크릴레이트, 트리프로필렌글리콜디(메트)아크릴레이트, 폴리에틸렌글리콜디(메트)아크릴레이트, 폴리프로필렌글리콜디(메트)아크릴레이트, 폴리테트라메틸렌글리콜디(메트)아크릴레이트, 실리콘디(메트)아크릴레이트, 히드록시피발산에스테르네오펜틸글리콜디(메트)아크릴레이트, 2,2-비스[4-(메트)아크릴로일옥시에톡시에톡시페닐]프로판, 2,2-비스[4-(메트)아크릴로일옥시에톡시에톡시시클로헥실]프로판, 수소 첨가 디시클로펜타디에닐디(메트)아크릴레이트, 트리시클로데칸디메탄올디(메트)아크릴레이트, 1,3-디옥산-2,5-디일디(메트)아크릴레이트, 2-(2-히드록시-1,1-디메틸에틸)-5-에틸-5-히드록시메틸-1,3-디옥산의 디(메트)아크릴레이트, 트리스(히드록시에틸)이소시아누레이트디(메트)아크릴레이트, 글리세린트리(메트)아크릴레이트, 트리메틸올프로판트리(메트)아크릴레이트, 디트리메틸올프로판트리(메트)아크릴레이트, 디트리메틸올프로판테트라(메트)아크릴레이트, 펜타에리트리톨트리(메트)아크릴레이트, 펜타에리트리톨테트라(메트)아크릴레이트, 디펜타에리트리톨테트라(메트)아크릴레이트, 디펜타에리트리톨펜타(메트)아크릴레이트, 디펜타에리트리톨헥사(메트)아크릴레이트 등을 들 수 있다. 이들은 단독으로 또는 혼합하여 사용할 수 있다.For example, in the present invention, examples of the polyfunctional (meth) acrylic compound include ethylene glycol di (meth) acrylate, 1,3-butanedioldi (meth) acrylate, and 1,4-butanedioldi (meth). Acrylate, 1,6-hexanedioldi (meth) acrylate, 1,9-nonanedioldi (meth) acrylate, neopentylglycoldi (meth) acrylate, trimethylolpropanedi (meth) acrylate, penta Erythritol di (meth) acrylate, ditrimethylolpropanedi (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycoldi (meth) acrylate, silicone di (meth) acrylate, hydroxide Pivalic acid ester neopentyl glycol di (meth) acrylate, 2,2-bis [4- (meth) acryloyloxyethoxyethoxyphenyl] propane, 2,2-bis [4- (meth) acryloyl Oxyethoxyethoxycyclohexyl] propane, hydrogenated dicyclopentadienyldi (meth) acrylate, tricyclodecanedimethanoldi (meth) acrylate, 1,3-dioxane-2,5-diyldi (meth ) Acrylate, di (meth) acrylate of 2- (2-hydroxy-1,1-dimethylethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane, tris (hydroxyethyl) Isocyanurate di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned. These can be used individually or in mixture.
한편, 이에 한정되는 것은 아니나, 상기 다관능성 (메트)아크릴계 화합물은 하기 [화학식 I] 내지 [화학식 Ⅲ]로 표시되는 화합물들로 이루어진 군으로 선택된 1종 이상인 것이 보다 바람직하다. 이 경우 내수성 개선 효과가 더욱 우수하기 때문이다.On the other hand, the present invention is not limited thereto, but the polyfunctional (meth) acrylic compound is more preferably one or more selected from the group consisting of compounds represented by the following [Formula I] to [Formula III]. This is because the water resistance improvement effect is more excellent.
[화학식 I][Formula I]
상기 [화학식 I]에서, R1 및 R2는 각각 독립적으로 (메트)아크릴로일옥시기 또는 (메트)아크릴로일옥시알킬기이다.In [Formula I], R 1 and R 2 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group.
이때, 상기 R1 및 R2에 있어서, 상기 (메트)아크릴로일옥시알킬기의 알킬은 1 내지 10개, 또는 1 내지 8개, 또는 1 내지 4개의 탄소 원자의 직쇄 또는 분지쇄의 탄화수소 부위를 의미하며, (메트)아크릴로일옥시기는 알킬기의 임의의 위치에 치환될 수 있다. 상기 알킬에 포함되어 있는 나머지 하나 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.At this time, in the R 1 and R 2 , the alkyl of the (meth) acryloyloxyalkyl group is a linear or branched hydrocarbon site of 1 to 10, or 1 to 8, or 1 to 4 carbon atoms Meaning, the (meth) acryloyloxy group may be substituted at any position of the alkyl group. The remaining one or more hydrogen atoms included in the alkyl may be substituted with any substituent.
[화학식 Ⅱ][Formula II]
상기 [화학식 Ⅱ]에서, R3, R4 및 R5는 각각 독립적으로 (메트)아크릴로일옥시기 또는 (메트)아크릴로일옥시알킬기이고, R6는 (메트)아크릴로일옥시기, (메트)아크릴로일옥시알킬기, 히드록시기, 또는 치환 또는 비치환된 C1~10 알킬기이다.In [Formula II], R 3 , R 4 and R 5 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group, and R 6 is a (meth) acryloyloxy group, (meth ) Acryloyloxyalkyl group, a hydroxy group, or a substituted or unsubstituted C 1-10 alkyl group.
이때, 상기 R3, R4, R5 및 R6에 있어서, 상기 (메트)아크릴로일옥시알킬기의 알킬은 1 내지 10개, 또는 1 내지 8개, 또는 1 내지 4개의 탄소 원자의 직쇄 또는 분지쇄의 탄화수소 부위를 의미하며, (메트)아크릴로일옥시기는 알킬기의 임의의 위치에 치환될 수 있다. 상기 알킬에 포함되어 있는 나머지 하나 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In this case, in the R 3 , R 4, R 5 and R 6 , the alkyl of the (meth) acryloyloxyalkyl group is 1 to 10, or 1 to 8, or a straight chain of 1 to 4 carbon atoms or A branched hydrocarbon moiety, wherein the (meth) acryloyloxy group can be substituted at any position of the alkyl group. The remaining one or more hydrogen atoms included in the alkyl may be substituted with any substituent.
또한, 상기 R6에 있어서, 상기 알킬기는 1 내지 10개, 또는 1 내지 8개, 또는 1 내지 4개의 탄소 원자의 직쇄 또는 분지쇄의 탄화수소 부위를 의미하며, 상기 알킬기에 포함되어 있는 1 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In addition, in R 6 , the alkyl group means a straight or branched chain hydrocarbon site of 1 to 10, or 1 to 8, or 1 to 4 carbon atoms, and at least one hydrogen contained in the alkyl group. The atom may be substituted with any substituent.
[화학식 Ⅲ][Formula III]
상기 [화학식 Ⅲ]에서, R7 치환 또는 비치환된 C1~10 알킬렌이고, R8 및 R9는 각각 독립적으로 (메트)아크릴로일옥시기 또는 (메트)아크릴로일옥시알킬기이다.In [Chemical Formula III], R 7 substituted or unsubstituted C 1-10 alkylene, and R 8 and R 9 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group.
이때, 상기 R7에 있어서, 상기 알킬렌은 1 내지 10개, 또는 1 내지 8개, 또는 1 내지 6개의 탄소 원자의 직쇄 또는 분지쇄의 2가 탄화수소 부위를 의미하며, 본 명세서에서 상기 알킬렌기는 분자 내에 적어도 하나의 불포화 결합을 포함할 수도 있다. 한편, 상기 알킬렌기로는, 이에 한정되는 것은 아니나, 메틸렌, 에틸렌, 트리메틸렌, 테트라메틸렌, 펜타메틸렌, 헥사메틸렌, 헵타메틸렌, 노나메틸렌, 데카메틸렌 등을 그 예로 들 수 있다. 상기 알킬렌에 포함되어 있는 하나 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In this case, in R 7 , the alkylene refers to a straight or branched chain divalent hydrocarbon moiety of 1 to 10, or 1 to 8, or 1 to 6 carbon atoms, in the present specification The group may comprise at least one unsaturated bond in the molecule. On the other hand, the alkylene group includes, but is not limited to, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, nonamethylene, decamethylene and the like. One or more hydrogen atoms included in the alkylene may be substituted with any substituent.
또한, 상기 R8 및 R9에 있어서, 상기 (메트)아크릴로일옥시알킬기의 알킬은 1 내지 10개, 또는 1 내지 8개, 또는 1 내지 4개의 탄소 원자의 직쇄 또는 분지쇄의 탄화수소 부위를 의미하며, (메트)아크릴로일옥시기는 알킬기의 임의의 위치에 치환될 수 있다. 상기 알킬에 포함되어 있는 나머지 하나 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In the above R 8 and R 9 , the alkyl of the (meth) acryloyloxyalkyl group is a straight or branched chain hydrocarbon site of 1 to 10, or 1 to 8, or 1 to 4 carbon atoms. Meaning, the (meth) acryloyloxy group may be substituted at any position of the alkyl group. The remaining one or more hydrogen atoms included in the alkyl may be substituted with any substituent.
보다 구체적으로, 이에 한정되는 것은 아니나, 상기 (B) 다관능성 (메트)아크릴계 화합물은 하기 [화학식 25] 내지 [화학식 28]로 표시되는 화합물들로 이루어진 군으로 선택된 1종 이상인 것이 특히 바람직하다.More specifically, although not limited thereto, the (B) polyfunctional (meth) acrylic compound is particularly preferably one or more selected from the group consisting of compounds represented by the following [Formula 25] to [Formula 28].
