WO2018056672A1 - Optical film exhibiting excellent adhesive force and ultraviolet-blocking function and polarizing plate comprising same - Google Patents
Optical film exhibiting excellent adhesive force and ultraviolet-blocking function and polarizing plate comprising same Download PDFInfo
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- WO2018056672A1 WO2018056672A1 PCT/KR2017/010255 KR2017010255W WO2018056672A1 WO 2018056672 A1 WO2018056672 A1 WO 2018056672A1 KR 2017010255 W KR2017010255 W KR 2017010255W WO 2018056672 A1 WO2018056672 A1 WO 2018056672A1
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- optical film
- biaxially stretched
- stretched optical
- weight
- acid
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/28—Interference filters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
Definitions
- the present invention relates to an optical film having excellent adhesion and UV blocking function, and a polarizing plate including the same.
- the liquid crystal display uses polarized light, and for this purpose, a polarizing plate is used, and a PVA element is typically used.
- a polarizing plate such as a PVA device has a weak mechanical property and is easily affected by an external environment, for example, temperature or humidity
- a protective film is required to protect it.
- Such protective films should be excellent in optical properties and in mechanical properties.
- a protective film for a PVA device used in a polarizing plate a conventional TAC film (Tr i-Acetyl-cel lulose Film) has been used, but recently, an acrylic film having better heat resistance and water absorption resistance than a TAC film has been used.
- Such a polarizing plate protective acrylic film is manufactured through a stretching process, so that the dimensional change at a high temperature and the optical properties can be stably maintained, an acrylic resin having a glass transition degree of 120 ° C or more is generally used.
- an acrylic resin having a glass transition degree of 120 ° C or more is generally used.
- the dimensional stability and optical properties of the acrylic resin In order to further improve, a ring structure is introduced into the main chain, and for this purpose, a monomer having a ring structure (cyc lic) that provides heat resistance is introduced.
- a monomer having a ring structure that provides heat resistance
- acrylic resins in particular polymethyl methacrylate (PMMA)
- PMMA polymethyl methacrylate
- the glass transition temperature is low, and thus there is a problem in that the dimensional stability is deteriorated due to the unwinding of the drawing history at high temperatures.
- the adhesive force with the PVA element which is a polarizing plate, varies depending on the stretching conditions.
- the present inventors have made diligent efforts to produce an optical film having excellent adhesion to a PVA device, which is a polarizing plate, and excellent UV blocking function while using an acrylic resin that does not contain a monomer having a ring structure in its main chain, as described below.
- stretching and including an absorber and a primer layer confirmed that this achieved the above, and completed this invention.
- An object of the present invention is to provide a biaxially stretched optical film having excellent adhesion to a polarizing plate and an ultraviolet blocking function.
- this invention is providing the polarizing plate containing the said biaxially stretched optical film.
- this invention is a biaxially stretched optical film containing a base material layer and the primer layer formed on the said base material layer,
- the said base material layer contains an acrylic resin and a ultraviolet absorber
- the primer layer provides a biaxially stretched optical film including 70 to 95 parts by weight of polyester resin and 5 to 30 parts by weight of polyurethane resin.
- Acrylic resin is excellent in transparency and can be used as an optical film, especially a polarizing plate protective film.
- the stretching process should be used to increase the mechanical strength. Since the acrylic resin has a low glass transition temperature, the optical film produced by stretching is released at high temperature, resulting in poor dimensional stability. there is a problem.
- acrylic resin used in the present invention means a resin produced by polymerizing an acrylate monomer, and is a main component constituting the base layer in the present invention.
- the 'acrylic resin' is characterized in that it does not contain a ring structure in the main chain.
- the acrylate monomer has no ring structure in the main chain, methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylnuclear methacrylate, lauryl methacrylate, and Any one or more selected from the group consisting of benzyl methacrylate can be used.
- the acrylic resin may further include a styrene monomer, for example, styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, m-methylstyrene, or benzoyl styrene, or acrylonitrile.
- the glass transition temperature of the acrylic resin is 10CTC to 120 ° C. If the glass transition temperature is less than ioo ° c there is a problem that the thermal stability is lowered when manufactured with a film.
- the weight average molecular weight of the acrylic resin is 100, 000 to 150, 000.
- methyl methacrylate and / or methyl acrylate may be used as the acrylate monomer, and preferably polymethyl methacrylate is a copolymer of methyl methacrylate and methyl acrylate.