[화학식 25][Formula 25]
[화학식 26][Formula 26]
[화학식 27][Formula 27]
[화학식 28][Formula 28]
한편, 본 발명의 상기 다관능 (메트)아크릴계 화합물의 함량은 라디칼 경화형 조성물 100 중량부에 대하여, 5 내지 40 중량부정도, 바람직하게는 5 내지 35 중량부정도, 더욱 바람직하게는 5 내지 30 중량부정도일 수 있다. 다관능 (메트)아크릴계 화합물의 함량이 상기 범위보다 많이 포함되는 경우 밀착성이 충분하지 않을 수 있으며, 상기 범위보다 적게 포함되는 경우 내수성이 취약해질 수 있다.Meanwhile, the content of the multifunctional (meth) acrylic compound of the present invention is about 5 to 40 parts by weight, preferably about 5 to 35 parts by weight, and more preferably 5 to 30 parts by weight based on 100 parts by weight of the radical curable composition. It can be negation. If the content of the polyfunctional (meth) acrylic compound is included in more than the above range may not be sufficient adhesion, if less than the above range may be weak in water resistance.
다. 포스페이트 화합물 (C)All. Phosphate Compound (C)
다음으로, 본 발명에 따른 라디칼 경화형 조성물에 포함되는 상기 포스페이트 화합물은 보호층의 밀착성과 내수성을 더욱 향상시키기 위한 성분으로, 분자 내에 하나 또는 두 개의 (메트)아크릴기를 포함하는 다양한 포스페이트 화합물을 사용할 수 있다. 본 발명의 발명자들의 연구 결과에 따르면, 상기 다관능성 (메트)아크릴계 화합물의 첨가만으로는 충분한 밀착성 및 내수성 확보가 어려우며, 상기 분자 내에 하나 또는 두 개의 (메트)아크릴기를 포함하는 포스페이트 화합물을 동시에 첨가하는 경우에 비로서 우수한 밀착성 및 내수성을 모두 만족시키는 보호층의 제조가 가능하다.Next, the phosphate compound included in the radical curable composition according to the present invention is a component for further improving the adhesion and water resistance of the protective layer, and various phosphate compounds including one or two (meth) acryl groups in a molecule may be used. have. According to the results of the inventors of the present invention, it is difficult to secure sufficient adhesion and water resistance only by adding the multifunctional (meth) acrylic compound, and when adding a phosphate compound containing one or two (meth) acryl groups in the molecule at the same time. It is possible to produce a protective layer that satisfies both excellent adhesion and water resistance as a cost.
한편, 이에 한정되는 것은 아니나, 상기 포스페이트 화합물은 하기 [화학식 V]로 표시되는 화합물인 것이 보다 바람직하다. 이 경우 밀착성 및 내수성 향상 효과가 특히 우수하기 때문이다.On the other hand, although not limited to this, the phosphate compound is more preferably a compound represented by the following [formula V]. This is because the adhesiveness and the water resistance improving effect are particularly excellent.
[화학식 Ⅳ][Formula IV]
상기 [화학식 Ⅳ]에서, R10은 치환 또는 비치환된 C1~10 알킬렌기, 치환 또는 비치환된 C4~14 시클로알킬렌기, 치환 또는 비치환된 C6~14 아릴렌기, 또는 이들의 조합이고; R11는 수소 또는 메틸기이고; n 은 1 내지 2의 정수이고, m은 1 내지 2의 정수이고, n+m=3이다. The Formula Ⅳ] in, R 10 is a substituted or unsubstituted C 1 ~ 10 alkyl group, a substituted or unsubstituted C 4 ~ 14 cycloalkyl group, a substituted or unsubstituted C 6 ~ 14 aryl group, or their Combination; R 11 is hydrogen or a methyl group; n is an integer of 1-2, m is an integer of 1-2, and n + m = 3.
이때, 상기 R10에 있어서, 상기 알킬렌기는 1 내지 10개, 또는 1 내지 8개, 또는 1 내지 4개의 탄소 원자의 직쇄 또는 분지쇄의 2가 탄화수소 부위를 의미하며, 본 명세서에서 상기 알킬렌기는 분자 내에 적어도 하나의 불포화 결합을 포함할 수도 있다. 한편, 상기 알킬렌기로는, 이에 한정되는 것은 아니나, 메틸렌, 에틸렌, 트리메틸렌, 테트라메틸렌, 펜타메틸렌, 헥사메틸렌, 헵타메틸렌, 노나메틸렌, 데카메틸렌 등을 그 예로 들 수 있다. 상기 알킬렌기에 포함되어 있는 하나 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In this case, in R 10 , the alkylene group refers to a straight or branched chain divalent hydrocarbon moiety of 1 to 10, or 1 to 8, or 1 to 4 carbon atoms, in the present specification The group may comprise at least one unsaturated bond in the molecule. On the other hand, the alkylene group includes, but is not limited to, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, nonamethylene, decamethylene and the like. One or more hydrogen atoms included in the alkylene group may be substituted with any substituent.
또한, 상기 R10에 있어서, 상기 시클로알킬렌기는 4 내지 14개, 또는 4 내지 10개, 또는 4 내지 6개의 고리 탄소의 비방향족 2가 모노사이클릭, 바이사이클릭 또는 트리사이클릭 탄화수소 부위를 의미하며, 본 명세서에서 상기 알킬렌기는 분자 내에 적어도 하나의 불포화 결합을 포함할 수도 있다. 한편, 상기 시클로알킬렌기로는, 이에 한정되는 것은 아니나, 2가의, 시클로펜탄 고리, 시클로헥산 고리 등을 그 예로 들 수 있다. 상기 시클로알킬렌기에 포함되어 있는 하나 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In addition, in R 10 , the cycloalkylene group may be selected from 4 to 14, or 4 to 10, or 4 to 6 non-aromatic divalent monocyclic, bicyclic or tricyclic hydrocarbon moieties. In the present specification, the alkylene group may include at least one unsaturated bond in the molecule. In addition, as said cycloalkylene group, although it is not limited to this, a bivalent cyclopentane ring, a cyclohexane ring, etc. are mentioned as an example. One or more hydrogen atoms included in the cycloalkylene group may be substituted with any substituent.
또한, 상기 R10에 있어서, 상기 아릴렌기는 6 내지 14개, 또는 6 내지 12개의 고리 원자를 가지는 2가 모노시클릭, 바이시클릭 또는 트리시클릭 방향족 탄화수소 부위를 의미하며, 이에 한정되는 것은 아니나, 2가의, 벤젠 고리, 나프탈렌 고리, 안트라센 고리, 비페닐 고리 등을 그 예로 들 수 있다. 상기 아릴렌기에 포함되어 있는 하나 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In addition, in the R 10 , the arylene group means a divalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having 6 to 14, or 6 to 12 ring atoms, but is not limited thereto. And divalent, benzene ring, naphthalene ring, anthracene ring, biphenyl ring and the like. One or more hydrogen atoms included in the arylene group may be substituted with any substituent.
한편, 상기 R10는, 이에 한정되는 것은 아니나, 그 중에서도 치환 또는 비치환된 C1~10 알킬렌기인 것이 바람직하고, 치환 또는 비치환된 C1~8 알킬렌기인 것이 보다 바람직하며, 치환 또는 비치환된 C1~4 알킬렌기인 것이 더욱 바람직하다.On the other hand, the R 10 include, but are not limited to this, it is preferable that among a substituted or unsubstituted C 1 ~ 10 alkylene group, and more preferably substituted or unsubstituted C 1 ~ 8 alkylene group, a substituted or unsubstituted C 1 ~ 4 alkylene group is more preferable.
보다 구체적으로, 이에 한정되는 것은 아니나, 상기 포스페이트 화합물은 하기 [화학식 29] 내지 [화학식 32]로 표시되는 화합물들로 이루어진 군으로 선택된 1종 이상인 것이 특히 바람직하다.More specifically, although not limited thereto, the phosphate compound is particularly preferably one or more selected from the group consisting of compounds represented by the following [Formula 29] to [Formula 32].
[화학식 29][Formula 29]
[화학식 30][Formula 30]
[화학식 31][Formula 31]
[화학식 32][Formula 32]
한편, 본 발명의 포스페이트 화합물의 함량은 라디칼 경화형 조성물 100 중량부에 대하여, 1 내지 40 중량부정도, 바람직하게는 1 내지 35 중량부정도, 더욱 바람직하게는 1 내지 30 중량부정도일 수 있다. 포스페이트 화합물의 함량이 상기 범위보다 많이 포함되는 경우 밀착성 및 유리전이온도가 하락할 수 있으며, 상기 범위보다 적게 포함되는 경우 내수성이 취약해질 수 있다.On the other hand, the content of the phosphate compound of the present invention may be about 1 to 40 parts by weight, preferably about 1 to 35 parts by weight, and more preferably about 1 to 30 parts by weight based on 100 parts by weight of the radical curable composition. When the amount of the phosphate compound is included in more than the above range, the adhesion and glass transition temperature may decrease, and when less than the above range, the water resistance may be weak.