- the polymethyl methacrylate comprises 90 to 99% by weight of methyl methacrylate, and preferably contains 1 to 10% by weight of methyl acrylate art monomer.
- the methyl acrylate serves to suppress decomposition of the copolymer.
- the polymethyl methacrylate can be produced by a known method, except that methyl acrylate is used in addition to methyl methacrylate.
- it may be prepared by an emulsion polymerization method, an emulsion-suspension polymerization method, a suspension polymerization method or the like.
- the polymethyl methacrylate in order to introduce the methyl acrylate monomer to the terminal of the polymethyl methacrylate, the polymethyl methacrylate may be polymerized first and then the methyl acrylate monomer may be polymerized.
- the ultraviolet absorber is included in the base layer, it is included to effectively block the ultraviolet rays introduced from the outside.
- the biaxially stretched optical film according to the present invention has a light transmittance of 20% or less at a wavelength of 380 nm under a condition that the thickness of the optical film is 40 urn, preferably Preferably, UV absorbers that can be up to 10% can be used without particular limitations.
- a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a triazine ultraviolet absorber, a salicylate ultraviolet absorber, and the like which are well known in the art, may be used.
- a triazine type ultraviolet absorber is preferable.
- it has excellent thermal stability and UV absorption effect, so it can have a sufficient UV blocking effect even at an appropriate amount of content, and can also prevent fume phenomenon and migration phenomenon that may occur during the film forming process.
- the triazine-based UV absorber include a compound having a 2, 4, 6-triphenyl-1, 3, 5-triazine skeleton as a main component, and various triazine-based UV absorbers commercially available in the art are It can be used without limitation.
- the ultraviolet absorber is preferably contained in 0.1 to 5 parts by weight based on 100 parts by weight of the acrylic resin.
- the base worm is made of a composition containing the acrylic resin described above.
- the base layer may be manufactured by manufacturing the acrylic resin into an unstretched film.
- the base layer may further include a phase difference regulator for phase difference control. When the acrylic resin is stretched, it has a negative birefringence characteristic in which the refractive index increases in a direction perpendicular to the stretching direction.
- the phase difference regulator may be a polycarbonate.
- the term 'polycarbonate' used in the present invention is formed by reacting an aromatic diol compound and a carbonate precursor, and may be prepared by interfacial polymerization or solution polymerization.
- bisphenol A and phosgene can be produced by interfacial polymerization.
- it is a component constituting the base layer together with the polymethyl methacrylate.
- the weight average molecular weight of the polycarbonate is preferably 10, 000 to 20, 000.
- the weight average molecular weight of the polycarbonate is more than 20, 000, the compatibility with the acrylic resin is poor, which becomes a totally opaque composition, which is not preferable for use as an optical film.
- the polycarbonate is preferably contained in 10% by weight or less in the base layer. When the content exceeds 10% by weight, it becomes an opaque composition as a whole, and the phase difference expression property is too large, which is not preferable to implement zero phase difference.
- the polycarbonate is preferably 1% by weight or more, or 2% by weight or more in the substrate layer.
- the composition may include additives such as heat stabilizers, lubricants, if necessary.
- the additives may be included in an appropriate amount within a range that does not impair the physical properties of the composition, for example, may be included in 0.1 to 5 parts by weight based on 100 parts by weight of the total composition.
- any method known in the art for example, a solution caster method, an extrusion method, or the like may be used, and for example, a melt extrusion method may be used.
- the film forming silver degree is preferably 150 ° C to 350 ° C, more preferably 200 ° C to 300 ° C.
- a T-die is attached to the tip of a known single screw extruder or twin screw extruder, and the film extruded in a film shape is obtained to obtain a film having a shape of. Can be.
- a polymer filter may be used to remove foreign substances in film forming.
- the primer layer is formed on the base layer, and may be formed on one side or both sides of the base layer as necessary.
- the primer layer of the present invention can improve the adhesive force with a polarizing plate, for example, a PVA device, when biaxially stretched to produce an optical film as described below.
- the primer layer contains 70 to 95 parts by weight and 5 to 30 parts by weight of a polyester resin and a polyurethane resin, respectively. More preferably, the primer layer is a polyester resin and a polyurethane resin, respectively 75 To 90 parts by weight and 10 to 25 parts by weight.
- the polyester-based resin refers to a resin containing an ester group formed by reaction of carboxylic acid and alcohol in the main chain, preferably a water-dispersible polyester resin, more preferably, polybasi c acid) and polyester glycols formed by the reaction of polyols.
- the polybasic acid component for example, ortho-phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, biphenyldi Aromatic dicarboxylic acids such as carboxylic acid and tetrahydrophthalic acid; Aliphatic dicarboxylic acids such as oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelline acid, sebacic acid, linoleic acid, maleic acid, fumaric acid, mesaconic acid and itaconic acid; Hex tetrahydro phthalic acid, tetrahydrophthalic acid, 1,3-cyclohexane dicarboxylic acid, 1, 4 _ cyclo aliphatic di-acid, such as dicarbox
- terephthalic acid, isophthalic acid, and succinic phase are particularly preferable.
- isophthalic acid substituted by sulfonic acid salt is used for salt time, it is especially preferable at the point of water dispersibility.
- the polyol is not particularly limited as long as it has two or more hydroxy groups in the molecule.
- the polyol may be ethylene glycol, 1'2 'propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentylglycol, pentanediol, 1,6-nucleic acid di, 1,8-octanediol, 1,10-decanediol, 4,4'-dihydroxyphenylpropane, 4,4'- Dihydrotoxymethylmethane, Diethylene glycol, Triethylene glycol, Polyethylene glycol (PEG), Dipropylene glycol, Polytetramethylene glycol (PTMG), Polypropylene glycol (PPG), 1,4-cyclonucleodimethanol 1,4 -Cyclonucleodiol diol, bisphenol A, bisphenol F, It is preferable to include at least one member selected from the group consisting of glycerin, 1,1,1-trifluor
- polyester glycol is formed by reacting polysalt time with a polyol in a molar ratio of 2.5: 1 to 1: 2.5, preferably in a molar ratio of 2.3: 1 to 1: 2.3, more preferably in a molar ratio of 2: 1 to 1: 2. It is preferable to be.
- the production method of the polyester resin is well known in the art, for example, by the method of condensation after the esterification reaction of polybasic acid and polyol, or the method of condensation polymerization after the esterification reaction of polybasic anhydride and poly, etc. Can be.
- the methods include (1) a raw material mixing step of mixing a polymerization raw material for polymerization of polyester to obtain a raw material mixture, (2) an esterification reaction step of esterifying the raw material mixture, and (3) an ester A polycondensation step may be obtained by polycondensing the pulverized raw material mixture to obtain a polyester.
- the polyester-based resin produced by the above method may include a repeating unit represented by the following formula (1):
- Ri are each independently a 3 ⁇ 4 (20 alkylene group, C 6 - 20 aryl group, or a C 5 _
- R 3 and 3 ⁇ 4 are each 3 ⁇ 4 and as the substituent substituted to 3 ⁇ 4, each independently selected from hydrogen, carboxy, hydroxy, sulfonic acid base, (20 alkyl, C 6 - 20 aryl, or C 5 - and 20 cycloalkyl, with the proviso that, R At least one of 3 and 3 ⁇ 4 is a carboxy, hydroxy, or sulfonate group, Preferably, 3 ⁇ 4 or 3 ⁇ 4 is a carboxy, or sulfonate group More preferably, the poly resin is a repeating unit represented by the following formula (2): May include:
- the polyester resin may further include additional components in addition to the above components in the range of not impairing the physical properties of the present specification.
- examples of the diocyanate include toluene isocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), toldine diisocyanate (T0DI), Nuxamethylene diisocyanate (HMDI), isopron diisocyanate (IPDI), p-phenylene diisocyanate, transcyclonucleic acid, 1,4-diisocyanate, and xylene diisocyanate (XDI), but are not limited thereto, These may be those containing one kind or two or more kinds.
- the polyester-based polyol may be obtained by reacting a polybasic acid component and a poly component, and examples of the polybasic acid component include ortho-phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, and 2,5-naphthalene.
- Aromatic dicarboxylic acids such as dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid and tetrahydrophthalic acid; Aliphatic dicarboxylic acids such as oxalic acid, succinic acid, malonic acid, glutaric acid adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, linoleic acid, maleic acid, fumaric acid, mesaconic acid and itaconic acid; Alicyclic dicarboxylic acids such as nucleated hydrophthalic acid, tetrahydrophthalic acid, 1,3-cyclonucleic acid dicarboxylic acid, and 1,4-cyclonucleic acid dicarboxylic acid; Or semi-ung derivatives such as acid anhydrides, alkyl esters, and acid halides thereof, and the like, but are not limited thereto, and may include one or two or more kinds from these groups.