라. 라디칼 개시제 (D)la. Radical initiator (D)
다음으로, 본 발명에 따른 라디칼 경화형 조성물에 포함되는 상기 라디칼 개시제는, 라디칼 중합성을 촉진하여 경화 속도를 향상시키기 위한 것이다. 이때, 상기 라디칼 개시제로는 당해 기술 분야에서 일반적으로 사용되는 라디칼 개시제들이 제한 없이 사용될 수 있으며, 예를 들면, 1-하이드록시-사이클로헥실-펜닐-케톤(1-Hydroxy-cyclohexyl-phenyl-ketone), 2-하이드록시-2-메틸-1-페닐-1-프로판온(2-Hydroxy-2-methyl-1-phenyl-1-propanone), 2-히드록시-1-[4-(2-하이드록시에톡시)페닐]-2-메틸-1-프로판온(2-Hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methyl-1-propanone), 메틸벤조일포르메이트(Methylbenzoylformate), 옥시-페닐-아세트산-2-[2-옥소-2-페닐-아세톡시-에톡시]-에틸 에스테르(oxy-phenyl-acetic acid -2-[2 oxo-2phenyl-acetoxy-ethoxy]-ethyl ester), 옥시-페닐-아세트산-2-[2-하이드록시-에톡시]-에틸 에스테르(oxy-phenyl-acetic acid-2-[2-hydroxy-ethoxy]-ethyl ester), 알파-디메톡시-알파-페닐아세토페논(alpha-dimethoxy-alpha-phenylacetophenone), 2-벤질-2-(디메틸아미노)1-[4-(4-모르폴리닐) 페닐]-1-부타논(2-Benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl) phenyl]-1-butanone), 2-메틸-1-[4-(메틸티오)페닐]-2-(4-모르폴리닐)-1-프로판온(2-Methyl-1-[4-(methylthio)phenyl] -2-(4-morpholinyl)-1-propanone), 디페닐 (2,4,6-트리메틸벤조일)-포스핀 옥사이드(Diphenyl (2,4,6-trimethylbenzoyl)-phosphine oxide), 페닐비스(2,4,6-트리메틸벤조일)-포스핀옥사이드(phenylbis(2,4,6-trimethylbenzoyl)-phosphineoxide)로 이루어진 그룹으로부터 선택된 1종 이상일 수 있다. 특히, 본 발명에 있어서, 페닐비스(2,4,6-트리메틸벤조일)-포스핀옥사이드(phenylbis(2,4,6-trimethylbenzoyl)-phosphineoxide)인 것이 바람직하다.Next, the radical initiator contained in the radical curable composition according to the present invention is for promoting radical polymerizability and improving the curing rate. In this case, as the radical initiator, radical initiators generally used in the art may be used without limitation, for example, 1-hydroxy-cyclohexyl-phenyl-ketone (1-Hydroxy-cyclohexyl-phenyl-ketone) , 2-hydroxy-2-methyl-1-phenyl-1-propanone (2-Hydroxy-2-methyl-1-phenyl-1-propanone), 2-hydroxy-1- [4- (2-hydroxy Hydroxyethoxy) phenyl] -2-methyl-1-propanone (2-Hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propanone), methylbenzoylformate, Oxy-phenyl-acetic acid-2- [2 oxo-2phenyl-acetoxy-ethoxy] -ethyl ester (oxy-phenyl-acetic acid-2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester) , Oxy-phenyl-acetic acid-2- [2-hydroxy-ethoxy] -ethyl ester, oxy-phenyl-acetic acid-2- [2-hydroxy-ethoxy] -ethyl ester, alpha-dimethoxy-alpha- Phenylacetophenone (alpha-dimethoxy-alpha-phenylacetophenone), 2-benzyl-2- (dimethylamino) 1- [4- (4-morpholi ) Phenyl] -1-butanone (2-Benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone), 2-methyl-1- [4- (methylthio) Phenyl] -2- (4-morpholinyl) -1-propanone (2-Methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone), diphenyl (2 (4,6-trimethylbenzoyl) -phosphine oxide (Diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide), phenylbis (2,4,6-trimethylbenzoyl) -phosphine oxide (phenylbis (2,4) , 6-trimethylbenzoyl) -phosphineoxide) may be one or more selected from the group consisting of. In particular, in the present invention, phenylbis (2,4,6-trimethylbenzoyl) -phosphine oxide (phenylbis (2,4,6-trimethylbenzoyl) -phosphineoxide) is preferable.
한편, 상기 라디칼 개시제의 함량은 라디칼 경화형 조성물 100 중량부에 대해 0.5 내지 20 중량부, 0.5 내지 15 중량부 또는 0.5 내지 10 중량부 정도인 것이 바람직하다. 라디칼 개시제의 함량이 상기 수치범위를 만족하는 경우, 보호층의 경화가 원활하게 이루어질 수 있기 때문이다.On the other hand, the content of the radical initiator is preferably about 0.5 to 20 parts by weight, 0.5 to 15 parts by weight or 0.5 to 10 parts by weight with respect to 100 parts by weight of the radical curable composition. This is because when the content of the radical initiator satisfies the numerical range, the protective layer may be smoothly cured.
마. 조성물의 물성hemp. Physical properties of the composition
한편, 상기와 같은 본 발명의 라디칼 경화형 조성물은 전체 수산기값(hydroxyl value)이 500 내지 900 mg·KOH/g, 보다 바람직하게는 500 내지 850 mg·KOH/g, 더욱 바람직하게는 500 내지 800 mg·KOH/g 정도이다. 이와 같이 라디칼 경화형 조성물의 수산기값(hydroxyl value)이 상기 수치 범위를 만족하는 경우에는, 이를 이용하여 형성되는 보호층이 비교적 높은 습도 상황에서도 편광자와 안정적으로 높은 밀착성을 유지할 수 있다는 장점이 있으며, 또한 경화된 보호층 내부의 결합력이 강하여 높은 유리전이온도를 가질 수 있는바, 열적으로 안정성을 확보할 수 있다는 장점이 있다.On the other hand, the radical curable composition of the present invention as described above has a total hydroxyl value (hydroxyl value) of 500 to 900 mg KOH / g, more preferably 500 to 850 mg KOH / g, more preferably 500 to 800 mg It is about KOH / g. As such, when the hydroxyl value of the radical curable composition satisfies the numerical range, there is an advantage that the protective layer formed by using the radical curable composition can stably maintain high adhesion with the polarizer even under relatively high humidity. Since the bonding force inside the cured protective layer is strong and may have a high glass transition temperature, there is an advantage that the thermal stability can be secured.
한편, 상기 수산기값(hydroxyl value)은 시료 1g을 아세틸화할 때 수산기와 결합한 초산을 중화시키는데 필요한 수산화칼륨(KOH)의 ㎎수를 의미하며, 측정 방법은 특별히 한정되지 않는다. 예를 들면, 하기 식 (1)을 통하여 샘플 내의 수산기값(hydroxyl value)을 계산할 수 있다.On the other hand, the hydroxyl value (hydroxyl value) means the number of mg of potassium hydroxide (KOH) required to neutralize the acetic acid bound to the hydroxyl group when acetylating the sample 1g, the measurement method is not particularly limited. For example, the hydroxyl value in the sample can be calculated through the following equation (1).
식 (1): (KOH 분자량 x 샘플 내의 -OH의 개수 x 1000) / 샘플의 분자량Formula (1): (KOH molecular weight x number of -OH in the sample x 1000) / molecular weight of the sample
또한, 상기 라디칼 경화형 조성물은 경화 후 유리전이온도가 50℃ 이상, 예를 들면, 80 내지 300℃ 또는 90 내지 200℃일 수 있다. 상기와 같은 수치 범위의 유리전이온도를 갖는 경우 보호층이 우수한 내열성 및 내수성을 가질 수 있다.In addition, the radical curable composition may have a glass transition temperature of 50 ° C. or higher after curing, for example, 80 ° C. to 300 ° C. or 90 ° C. to 200 ° C. When the glass transition temperature in the numerical range as described above may have a good heat resistance and water resistance.
또한, 상기 라디칼 경화형 조성물은 점도가 10 내지 300cP 또는 20 내지 100cP 정도인 것이 바람직하다. 조성물의 점도가 상기 수치범위를 만족하는 경우 보호층의 두께를 얇게 형성할 수 있고, 저점도를 갖기 때문에 작업성이 우수한 장점이 있다.In addition, the radical curable composition preferably has a viscosity of about 10 to 300 cP or about 20 to 100 cP. When the viscosity of the composition satisfies the numerical range, the thickness of the protective layer may be thinly formed, and since the composition has a low viscosity, there is an excellent workability.
한편, 상기 라디칼 경화형 조성물을 이용하여 형성된 보호층의 두께는 0.5 내지 20 ㎛인 것이 바람직하며, 예를 들면, 0.5 내지 15 ㎛ 또는 0.5 내지 10 ㎛ 일 수 있다. 보호층의 두께가 상기 범위를 만족하는 경우 제조되는 편광판의 박형 경량화가 가능하기 때문이다. 0.5 ㎛ 미만인 경우 편광자의 열충격 안정성 및 컬 특성이 취약하고, 20㎛ 이상인 경우에는 편광판의 박형화가 어렵다.On the other hand, the thickness of the protective layer formed using the radical curable composition is preferably 0.5 to 20 ㎛, for example, may be 0.5 to 15 ㎛ or 0.5 to 10 ㎛. This is because when the thickness of the protective layer satisfies the above range, the thickness of the polarizing plate produced can be reduced. If it is less than 0.5 μm, the thermal shock stability and curl characteristics of the polarizer are weak, and if it is 20 μm or more, the thickness of the polarizing plate is difficult.