- the polycarbonate-based polyol may be obtained by reacting a compound having a carbonate group and a polyol component.
- the compound having the carbonate group include diphenyl carbonate, Dialkyl carbonate, alkylene carbonate, and the like, but is not limited thereto.
- the polyether poly.ol can be obtained by adding a poly ring-opening polymerization of alkylene oxide to the component.
- the polyol component is not particularly limited as long as it has two or more hydroxyl groups in the molecule.
- polyolefin ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentylglycol, pentanedi, 1,6- Nucleic acid diols, 1,8-octanediol, 1,10-decanediol, 4,4'-dihydroxyphenylpropane, 4,4'-dihydroxymethylmethane, diethylene glycol, triethylene glycol, polyethylene glycol ( PEG), dipropylene glycol, polytetramethylene glycol (PTMG), polypropylene glycol (PPG), 1,4-cyclonucleodimethane, 1,4-cyclonucleodiol, bisphenol A, bisphenol F, glycerin, 1, It is preferable to include at least one member selected from the group consisting of 1,1—trimethylolpropane
- the polyurethane-based resin may further include other polyols or chain extenders in the additive components in a range that does not impair the physical properties of the present specification.
- the other chain extender for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanedi, 1,3-butanedi, 1,4-butanedi, Glycols such as neopentyl glycol, pentanediol, 1, 6-nucleic acid diol, propylene glycol, and the like, but are not limited thereto.
- the polyurethane-based resin may further include a neutralizing agent, if necessary. When it contains a neutralizing agent, the stability of the urethane resin in a crystal
- the neutralizing agent is selected from the group consisting of, for example, ammonia N—methylmorpholine, triethylamine, dimethylethanolamine, methyldiethanolamine, triethanolalkyne, morpholine, tripropylamine, ethane, amine and triisopropanolamine. It may be one or two or more. Preparation of the polyurethane-based resin is preferably carried out in an organic solvent inert to the isocyanate and compatible with water.
- the organic solvent is selected from the group consisting of ester solvents such as ethyl acetate, ethyl cellosolve acetate, ketone solvents such as acetone, methane ethyl ketone and methyl isobutyl ketone, and ether solvents such as dioxane tetrahydrofuran. It may be one or two or more.
- the polyurethane-based resin can be prepared through a one-shot method and a multi-stage method well known in the art. Specifically, the one-shot method is a method of reacting each component at a time, and the multi-stage method is a method of reacting each component in steps.
- the production of the polyurethane-based resin may further include a urethane reaction catalyst.
- the polyurethane resin is a carbonate-based polyurethane resin using a polycarbonate polyol as a reactant or an ester-based polyurethane resin using a polyester-based poly as a reaction product Is particularly preferred.
- the increase average molecular weight of the polyurethane-based resin is preferably from 10,000 to 1,000, 000. If the above numerical range is satisfied Adhesion can be achieved, and water dispersibility is excellent.
- the polyurethane resin preferably includes one or more functional groups selected from the group consisting of carboxy, hydroxy, sulfonate groups, and tertiary amine groups.
- the functional groups are included in the polyurethane-based resin, adhesion to the adhesive layer and water dispersibility are greatly improved.
- the polyurethane-based resin containing the functional group can be prepared by using a compound containing the functional groups as the polyol and / or isocyanate, or by adding a chain extender containing the functional groups to the poly and isocyanate reaction. Can be.
- a polyurethane-based resin containing a carboxyl or tertiary amine group may be prepared by adding a chain extender having a polyester polyol and an isocyanate half-oxygen free carboxyl group or free amine group.
- a chain extender having the free carboxyl group for example, dihydroxy carboxylic acid, dihydroxy succinic acid and the like, but is not limited thereto.
- Dihydroxy carboxylic acid with, for example, dimethylolpropionic acid, dimethyl olbu acid, dimethylol propionic acid, dimethylol butyric acid, dimethyl olpen a dialkyl all acids including a dimethylol alkanoic acid such as carbonic acid, selected from the group consisting of It may be one or two or more.
- chain extender which has the said free amine group
- Aliphatic diamines such as ethylenediamine propylene dinime, nuxa methylenediamine, 1, 4- butanediamine, aminoethylethanolamine
- Alicyclic diamines such as isophorone diamine and 4,4'-dicyclonucleosilmethanediamine
- Aromatic diamines such as xylylenediamine, rylenediamine, and the like, but are not limited thereto, and may include one or two or more selected from the group consisting of these.