1-3. 보호 필름1-3. Protective film
한편, 본 발명의 상기 편광판은 필요에 따라서 편광자의 일면에 보호 필름을 더 구비할 수 있다. 보다 구체적으로, 본 발명의 상기 편광판은 상기 보호층이 편광자의 일면에 형성된 경우, 보호층이 형성된 면의 반대면에 편광자를 지지 및 보호하기 위하여 접착제층을 매개로 별도의 보호 필름을 부착할 수 있다.On the other hand, the polarizing plate of the present invention may further include a protective film on one surface of the polarizer as needed. More specifically, in the polarizing plate of the present invention, when the protective layer is formed on one surface of the polarizer, a separate protective film may be attached through the adhesive layer to support and protect the polarizer on the opposite side of the surface on which the protective layer is formed. have.
이때, 상기 보호 필름은 편광자를 지지 및 보호하기 위한 것으로, 당해 기술 분야에 일반적으로 알려져 있는 다양한 재질의 보호 필름들, 예를 들면, 셀룰로오스계 필름, 폴리에틸렌테레프탈레이트(PET, polyethylene terephthalate) 필름, 싸이클로올레핀 폴리머(COP, cycloolefin polymer) 필름, 아크릴계 필름 등이 제한없이 사용될 수 있다. 이 중에서도 광학 특성, 내구성, 경제성 등을 고려할 때, 아크릴계 필름을 사용하는 것이 특히 바람직하다. In this case, the protective film is for supporting and protecting the polarizer, protective films of various materials generally known in the art, for example, cellulose-based film, polyethylene terephthalate (PET) film, cyclo An olefin polymer (COP, cycloolefin polymer) film, acrylic film, or the like can be used without limitation. Among them, it is particularly preferable to use an acrylic film in view of optical properties, durability, economy and the like.
한편, 본 발명에서 사용 가능한 아크릴계 필름은 (메트)아크릴레이트계 수지를 주성분으로 포함하는 성형 재료를 압출 성형에 의해 성형하여 획득할 수 있다. 이때, 상기 (메트)아크릴레이트계 수지는 (메트)아크릴레이트계 단위를 포함하는 수지를 주 성분으로 하는 것으로, (메트)아크릴레이트계 단위로 이루어진 호모 폴리머 수지뿐 아니라 (메트)아크릴레이트계 단위 이외에 다른 단량체 단위가 공중합된 공중합체 수지 및 상기와 같은 (메트)아크릴레이트계 수지에 다른 수지가 블랜드된 블랜드 수지도 포함하는 개념이다.On the other hand, the acrylic film usable in the present invention can be obtained by molding a molding material containing (meth) acrylate-based resin as a main component by extrusion molding. In this case, the (meth) acrylate-based resin is a resin containing a (meth) acrylate-based unit as a main component, as well as a homopolymer resin consisting of (meth) acrylate-based units, as well as (meth) acrylate-based units In addition to the copolymer resin copolymerized with other monomer units and the (meth) acrylate-based resin as described above, the concept also includes a blend resin blended with other resin.
한편, 상기 (메트)아크릴레이트계 단위는, 예를 들면, 알킬(메트)아크릴레이트계 단위일 수 있다. 여기서, 상기 알킬(메트)아크릴레이트계 단위는 알킬아크릴레이트계 단위 및 알킬메타크릴레이트계 단위를 모두 의미하는 것으로, 상기 알킬(메트)아크릴레이트계 단위의 알킬기는 탄소수 1 ~ 10인 것이 바람직하며, 탄소수 1 ~ 4인 것이 더욱 바람직하다. Meanwhile, the (meth) acrylate-based unit may be, for example, an alkyl (meth) acrylate-based unit. Here, the alkyl (meth) acrylate-based unit means both an alkyl acrylate-based unit and an alkyl methacrylate-based unit, the alkyl group of the alkyl (meth) acrylate-based unit is preferably 1 to 10 carbon atoms, It is more preferable that it is C1-C4.
또한, 상기 (메트)아크릴레이트계 단위와 공중합이 가능한 단량체 단위로는, 스티렌계 단위, 말레산 무수물계 단위, 말레이미드계 단위 등을 들 수 있다. 이때, 상기 스티렌계 단위로는, 이에 한정되는 것은 아니나, 스티렌, α-메틸스티렌 등을 그 예로 들 수 있고; 상기 말레산 무수물계 단량체로는, 이에 한정되는 것은 아니나, 말레산 무수물, 메틸 말레산 무수물, 시클로헥실 말레산 무수물, 페닐 말레산 무수물 등을 그 예로 들 수 있으며; 상기 말레이미드계 단량체로는, 이에 한정되는 것은 아니나, 말레이미드, N-메틸 말레이미드, N-시클로헥실 말레이미드, N-페닐 말레이미드 등을 그 예로 들 수 있다. 이들은 단독으로 또는 혼합하여 사용될 수 있다.Moreover, a styrene type unit, a maleic anhydride type unit, a maleimide type unit, etc. are mentioned as a monomeric unit copolymerizable with the said (meth) acrylate type unit. In this case, the styrene-based unit is not limited thereto, and examples thereof include styrene, α-methylstyrene, and the like; Examples of the maleic anhydride monomer include, but are not limited to, maleic anhydride, methyl maleic anhydride, cyclohexyl maleic anhydride, phenyl maleic anhydride, and the like; Examples of the maleimide monomers include, but are not limited to, maleimide, N-methyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, and the like. These may be used alone or in combination.
한편, 상기 아크릴계 필름은 락톤 고리 구조를 갖는 (메트)아크릴레이트계 수지를 포함하는 필름일 수 있다. 락톤 고리 구조를 갖는 (메트)아크릴레이트계 수지의 구체적인 예로서는 예를 들어 일본 공개특허공보 제2000-230016호, 일본공개특허공보 제 2001-151814호, 일본 공개특허공보 제 2002-120326호 등에 기재된 락톤 고리 구조를 갖는 (메트)아크릴레이트계 수지를 들 수 있다. On the other hand, the acrylic film may be a film containing a (meth) acrylate resin having a lactone ring structure. As a specific example of (meth) acrylate type resin which has a lactone ring structure, it is the lactone described, for example in Unexamined-Japanese-Patent No. 2000-230016, Unexamined-Japanese-Patent No. 2001-151814, 2002-120326, etc. (Meth) acrylate type resin which has a ring structure is mentioned.
상기 아크릴계 필름의 제조 방법은 특별히 한정되지 않으며, 예를 들어 (메트)아크릴레이트계 수지와 그 밖의 중합체, 첨가제 등을 임의의 적절한 혼합 방법에 의해 충분히 혼합하여 열가소성 수지 조성물을 제조한 후 이를 필름 성형하여 제조하거나, 또는 (메트) 아크릴레이트계 수지와, 그 밖의 중합체, 첨가제 등을 별도의 용액으로 제조한 후 혼합하여 균일한 혼합액을 형성한 후 이를 필름 성형할 수도 있다. 또한, 상기 아크릴계 필름은 미연신 필름 또는 연신 필름 중 어느 것일 수 있다. 연신 필름인 경우에는 1축 연신 필름 또는 2축 연신 필름 일 수 있고, 2축 연신 필름인 경우에는 동시 2축 연신 필름 또는 축차 2축 연신 필름 중 어느 것일 수 있다.The method for producing the acrylic film is not particularly limited, and for example, (meth) acrylate-based resin and other polymers, additives, and the like are sufficiently mixed by any suitable mixing method to prepare a thermoplastic resin composition, which is then film-molded. Or (meth) acrylate-based resin and other polymers, additives and the like may be prepared in a separate solution and then mixed to form a uniform mixed solution and then film-molded. In addition, the acrylic film may be any of an unstretched film or a stretched film. In the case of a stretched film, it may be a uniaxial stretched film or a biaxially stretched film, and in the case of a biaxially stretched film, it may be either a simultaneous biaxially stretched film or a successive biaxially stretched film.
한편, 본 발명의 상기 편광판은, 접착력을 더욱 향상시키기 위하여, 상기 접착제층과 상기 보호 필름 사이에 프라이머층을 더 포함할 수도 있다. 이때, 상기 프라이머층은 수분산성 고분자 수지, 수분산성 미립자 및 물을 포함하는 코팅액을 바 코팅법, 그라비어 코팅법 등을 이용하여 보호 필름 상에 도포하고 건조하는 방법에 의해 형성될 수 있다. 상기 수분산성 고분자 수지는 예를 들면, 수분산 폴리우레탄계 수지, 수분산 아크릴계 수지, 수분산 폴리에스테르계 수지 또는 이들의 조합 등일 수 있으며, 수분산성 미립자는 실리카, 티타니아, 알루미나, 지르코니아 등의 무기계 미립자나, 실리콘계 수지, 불소계 수지, (메트)아크릴계 수지, 가교 폴리비닐알코올 및 멜라민계 수지로 이루어진 유기계 미립자 또는 이들의 조합을 이용할 수 있으나, 이에 한정되는 것은 아니다.On the other hand, the polarizing plate of the present invention may further include a primer layer between the adhesive layer and the protective film in order to further improve the adhesive force. In this case, the primer layer may be formed by coating and drying a coating solution containing a water dispersible polymer resin, water dispersible fine particles and water on a protective film using a bar coating method, a gravure coating method, or the like. The water-dispersible polymer resin may be, for example, a water-based polyurethane resin, a water-based acrylic resin, a water-based polyester resin, or a combination thereof, and the water-dispersible microparticles may be inorganic fine particles such as silica, titania, alumina, zirconia, or the like. B, organic fine particles made of silicone resin, fluorine resin, (meth) acrylic resin, crosslinked polyvinyl alcohol and melamine resin, or a combination thereof may be used, but are not limited thereto.