- the polyurethane resin may further include additional components in addition to the components within a range that does not impair the physical properties of the present specification.
- the primer layer may further include a water-soluble fine particles and a water-dispersible crosslinking agent as necessary.
- a water-dispersible fine particles one or more selected from the group consisting of silica, titania, alumina, zirconia, and antimony-based fine particles can be used, and preferably silica can be used. When using silica, it is preferable to use it as colloidal silica.
- the diameter of the water dispersible fine particles is 50 nm to 500 nm, preferably 70 nm to 300 nm.
- the primer layer may be prepared by coating a primer solution containing a polyester resin and a polyurethane resin, and the coating method is not particularly limited.
- the primer layer may have an antistatic property.
- the primer layer may contain a surfactant, an organic salt, an inorganic salt, a conductive filler, a conductive polymer, a block copolymer, a metal oxide, or the like. 10 weight 3 ⁇ 4 ".
- the primer layer may have ultraviolet ray blocking properties, and for this purpose, the primer layer may include 0.1 to 10 wt% of an ultraviolet absorber.
- the ultraviolet absorber is not particularly limited as long as it is used in an optical film, and for example, a triazine-based, benzotriazole-based benzophenol-based ultraviolet absorber can be used.
- the primer layer may have an ant i-blocking property, and for this purpose, the primer layer may include organic beads or inorganic beads.
- the biaxially stretched optical film according to the present invention includes the base layer described above and a primer layer formed on the base layer.
- Said biaxial stretching means biaxial stretching of the unstretched film containing a base material layer and a primer layer, or uniaxially stretches a base material layer to a longitudinal direction, forms a primer layer, and extends this to a horizontal direction. I mean. Specifically, forming a primer layer on the above-described substrate layer, and the substrate layer to produce an unstretched film; And biaxially stretching the non-stretched film to produce a biaxially stretched optical film.
- the biaxially stretched optical film according to the present invention comprises the steps of uniaxially stretching the substrate layer described above in the longitudinal direction; Forming a primer layer on the substrate layer; And a step of stretching the substrate layer and the primer layer in the transverse direction, to prepare a biaxially stretched optical film.
- the draw ratio is preferably 1.2 times to 3.0 times in the MD direction and 1.5 times to 4.0 times in the TD direction.
- the stretching is to align the polymer, affecting the properties of the biaxially stretched optical film produced according to the degree of stretching. More preferably, ratio (TD draw ratio / MD draw ratio) of the draw ratio of the said MD direction and the draw ratio of a TD direction is 1.0-2.5.
- the stretching silver is preferably carried out in a temperature range of -10 ° C to +2 CTC based on the glass transition temperature of the acrylic resin.
- the stretching temperature affects the adhesive force of the biaxially stretched optical film, and there is a problem that the adhesive force is not sufficient outside the temperature range.
- the biaxially stretched optical film according to the present invention has excellent dimensional stability, and in order to evaluate such thermal dimensional stability, TTS (Temperature of Thermal) Shr inkage) is introduced.
- TTS refers to the temperature at which the optical film produced by the stretching process begins to shrink rapidly as the stretching history is relaxed. Specifically, when the temperature is applied to the optical film, it means the temperature at which shrinkage starts after expansion as the temperature increases.
- the TTS in the MD direction and the TTS in the TD direction of the biaxially stretched optical film according to the present invention are each 95 ° C. or more, preferably 100 ° C. to 120 ° C.
- the optical film according to the present invention is excellent in UV blocking function, specifically, under the condition that the thickness of the optical film is 40 um, the light transmittance having a wavelength of 380 nm is 20% or less, preferably 10% or less. . This is due to the inclusion of an ultraviolet absorber in the substrate layer.
- the 380 nm transmittance is 9% or less,> or less, ⁇ or less, 6% or less, or 5% or less.
- the lower limit is theoretically 0%, for example, the lower limit may be 0.5%, 1%, or 2%.
- the thickness of the biaxially stretched optical film according to the present invention can be appropriately adjusted as needed, for example, it is preferably 10um to 100um.
- this invention provides the polarizing plate containing the said biaxially stretched optical film.
- the biaxially stretched optical film according to the present invention can be used as a protective film of a polarizing plate, thereby compensating the mechanical properties of the polarizing plate and protecting the polarizing plate from the influence of external environment, for example, silver or humidity.