한편, 상기 편광자와 보호 필름의 부착은 롤 코터, 그라비어 코터, 바 코터, 나이프 코터 또는 캐필러리 코터 등을 사용하여 편광자 또는 보호 필름의 표면에 접착제를 도포한 후, 이들을 합지 롤로 가열 합지하거나, 상온 압착하여 합지하는 방법 또는 합지 후 UV 조사하는 방법 등에 의해 수행될 수 있다. 한편, 상기 접착제로는 당해 기술 분야에서 사용되는 다양한 편광판용 접착제들, 예를 들면, 폴리비닐알코올계 접착제, 폴리우레탄계 접착제, 아크릴계 접착제, 양이온계 또는 라디칼계 접착제 등이 제한 없이 사용될 수 있다.On the other hand, the polarizer and the protective film is attached to the surface of the polarizer or the protective film using a roll coater, gravure coater, bar coater, knife coater or capillary coater, etc., and then heat lamination with a lamination roll, It may be carried out by a method of pressing at room temperature and laminating or a method of UV irradiation after lamination. On the other hand, as the adhesive, various polarizing plate adhesives used in the art, for example, polyvinyl alcohol-based adhesives, polyurethane-based adhesives, acrylic adhesives, cationic or radical-based adhesives and the like can be used without limitation.
1-4. 점착층1-4. Adhesive layer
한편, 본 발명의 편광판은, 표시장치 패널 또는 위상차 필름과 같은 광학 필름과의 부착을 위해, 필요에 따라, 상기 보호층의 상부에 점착층을 포함할 수 있다. Meanwhile, the polarizing plate of the present invention may include an adhesive layer on an upper portion of the protective layer, if necessary, for attachment to an optical film such as a display panel or a retardation film.
이때, 상기 점착층은 당해 기술 분야에 잘 알려져 있는 다양한 점착제들을 사용하여 형성될 수 있으며, 그 종류가 특별히 제한되는 것은 아니다. 예를 들면, 상기 점착층은 고무계 점착제, 아크릴계 점착제, 실리콘계 점착제, 우레탄계 점착제, 폴리비닐알코올계 점착제, 폴리비닐피롤리돈계 점착제, 폴리아크릴아미드계 점착제, 셀룰로오스계 점착제, 비닐알킬에테르계 점착제 등을 이용하여 형성될 수 있다. 이 중에서도 투명성 및 내열성 등을 고려할 때, 아크릴계 점착제를 사용하는 것이 특히 바람직하다. In this case, the pressure-sensitive adhesive layer may be formed using various pressure-sensitive adhesives well known in the art, and the kind thereof is not particularly limited. For example, the pressure-sensitive adhesive layer may be a rubber pressure sensitive adhesive, an acrylic pressure sensitive adhesive, a silicone pressure sensitive adhesive, a urethane pressure sensitive adhesive, a polyvinyl alcohol pressure sensitive adhesive, a polyvinylpyrrolidone pressure sensitive adhesive, a polyacrylamide pressure sensitive adhesive, a cellulose pressure sensitive adhesive, a vinyl alkyl ether pressure sensitive adhesive, or the like. It can be formed using. Among these, in consideration of transparency, heat resistance and the like, it is particularly preferable to use an acrylic pressure-sensitive adhesive.
한편, 상기 점착층은 보호층 상부에 점착제를 도포하는 방법으로 형성될 수도 있고, 이형 시트 상에 점착제를 도포한 후 건조시켜 제조되는 점착 시트를 보호층 상부에 부착하는 방법으로 형성될 수도 있다. On the other hand, the pressure-sensitive adhesive layer may be formed by applying a pressure-sensitive adhesive on the protective layer, or may be formed by a method of attaching the pressure-sensitive adhesive sheet prepared by applying the pressure-sensitive adhesive on the release sheet and dried on the protective layer.
2. 화상표시장치2. Image display device
상기와 같은 본 발명의 편광판은 액정표시장치 등과 같은 화상표시장치에 유용하게 적용될 수 있다. 상기 화상표시장치는 예를 들면, 액정 패널 및 이 액정 패널의 양면에 각각 구비된 편광판들을 포함하는 액정 표시장치일 수 있으며, 이때, 상기 편광판 중 적어도 하나가 본 발명에 따른 편광판일 수 있다. 이때, 상기 액정표시장치에 포함되는 액정 패널의 종류는 특별히 한정되지 않는다. 예를 들면, 그 종류에 제한되지 않고, TN(twisted nematic)형, STN(super twisted nematic)형, F(ferroelectic)형 또는 PD(polymer dispersed)형과 같은 수동 행렬 방식의 패널; 2단자형(two terminal) 또는 3단자형(three terminal)과 같은 능동행렬 방식의 패널; 횡전계형(IPS; In Plane Switching) 패널 및 수직배향형(VA; Vertical Alignment) 패널 등의 공지의 패널이 모두 적용될 수 있다. 또한, 액정표시장치를 구성하는 기타 구성, 예를 들면, 상부 및 하부 기판(ex. 컬러 필터 기판 또는 어레이 기판) 등의 종류 역시 특별히 제한되지 않고, 이 분야에 공지되어 있는 구성이 제한 없이 채용될 수 있다.The polarizing plate of the present invention as described above can be usefully applied to an image display device such as a liquid crystal display device. The image display apparatus may be, for example, a liquid crystal display including a liquid crystal panel and polarizing plates provided on both surfaces of the liquid crystal panel, wherein at least one of the polarizing plates may be a polarizing plate according to the present invention. In this case, the type of liquid crystal panel included in the liquid crystal display device is not particularly limited. For example, a panel of a passive matrix type such as, but not limited to, a twisted nematic (TN) type, a super twisted nematic (STN) type, a ferrolectic (F) type, or a polymer dispersed (PD) type; Active matrix panels such as two-terminal or three-terminal; All known panels, such as an In Plane Switching (IPS) panel and a Vertical Alignment (VA) panel, can be applied. In addition, other configurations constituting the liquid crystal display device, for example, types of upper and lower substrates (eg, color filter substrates or array substrates) are not particularly limited, and configurations known in the art may be employed without limitation. Can be.
이하에서는 구체적인 실시예를 통해 본 발명을 보다 자세히 설명하기로 한다.Hereinafter, the present invention will be described in more detail with reference to specific examples.
제조예 1 - 아크릴계 보호 필름의 제조Preparation Example 1-Preparation of Acrylic Protective Film
폴리(N-시클로헥실말레이미드-co-메틸메타크릴레이트), 스티렌-무수말레산 공중합체 수지 및 페녹시계 수지를 100:2.5:5의 중량비로 균일하게 혼합한 수지 조성물을 원료 호퍼(hopper)로부터 압출기까지를 질소 치환한 24φ의 압출기에 공급하여 250℃에서 용융하여 원료 펠렛(pellet)을 제조하였다.The raw material hopper is a resin composition obtained by uniformly mixing poly (N-cyclohexylmaleimide-co-methylmethacrylate), styrene-maleic anhydride copolymer resin and phenoxy resin in a weight ratio of 100: 2.5: 5. From the extruder to a nitrogen-substituted 24φ extruder and melted at 250 ° C. to prepare a raw material pellet.
페녹시계 수지는 InChemRez사의 PKFE(Mw=60,000, Mn=16,000, Tg=95℃)을 사용하였고, 스티렌-무수말레산 공중합체 수지는 스티렌 85 중량%, 무수말레익안하이드라이드 15 중량%인 Dylaeck 332를 사용하였으며, 폴리(N-시클로헥실말레이미드-co-메틸메타크릴레이트) 수지는 NMR 분석 결과 N-시클로헥실말레이미드의 함량이 6.5 중량%인 것을 사용하였다.The phenoxy resin was PKFE (Mw = 60,000, Mn = 16,000, Tg = 95 ° C.) manufactured by InChemRez, and the styrene-maleic anhydride copolymer resin was Dylaeck 332 having 85% by weight of styrene and 15% by weight of maleic anhydride. The poly (N-cyclohexylmaleimide-co-methylmethacrylate) resin was used in which the content of N-cyclohexylmaleimide was 6.5% by weight as a result of NMR analysis.
얻어진 원료 펠렛을 진공 건조하고 260℃에서 압출기로 용융, 코트 행거 타입의 티-다이(T-die)에 통과시키고, 크롬 도금 캐스팅 롤 및 건조 롤 등을 거쳐 두께 150 ㎛의 필름을 제조하였다. 이 필름을 파일로트 연신 장비를 사용하여 125℃에서 MD 방향으로 롤의 속도 차를 이용하여 170% 비율로 연신하여 아크릴 필름을 제조하였다. The obtained raw material pellets were vacuum-dried and melted with an extruder at 260 degreeC, passed through the T-die of a coat hanger type, and the film of 150 micrometers in thickness was produced through the chrome plating casting roll, a drying roll, etc. The film was stretched at a rate of 170% using a speed difference of the roll in the MD direction at 125 ° C. using a pilot stretching equipment to produce an acrylic film.