- a polarizing plate means the state containing a polarizer and a protective film.
- the primer layer of the protective film according to the present invention may be in contact with the polarizer, or the base layer of the protective film according to the present invention may be in contact with the polarizer. have.
- polarizer a film made of polyvinyl alcohol (PVA) containing iodine or dichroic dye may be used.
- the polarizer may be prepared by dyeing iodine or dichroic dye on the PVA film, but a method of manufacturing the polarizer is not particularly limited.
- the protective film according to the present invention may be provided on both sides of the polarizer, or may be provided only on one surface.
- a polarizer protective film well known in the art for example, acrylic film, TAC film, PET film, COP film, PC film, norbornene-based Films and the like can be used without limitation.
- the adhesive agent which is equipped with the protective film which concerns on this invention to a polarizer can be used. It is preferable to use a non-aqueous adhesive as said adhesive agent, and it is more preferable to use an ultraviolet curing type.
- the adhesive agent which uses radical photopolymerization reaction such as a (meth) acrylate type adhesive agent, an N / thiol type adhesive agent, an unsaturated polyester type adhesive agent; Or an adhesive using an optical cationic polymerization reaction of an epoxy adhesive, an oxetane adhesive, an epoxy / oxetane adhesive, or a vinyl ether adhesive, but is not limited thereto.
- a non-aqueous adhesive may be applied to one surface of the polarizer or the protective film to form an adhesive layer, and then, the polarizer and the protective film may be laminated, and the adhesive layer may be cured through light irradiation.
- the present invention provides an image display device including the polarizing plate, more preferably may be a liquid crystal display device.
- the liquid crystal display device is a liquid crystal display device comprising a liquid crystal cell and a first polarizing plate and a second polarizing plate respectively provided on both sides of the liquid crystal cell, wherein at least one of the first polarizing plate and the second polarizing plate is It is characterized in that the polarizing plate according to the present invention. That is, the optical film according to the present invention has a surface opposite to the liquid crystal cell surface based on the C1 polarizing plate, the surface opposite to the axel cell surface based on the C2 polarizing plate, or both. It may be provided.
- the optical film or polarizer protective film provided on the side opposite to the liquid crystal cell of the polarizing plate may be surface coated such as AG, LR.
- the biaxially stretched optical film according to the present invention is characterized in that it is excellent in adhesive strength and excellent in UV blocking function while using an acrylic resin that does not contain a monomer having a ring structure.
- n octylmercaptan 2 5 g as a chain transfer agent and 1.5 g of 2,2′-azobisisobutyronitrile were added as a polymerization initiator and dispersed in an aqueous phase while stirring at 400 rpm to prepare a suspension. After heating to 80 ° C.
- a polycarbonate resin F 1004A As the polycarbonate, a polycarbonate resin F 1004A, LG Chemical Co., Ltd. having a glass transition temperature of 134 ° C. and a weight average molecular weight of 16, 000 was used.
- Preparation Example 3 Primer Solution Polyester-based resin (A-645GH; Takamatsu oil &fat; total solid content except water is 30 wt%? 0 and polyurethane-based resin (CK-PUD-PF; light-glow paint yarn; total solid except water) 30 weight 3 ⁇ 4) was mixed at a weight ratio of solid content of 80:20, and aqueous silica was mixed at 5 weight% to prepare a primer solution
- Preparation Example 4 Primer solution
- Polymethyl methacrylate prepared in Preparation Example 1, polycarbonate of Preparation Example 2, and UV absorbers (LAF70, Adeka Co., Ltd.) were respectively added as shown in Table 1 below, and an antioxidant (Irganox 1010, BASF Corporation) was added.
- an antioxidant Irganox 1010, BASF Corporation
- the resin composition was formulated in a 0.4 phr content, dry blended, and compounded with a twin extruder to prepare a resin composition.
- the resin composition at 265 ° C.
- the sheet was melted and extrusion cast in the form of a sheet through T-Die to obtain a sheet of 180 urn.
- the optical film manufactured by the said Example and the comparative example was evaluated by the following method. ,
- TTS Temporal of Thermal Shr inkage: After preparing a sample of the optical film to the dimensions of 10 x 4.5 mm, it was measured using a TMA (Q400) equipment. Specifically, when the temperature is applied under conditions of a temperature increase rate of 10 ° C / min and a descent 0.02 N, the TTS value of the inflection point (the tangent slope is 0) at which the sample starts to contract after expansion in the ⁇ and TD directions, respectively It was made. 3) Phase difference: The phase difference was measured at a wavelength of 550 nm using a birefringence measuring instrument (AxoScan, Axometr i cs).