상기와 같은 과정을 통해 제조된 아크릴 필름을 코로나 처리한 후, 상기 아크릴 필름의 일면에 CK-PUD-F(조광 우레탄 분산액)을 순수로 희석하여 제조된 고형분 함량 10중량%의 프라이머 조성물에 옥사졸린 가교제 (일본촉매사, WS700) 20중량부를 첨가한 프라이머 조성물을 #7 바(bar)로 코팅한 후 TD 방향으로 130℃에서 텐더를 이용하여 190% 연신하여 최종적으로 프라이머층 두께가 400nm인 아크릴계 보호 필름을 제조하였다. After the corona treatment of the acrylic film prepared through the process described above, oxazoline in a primer composition of 10% by weight of solid content prepared by diluting CK-PUD-F (dilute urethane dispersion) with pure water on one surface of the acrylic film. After coating 20 parts by weight of a crosslinking agent (Japan Catalyst Co., Ltd., WS700) with a primer composition # 7 bar, stretched 190% using a tender at 130 ° C. in the TD direction, and finally, an acrylic protective material having a primer thickness of 400 nm. A film was prepared.
제조예 2 - 라디칼 경화형 조성물의 제조Preparation Example 2-Preparation of Radical Curable Composition
(1) 라디칼 경화형 조성물 A(1) Radical Curable Composition A
GLA(glyceryl monoacrylate) 64.5 중량%, HEA(hydroxyethyl acrylate) 16.1 중량%, DCPDA(Dimethylol tricyclodecane diacrylate) 16.1중량%, di-(methacryloyloxy ethyl)phosphate 3.3중량%를 넣어 제조한 수지 조성물 100 중량부에 라디칼 개시제인 irgacure-819(Ciba 사) 3 중량부를 첨가하여 편광판용 라디칼 경화형 조성물 A를 제조하였다.Radical initiator was added to 100 parts by weight of the resin composition prepared by adding 64.5% by weight of GLA (glyceryl monoacrylate), 16.1% by weight of HEA (hydroxyethyl acrylate), 16.1% by weight of dimethylol tricyclodecane diacrylate (DCPDA), and 3.3% by weight of di- (methacryloyloxy ethyl) phosphate. 3 parts by weight of phosphorus irgacure-819 (Ciba) was added to prepare a radical curable composition A for polarizing plates.
(2) 라디칼 경화형 조성물 B(2) Radical Curable Composition B
GLA(glyceryl monoacrylate) 56.5 중량%, HEA(hydroxyethyl acrylate) 24.2 중량%, DCPDA(Dimethylol tricyclodecane diacrylate) 16.1중량%, di-(methacryloyloxy ethyl)phosphate 3.2중량%를 넣어 제조한 수지 조성물 100 중량부에 라디칼 개시제인 irgacure-819(Ciba 사) 3 중량부를 첨가하여 편광판용 라디칼 경화형 조성물 B를 제조하였다.Radical initiator was added to 100 parts by weight of the resin composition prepared by adding 56.5% by weight of GLA (glyceryl monoacrylate), 24.2% by weight of HEA (hydroxyethyl acrylate), 16.1% by weight of dimethylol tricyclodecane diacrylate (DCPDA), and 3.2% by weight of di- (methacryloyloxy ethyl) phosphate. 3 parts by weight of phosphorus irgacure-819 (Ciba) was added to prepare a radical curable composition B for a polarizing plate.
(3) 라디칼 경화형 조성물 C(3) Radical Curable Composition C
GLA(glyceryl monoacrylate) 32.3 중량%, GLM(glyceryl methacrylate) 32.3 중량%, HEA(hydroxyethyl acrylate) 16.1 중량%, DCPDA(Dimethylol tricyclodecane diacrylate) 16.1중량%, di-(methacryloyloxy ethyl)phosphate 3.2중량%를 넣어 제조한 수지 조성물 100 중량부에 라디칼 개시제인 irgacure-819(Ciba 사) 3 중량부를 첨가하여 편광판용 라디칼 경화형 조성물 C를 제조하였다.Manufactured by adding 32.3 wt% GLA (glyceryl monoacrylate), 32.3 wt% GLM (glyceryl methacrylate), 16.1 wt% HEA (hydroxyethyl acrylate), 16.1 wt% DCPDA (Dimethylol tricyclodecane diacrylate), 3.2 wt% di- (methacryloyloxy ethyl) phosphate To 100 parts by weight of one resin composition, 3 parts by weight of irgacure-819 (Ciba), which is a radical initiator, was added to prepare a radical curable composition C for polarizing plates.
(4) 라디칼 경화형 조성물 D(4) Radical Curable Composition D
GLA(glyceryl monoacrylate) 16.1 중량%, GLM(glyceryl methacrylate) 48.4 중량%, HEA(hydroxyethyl acrylate) 16.1 중량%, DCPDA(Dimethylol tricyclodecane diacrylate) 16.1중량%, di-(methacryloyloxy ethyl)phosphate 3.3중량%를 넣어 제조한 수지 조성물 100 중량부에 라디칼 개시제인 irgacure-819(Ciba 사) 3 중량부를 첨가하여 편광판용 라디칼 경화형 조성물 D를 제조하였다.Manufactured by adding 16.1% by weight of GLA (glyceryl monoacrylate), 48.4% by weight of GLM (glyceryl methacrylate), 16.1% by weight of HEA (hydroxyethyl acrylate), 16.1% by weight of dimethylol tricyclodecane diacrylate (DCPDA), 3.3% by weight of di- (methacryloyloxy ethyl) phosphate To 100 parts by weight of one resin composition, 3 parts by weight of irgacure-819 (Ciba), which is a radical initiator, was added to prepare a radical curable composition D for polarizing plates.
(5) 라디칼 경화형 조성물 E(5) Radical Curable Composition E
GLA(glyceryl monoacrylate) 55.5 중량%, HEA(hydroxyethyl acrylate) 13.9 중량%, DCPDA(Dimethylol tricyclodecane diacrylate) 27.8 중량%, di-(methacryloyloxy ethyl)phosphate 2.8 중량%를 넣어 제조한 수지 조성물 100 중량부에 라디칼 개시제인 irgacure-819(Ciba 사) 3 중량부를 첨가하여 편광판용 라디칼 경화형 조성물 E를 제조하였다.Radical initiator was added to 100 parts by weight of the resin composition prepared by adding 55.5% by weight of GLA (glyceryl monoacrylate), 13.9% by weight of HEA (hydroxyethyl acrylate), 27.8% by weight of dimethylol tricyclodecane diacrylate (DCPDA), and 2.8% by weight of di- (methacryloyloxy ethyl) phosphate. 3 parts by weight of phosphorus irgacure-819 (Ciba) was added to prepare a radical curable composition E for polarizing plates.
(6) 라디칼 경화형 조성물 F(6) Radical Curable Composition F
GLA(glyceryl monoacrylate) 72.6 중량%, HEA(hydroxyethyl acrylate) 8.1 중량%, DCPDA(Dimethylol tricyclodecane diacrylate) 16.1 중량%, di-(methacryloyloxy ethyl)phosphate 3.2 중량%를 넣어 제조한 수지 조성물 100 중량부에 라디칼 개시제인 irgacure-819(Ciba 사) 3 중량부를 첨가하여 편광판용 라디칼 경화형 조성물 F를 제조하였다.A radical initiator was added to 100 parts by weight of a resin composition prepared by adding 72.6% by weight of GLA (glyceryl monoacrylate), 8.1% by weight of HEA (hydroxyethyl acrylate), 16.1% by weight of dimethylol tricyclodecane diacrylate (DCPDA), and 3.2% by weight of di- (methacryloyloxy ethyl) phosphate. 3 parts by weight of phosphorus irgacure-819 (Ciba) was added to prepare a radical curable composition F for polarizing plates.
(7) 라디칼 경화형 조성물 G(7) Radical Curable Composition G
GLA(glyceryl monoacrylate) 76 중량%, HEA(hydroxyethyl acrylate) 19 중량%, di-(methacryloyloxy ethyl)phosphate 5 중량%를 넣어 제조한 수지 조성물 100 중량부에 라디칼 개시제인 irgacure-819(Ciba 사) 3 중량부를 첨가하여 편광판용 라디칼 경화형 조성물 N를 제조하였다.76 wt% GLA (glyceryl monoacrylate), 19 wt% HEA (hydroxyethyl acrylate), 5 wt% di- (methacryloyloxy ethyl) phosphate was added to 100 parts by weight of the resin composition irgacure-819 (Ciba) 3 wt% Part was added to prepare radical curable composition N for polarizing plate.
(8) 라디칼 경화형 조성물 H(8) Radical Curable Composition H
GLA(glyceryl monoacrylate) 66.7 중량%, HEA(hydroxyethyl acrylate) 16.65 중량%, DCPDA(Dimethylol tricyclodecane diacrylate) 16.65 중량%를 넣어 제조한 수지 조성물 100 중량부에 라디칼 개시제인 irgacure-819(Ciba 사) 3 중량부를 첨가하여 편광판용 라디칼 경화형 조성물 O를 제조하였다.3 parts by weight of a radical initiator irgacure-819 (Ciba) in 100 parts by weight of 66.7% by weight of GLA (glyceryl monoacrylate), 16.65% by weight of HEA (hydroxyethyl acrylate) and 16.65% by weight of dimethylol tricyclodecane diacrylate (DCPDA). It added and produced the radical curable composition O for polarizing plates.
(9) 라디칼 경화형 조성물 I(9) Radical Curable Composition I
HEA(hydroxyethyl acrylate) 80.6 중량%, DCPDA(Dimethylol tricyclodecane diacrylate) 16.1 중량%, tri-(acryloyloxy ethyl)phosphate 3.3 중량%를 넣어 제조한 수지 조성물 100 중량부에 라디칼 개시제인 irgacure-819(Ciba 사) 3 중량부를 첨가하여 편광판용 라디칼 경화형 조성물 P를 제조하였다.Into the resin composition prepared by adding 80.6% by weight of HEA (hydroxyethyl acrylate), 16.1% by weight of dimethylol tricyclodecane diacrylate (DCPDA) and 3.3% by weight of tri- (acryloyloxy ethyl) phosphate, irgacure-819 (Ciba) 3 A weight part was added and the radical curable composition P for polarizing plates was manufactured.