- the in-plane phase difference (Rin) and the thickness direction phase difference (Rth) are calculated using the measured values of the refractive index ( nx ) in the X-axis direction, the refractive index (ny) in the y- axis direction, and the refraction in the z-axis direction (nz). It was.
- nx represents the refractive index of the direction of the largest refractive index in the plane of the optical film
- ny represents the refractive index of the direction perpendicular to nx
- nz represents the refractive index of the thickness direction of the optical film
- d means the thickness (nm) of an optical film.
- Adhesion 90 ° peel peel: The adhesion was measured using a physical property analyzer (TA.XT.plus Texture Analyser; Stable Micro Systems). Specifically, it was laminated in the order of the general acrylic optical film / PVA device / the optical film prepared above. At this time, the primer surface of the optical film was faced to the PVA device, and the opposite surface (substrate surface) of the primer surface of the optical film to face the PVA device, two types were prepared. After apply
- TA.XT.plus Texture Analyser Stable Micro Systems
- the specimen was prepared with a width of 2 cm, and the peeling force was measured by peeling an optical film from the PVA device at a speed of 300 mm / min and 90 ° using a property analyzer. In addition, after the rest of the specimen was stored at 80 ° C. for 500 hours, the peel force was measured in the same manner. The results are shown in Tables 1 and 2 below.
- Examples 1 to 3 according to the present invention all showed a 380 nm transmittance of less than 5%, the adhesion was also excellent in more than 1 N / 20 kPa.
- the drawing temperature was too high, and the adhesive strength was lower than 0.5 N / 20 Pa.
- Comparative Examples 1 and 2 stretching temperature is too high, the adhesion was lower than 0.5 N / 20 Pa.
- Comparative Example 3 does not include a UV absorber, so the transmittance of 380 nm was high, and thus, the UV absorber could not be absorbed substantially.
- Comparative Examples 4 to 7 compared to Example 1 according to the present invention was confirmed that the composition of the primer layer is not satisfied with the present invention, the effective adhesion is not implemented, Comparative Example 7 In the case of the initial adhesive strength is implemented, after a long time exposure to high temperature was confirmed that the adhesive strength is lowered. Therefore, the optical film according to the present invention was confirmed that the excellent ultraviolet absorption function while excellent adhesion.
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Abstract
An optical film, according to the present invention, exhibits excellent adhesive force and an excellent ultraviolet-blocking function even when using an acrylic resin having a main chain which does not include a cyclic structure.
Description
【명세서】 【Specification】
【발명의 명칭】 [Name of invention]
접착력 및 자외선 차단 기능이 우수한 광학 필름, 및 이를 포함하는 편광판 Optical film having excellent adhesion and UV blocking function, and polarizing plate comprising the same
【기술분야】 Technical Field
관련 출원 (들)과의 상호 인용 Cross Citation with Related Application (s)
본 출원은 2016년 9월 20일자 한국 특허 출원 제 10-2016-0120102호 및 2017년 9월 18일자 한국 특허 출원 제 10-2017-0119828호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원들의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다. 본 발명은 접착력 및 자외선 차단 기능이 우수한 광학 필름, 및 이를 포함하는 편광판에 관한 것이다. This application claims the benefit of priority based on Korean Patent Application No. 10-2016-0120102 dated September 20, 2016 and Korean Patent Application No. 10-2017-0119828 dated September 18, 2017. All content disclosed in the literature is included as part of this specification. The present invention relates to an optical film having excellent adhesion and UV blocking function, and a polarizing plate including the same.