실시예 1Example 1
제조예 1에 의해 제조된 아크릴 필름계 보호 필름의 프라이머 층에 스포이드로 라디칼 경화형 조성물 A를 도포하고, 편광자(PVA 소자)의 일면에 적층 한 다음, 최종 접착층의 두께가 1~2㎛이 되도록 조건을 설정한 후, 라미네이터(5m/min)를 통과시켰다. 그런 다음, 상기 아크릴 필름이 적층된 면에 UV 조사장치(Metal halide lamp)를 이용하여, 1000mJ/cm2의 자외선을 조사하여, 편광자의 일면에 보호 필름을 구비하는 편광판을 제조 하였다.Radical curable composition A was applied to the primer layer of the acrylic film-based protective film prepared in Preparation Example 1 with a dropper, laminated on one surface of a polarizer (PVA device), and then the conditions were such that the thickness of the final adhesive layer was 1 to 2 μm. After setting, passed the laminator (5m / min). Then, the surface of the acrylic film is laminated using a UV irradiation device (metal halide lamp), by irradiating ultraviolet light of 1000mJ / cm 2 , to prepare a polarizing plate having a protective film on one surface of the polarizer.
다음으로, 상기 제조한 편광판의 편광자의 보호 필름이 적층된 면의 타면에 라디칼 경화형 조성물 A를 도포하고, 이형력이 있는 PET 필름을 적층한 다음, 최종 보호층 두께가 4~5㎛이 되도록 조건을 설정한 후, 라미네이터(5m/min)를 통과시켰다. 그런 다음, 이형 PET가 적층된 면에 자외선 조사장치(Metal halide lamp)를 이용하여, 1000mJ/cm2의 자외선을 조사하고, PET 필름을 제거하여, 편광자의 일면에는 보호 필름을 구비하고, 타면에는 보호층을 구비하는 편광판을 제조하였다.Next, the radical curable composition A is applied to the other surface of the surface on which the protective film of the polarizer of the prepared polarizer is laminated, the PET film having a releasing force is laminated, and the final protective layer thickness is 4 to 5 μm. After setting, passed the laminator (5m / min). Then, the surface on which the release PET is laminated is irradiated with ultraviolet light of 1000 mJ / cm 2 using a ultraviolet halide lamp, and the PET film is removed, and a protective film is provided on one side of the polarizer, and on the other side. The polarizing plate provided with a protective layer was manufactured.
실시예 2Example 2
라디칼 경화형 조성물로 B를 사용한 점을 제외하고는, 실시예 1과 동일한 방법으로 편광판을 제조하였다.A polarizing plate was manufactured in the same manner as in Example 1, except that B was used as the radical curable composition.
실시예 3Example 3
라디칼 경화형 조성물로 C를 사용한 점을 제외하고는, 실시예 1과 동일한 방법으로 편광판을 제조하였다.A polarizing plate was manufactured in the same manner as in Example 1 except that C was used as the radical curable composition.
실시예 4Example 4
라디칼 경화형 조성물로 D를 사용한 점을 제외하고는, 실시예 1과 동일한 방법으로 편광판을 제조하였다.A polarizing plate was manufactured in the same manner as in Example 1 except that D was used as the radical curable composition.
실시예 5Example 5
라디칼 경화형 조성물로 E를 사용한 점을 제외하고는, 실시예 1과 동일한 방법으로 편광판을 제조하였다.A polarizing plate was manufactured in the same manner as in Example 1 except that E was used as the radical curable composition.
실시예 6Example 6
라디칼 경화형 조성물로 F를 사용한 점을 제외하고는, 실시예 1과 동일한 방법으로 편광판을 제조하였다.A polarizing plate was manufactured in the same manner as in Example 1, except that F was used as the radical curable composition.
비교예 1Comparative Example 1
라디칼 경화형 조성물로 G를 사용한 점을 제외하고는, 실시예 1과 동일한 방법으로 편광판을 제조하였다.A polarizing plate was manufactured in the same manner as in Example 1, except that G was used as the radical curable composition.
비교예 2Comparative Example 2
라디칼 경화형 조성물로 H를 사용한 점을 제외하고는, 실시예 1과 동일한 방법으로 편광판을 제조하였다.A polarizing plate was manufactured in the same manner as in Example 1 except that H was used as the radical curable composition.
비교예 3Comparative Example 3
라디칼 경화형 조성물로 I를 사용한 점을 제외하고는, 실시예 1과 동일한 방법으로 편광판을 제조하였다.A polarizing plate was manufactured in the same manner as in Example 1 except that I was used as the radical curable composition.
실험예 1 - 수산기값Experimental Example 1-hydroxyl value
상기 실시예 및 비교예에서 사용한 라디칼 경화형 조성물의 전체 수사기값을 측정하여 하기 [표 1]에 나타내었다. 이때 라디칼 경화형 조성물의 전체 수산기값은 하기 식 (1)를 이용하여 계산하였다.The total hydrometer values of the radical curable composition used in the said Example and the comparative example were measured, and are shown in following [Table 1]. At this time, the total hydroxyl value of the radical curable composition was calculated using the following formula (1).
식 (1): (KOH 분자량 x 샘플 내의 -OH의 개수 x 1000) / 샘플의 분자량Formula (1): (KOH molecular weight x number of -OH in the sample x 1000) / molecular weight of the sample
실험예 2 - 밀착성 평가Experimental Example 2-Evaluation of Adhesion
상기 실시예 및 비교예에서 제조한 편광판의 보호층의 밀착성을 측정하여 하기 [표 1]에 나타내었다. 구체적으로, 편광자(PVA 소자) 위에 상기 실시예 및 비교예에서 사용한 라디칼 경화형 조성물을 4~5㎛으로 도포하고 그 위에 편광자(PVA 소자)를 적층하여 라미네이터를 통과시킨 다음, 자외선 조사장치(Metal halide lamp)를 이용하여 1000mJ/cm2로 UV를 조사하여, 편광자/보호층/편광자로 이루어진 박리력 샘플을 제조하였다. 제조된 샘풀을 온도 20℃, 습도 70% 조건에서 4 일간 방치한 후, 폭 20mm, 길이 100mm로 재단하고, Texture Analyzer장비(Stable Micro Systems사 TA-XT Plus)로, 속도 300m/min, 90도로 박리력을 측정하였다. 이때, 박리력이 1.0N/2cm 내지 2.0N/2cm 이면 우수, 0.5N/2cm 이상 1.0N/2cm 미만이면 양호, 0.5N/2cm 미만이면 나쁨으로 표시하였다.The adhesiveness of the protective layer of the polarizing plates manufactured by the said Example and the comparative example was measured, and is shown in following [Table 1]. Specifically, the radical curable composition used in the above Examples and Comparative Examples on the polarizer (PVA device) is applied to 4 ~ 5㎛, laminated on the polarizer (PVA device) and passed through the laminator, and then UV irradiation device (Metal halide) UV) was irradiated at 1000 mJ / cm 2 using a lamp) to prepare a peel force sample consisting of a polarizer / protective layer / polarizer. The sample was left for 4 days at a temperature of 20 ° C. and a humidity of 70%, and then cut into a width of 20 mm and a length of 100 mm, and then subjected to a texture analyzer (TA-XT Plus from Stable Micro Systems) at a speed of 300 m / min and 90 degrees. Peel force was measured. At this time, when peeling force was 1.0N / 2cm-2.0N / 2cm, it was excellent, 0.5N / 2cm or more and less than 1.0N / 2cm, and it displayed as bad if it was less than 0.5N / 2cm.
실험예 3 - 내수성 평가Experimental Example 3-Water Resistance Evaluation
상기 실시예 및 비교예에서 제조된 편광판의 내수성을 측정하여 하기 [표 1]에 나타내었다. 구체적으로, 상기 실시예 및 비교예의 편광판을 유리 기판에 라미네이션(glass lamination)한 후에 60℃ 항온조에 침지시키고, 8 시간 경과 후 편광판 단부의 탈색여부로 내수성을 판단하였으며, 변형이 없는 경우를 우수로, 탈색이 일어난 경우를 나쁨으로 표시하였다.The water resistance of the polarizing plates prepared in Examples and Comparative Examples was measured and shown in the following [Table 1]. Specifically, after laminating the polarizing plates of the above Examples and Comparative Examples on a glass substrate (glass lamination), the polarizing plate was immersed in a 60 ° C thermostat, and after 8 hours, the water resistance was judged by the discoloration of the ends of the polarizing plate, and the case of no deformation was excellent. , The case where discoloration occurred was marked as bad.
표 1
Table 1
| 구분 | 조성물 | 수산기값 [mgKOH/g] | 밀착성 | 내수성 |
| 실시예 1 | A | 591 | 우수 | 우수 |
| 실시예 2 | B | 568 | 우수 | 우수 |
| 실시예 3 | C | 569 | 우수 | 우수 |
| 실시예 4 | D | 558 | 우수 | 우수 |
| 실시예 5 | E | 508 | 우수 | 우수 |
| 실시예 6 | F | 614 | 우수 | 우수 |
| 비교예 1 | G | 702 | 우수 | 나쁨 |
| 비교예 2 | H | 593 | 양호 | 나쁨 |
| 비교예 3 | I | 389 | 나쁨 | 나쁨 |
| division | Composition | Hydroxyl value [mgKOH / g] | Adhesiveness | Water resistance |
| Example 1 | A | 591 | Great | Great |
| Example 2 | B | 568 | Great | Great |
| Example 3 | C | 569 | Great | Great |
| Example 4 | D | 558 | Great | Great |
| Example 5 | E | 508 | Great | Great |
| Example 6 | F | 614 | Great | Great |
| Comparative Example 1 | G | 702 | Great | Bad |
| Comparative Example 2 | H | 593 | Good | Bad |
| Comparative Example 3 | I | 389 | Bad | Bad |
상기 표 1에서 볼 수 있듯이, 본 발명의 실시예 1 ~ 6의 경우 밀착성이 우수할 뿐 아니라, 내수성 역시 우수하다는 것을 알 수 있다.As can be seen in Table 1, in the case of Examples 1 to 6 of the present invention it can be seen that not only excellent adhesion, but also excellent water resistance.
반면, (B) 화합물을 포함하지 않는 비교예 1의 경우 내수성에 취약한 것을 알 수 있으며, 마찬가지로 (C) 화합물을 포함하지 않는 비교예 2의 경우도 내수성에 취약한 것을 알 수 있다.On the other hand, it can be seen that Comparative Example 1, which does not contain the compound (B), is vulnerable to water resistance, and similarly, Comparative Example 2, which does not include the compound (C), is also vulnerable to water resistance.
또한, (C) 화합물로 3개의 아크릴로일기를 갖는 포스페이트 화합물을 사용하는 비교예 3의 경우는 접착력 및 내수성이 모두 나쁜 것을 알 수 있다.In addition, in the case of the comparative example 3 using the phosphate compound which has three acryloyl groups as a compound (C), it turns out that both adhesive force and water resistance are bad.
한편, 상기 실시예의 경우 편광판 제조 시 접착제층과 보호층을 편의상 동일한 라디칼 경화형 조성물을 사용하여 제조하였으나, 반드시 이에 구속되는 것은 아니다.Meanwhile, in the case of the above embodiment, the adhesive layer and the protective layer were manufactured using the same radical curable composition for convenience, but the present invention is not necessarily limited thereto.
이상에서 본 발명의 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고, 청구범위에 기재된 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 수정 및 변형이 가능하다는 것은 당 기술분야의 통상의 지식을 가진 자에게는 자명할 것이다.Although the embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and changes can be made without departing from the technical spirit of the present invention described in the claims. It will be obvious to those of ordinary skill in the field.
Claims (11)
- 편광자; 및Polarizer; And상기 편광자의 적어도 일면에 형성되는 보호층을 포함하는 편광판이며,It is a polarizing plate including a protective layer formed on at least one surface of the polarizer,상기 보호층이 (A) 분자 내에 적어도 하나의 친수성 관능기를 포함하는 라디칼 중합성 화합물; (B) 다관능성 (메트)아크릴계 화합물; (C) 분자 내에 하나 또는 두 개의 (메트)아크릴기를 포함하는 포스페이트 화합물; 및 (D) 라디칼 개시제를 포함하는 라디칼 경화형 조성물의 경화물인 편광판.A radically polymerizable compound wherein the protective layer comprises at least one hydrophilic functional group in the molecule (A); (B) a polyfunctional (meth) acrylic compound; (C) phosphate compounds containing one or two (meth) acryl groups in a molecule; And (D) a polarizing plate which is a cured product of a radical curable composition containing a radical initiator.
- 제 1 항에 있어서,The method of claim 1,상기 라디칼 경화형 조성물은 라디칼 경화형 조성물 100 중량부에 대하여, (A) 분자 내에 적어도 하나의 친수성 관능기를 포함하는 라디칼 중합성 화합물 30 중량부 초과 93 중량부 이하; (B) 다관능성 (메트)아크릴계 화합물 5 내지 40 중량부; (C) 분자 내에 하나 또는 두 개의 (메트)아크릴기를 포함하는 포스페이트 화합물 1 내지 40 중량부; 및 (D) 라디칼 개시제 0.5 내지 20 중량부를 포함하는 것인 편광판.The radically curable composition may include, based on 100 parts by weight of the radical curable composition, (A) more than 30 parts by weight and 93 parts by weight or less of a radically polymerizable compound including at least one hydrophilic functional group in a molecule; (B) 5 to 40 parts by weight of the multifunctional (meth) acrylic compound; (C) 1 to 40 parts by weight of a phosphate compound containing one or two (meth) acryl groups in the molecule; And (D) 0.5 to 20 parts by weight of a radical initiator.
- 제 1 항에 있어서,The method of claim 1,상기 라디칼 경화형 조성물의 전체 수산기값(hydroxyl value)는 500 내지 900 mg·KOH/g인 편광판.The total hydroxyl value of the radical curable composition is a polarizing plate of 500 to 900 mg · KOH / g.
- 제 1 항에 있어서,The method of claim 1,상기 (A) 라디칼 중합성 화합물의 친수성 관능기는 히드록시기인 편광판.The hydrophilic functional group of said (A) radically polymerizable compound is a hydroxyl group.
- 제 4 항에 있어서,The method of claim 4, wherein상기 (A) 라디칼 중합성 화합물은 (a-1) 분자 내에 하나의 히드록시기를 갖는 라디칼 중합성 화합물과 (a-2) 분자 내에 적어도 두 개의 히드록시기를 갖는 라디칼 중합성 화합물의 혼합물인 편광판.The said (A) radically polymerizable compound is a polarizing plate which is a mixture of the radically polymerizable compound which has one hydroxyl group in a molecule | numerator (a-1), and the radically polymerizable compound which has at least two hydroxyl group in a molecule | numerator (a-2).
- 제 1 항에 있어서,The method of claim 1,상기 (B) 다관능성 (메트)아크릴계 화합물은 하기 [화학식 I] 내지 [화학식 Ⅲ]로 표시되는 화합물들로 이루어진 군으로 선택된 1종 이상을 포함하는 것인 편광판.The (B) polyfunctional (meth) acrylic compound is a polarizing plate containing at least one selected from the group consisting of compounds represented by the following [Formula I] to [Formula III].[화학식 I][Formula I]
상기 [화학식 I]에서, R1 및 R2는 각각 독립적으로 (메트)아크릴로일옥시기 또는 (메트)아크릴로일옥시알킬기임.In [Formula I], R 1 and R 2 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group.[화학식 Ⅱ][Formula II]
상기 [화학식 Ⅱ]에서, R3, R4 및 R5는 각각 독립적으로 (메트)아크릴로일옥시기 또는 (메트)아크릴로일옥시알킬기이고, R6는 (메트)아크릴로일옥시기, (메트)아크릴로일옥시알킬기, 히드록시기, 또는 치환 또는 비치환된 C1~10 알킬기임.In [Formula II], R 3 , R 4 and R 5 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group, and R 6 is a (meth) acryloyloxy group, (meth ) Acryloyloxyalkyl group, a hydroxy group, or a substituted or unsubstituted C 1-10 alkyl group.[화학식 Ⅲ][Formula III]
상기 [화학식 Ⅲ]에서, R7은 치환 또는 비치환된 C1~10 알킬렌이고, R8 및 R9는 각각 독립적으로 (메트)아크릴로일옥시기 또는 (메트)아크릴로일옥시알킬기임.In [Chemical Formula III], R 7 is substituted or unsubstituted C 1-10 alkylene, and R 8 and R 9 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group. - 제 1 항에 있어서,The method of claim 1,상기 (C) 포스페이트 화합물은 하기 [화학식 Ⅳ]로 표시되는 화합물을 포함하는 것인 편광판.The (C) phosphate compound is a polarizing plate containing a compound represented by the following [Formula IV].[화학식 Ⅳ][Formula IV]
상기 [화학식 Ⅳ]에서, R10은 치환 또는 비치환된 C1~10 알킬렌기, 치환 또는 비치환된 C4~14 시클로알킬렌기, 치환 또는 비치환된 C6~14 아릴렌기, 또는 이들의 조합이고; R11는 수소 또는 메틸기이고; n 은 1 내지 2의 정수이고, m은 1 내지 2의 정수이고, n+m=3임.The Formula Ⅳ] in, R 10 is a substituted or unsubstituted C 1 ~ 10 alkyl group, a substituted or unsubstituted C 4 ~ 14 cycloalkyl group, a substituted or unsubstituted C 6 ~ 14 aryl group, or their Combination; R 11 is hydrogen or a methyl group; n is an integer of 1-2, m is an integer of 1-2, and n + m = 3. - 제 1 항에 있어서,The method of claim 1,상기 보호층의 두께는 0.5 내지 20㎛인 편광판.The protective layer has a thickness of 0.5 to 20㎛.
- 제 1 항에 있어서,The method of claim 1,상기 편광자의 보호층이 형성된 면의 반대면에 접착제층을 매개로 보호 필름이 부착된 편광판.Polarizing plate attached to the protective film via the adhesive layer on the opposite side of the surface on which the protective layer of the polarizer is formed.
- 제 1 항에 있어서,The method of claim 1,상기 보호층 상부에 점착층을 더 포함하는 편광판.Polarizing plate further comprises an adhesive layer on the protective layer.
- 제 1 항 내지 제 10 항 중 어느 한 항의 편광판을 포함하는 화상표시장치.An image display device comprising the polarizing plate of any one of claims 1 to 10.
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