【배경기술】 Background Art
액정 표시 장치는 편광된 빛을 이용하는 것으로 이를 위하여 편광판이 사용되고 있으며, 대표적으로 PVA 소자가 사용되고 있다. 그러나, PVA 소자와 같은 편광판은 자체의 기계적 특성이 약하고 외부 환경, 예를 들어 온도나 습도의 영향을 쉽게 받기 때문에 이를 보호하기 위한 보호 필름이 필요하다. 이러한 보호 필름은 광학적 특성이 우수하여야 하고 기계적 특성이 우수하여야 한다. 편광판에 사용되는 PVA 소자의 보호 필름으로 종래에는 TAC 팔름 (Tr i-Acetyl-cel lulose Fi lm)이 사용되어 왔으나, 최근에는 TAC 필름보다 우수한 내열성 및 내흡수성 특성을 가지는 아크릴계 필름이 사용되고 있다. 이러한 편광판 보호용 아크릴계 필름은 연신 가공을 통하여 제조되는데, 고온에서의 치수 변화가 적고 광학적 특성이 안정적으로 유지될 수 있도록, 일반적으로 유리전이은도가 120°C 이상인 아크릴계 수지가 사용된다. 또한, 아크릴계 수지의 치수 안정성과 광학적 특성을
보다 향상시키기 위하여 주쇄에 고리 구조를 도입하고 있으며, 이를 위하여 내열성을 부여하는 고리 (cyc l i c) 구조의 단량체를 도입하고 있다. 그러나, 고리 구조의 단량체를 도입할 경우, 원료의 단가가 높아질 뿐만 아니라, 보다 고온에서의 가공을 하여야 하는 문제가 있다. 한편, 아크릴계 수지, 특히 폴리메틸메타크릴레이트 (PMMA)는 투명성이 우수하여 편광판 보호용 필름으로의 가능성이 있으나, 유리전이온도가 낮으몌 이에 따라 고온에서 연신 이력이 풀려 치수 안정성이 나빠지는 문제가 있다. 또한, 폴리메틸메타크릴레이트는 연신하여 필름으로 제조하면 연신 조건에 따라 편광판인 PVA 소자와의 접착력이 달라지게 되는 문제가 있다. 이에 본 발명자들은, 주쇄에 고리 구조의 단량체를 포함하지 않는 아크릴계 수지를 사용하면서도 편광판인 PVA 소자와의 접착력이 우수하고 자외선 차단 기능이 우수한 광학 필름을 제조하기 위하여 예의 노력한 결과, 후술할 바와 같이 자외선 흡수제 및 프라이머층을 포함시켜 연신하여 제조한 광학 필름이, 상기를 달성함을 확인하여 본 발명을 완성하였다. The liquid crystal display uses polarized light, and for this purpose, a polarizing plate is used, and a PVA element is typically used. However, since a polarizing plate such as a PVA device has a weak mechanical property and is easily affected by an external environment, for example, temperature or humidity, a protective film is required to protect it. Such protective films should be excellent in optical properties and in mechanical properties. As a protective film for a PVA device used in a polarizing plate, a conventional TAC film (Tr i-Acetyl-cel lulose Film) has been used, but recently, an acrylic film having better heat resistance and water absorption resistance than a TAC film has been used. Such a polarizing plate protective acrylic film is manufactured through a stretching process, so that the dimensional change at a high temperature and the optical properties can be stably maintained, an acrylic resin having a glass transition degree of 120 ° C or more is generally used. In addition, the dimensional stability and optical properties of the acrylic resin In order to further improve, a ring structure is introduced into the main chain, and for this purpose, a monomer having a ring structure (cyc lic) that provides heat resistance is introduced. However, when introducing a monomer having a cyclic structure, not only the unit cost of the raw material is increased, but also a problem of processing at a higher temperature is required. On the other hand, acrylic resins, in particular polymethyl methacrylate (PMMA), have excellent transparency and may be a protective film for polarizing plates. However, the glass transition temperature is low, and thus there is a problem in that the dimensional stability is deteriorated due to the unwinding of the drawing history at high temperatures. . In addition, when the polymethyl methacrylate is stretched and manufactured into a film, there is a problem in that the adhesive force with the PVA element, which is a polarizing plate, varies depending on the stretching conditions. Accordingly, the present inventors have made diligent efforts to produce an optical film having excellent adhesion to a PVA device, which is a polarizing plate, and excellent UV blocking function while using an acrylic resin that does not contain a monomer having a ring structure in its main chain, as described below. The optical film manufactured by extending | stretching and including an absorber and a primer layer confirmed that this achieved the above, and completed this invention.
【발명의 내용】 [Content of invention]
【해결하려는 과제】 [Problem to solve]
본 발명은 편광판과의 접착력 및 자외선 차단 기능이 우수한 2축 연신 광학 필름을 제공하기 위한 것이다. An object of the present invention is to provide a biaxially stretched optical film having excellent adhesion to a polarizing plate and an ultraviolet blocking function.
또한, 본 발명은 상기 2축 연신 광학 필름을 포함하는 편광판을 제공하기 위한 것이다. Moreover, this invention is providing the polarizing plate containing the said biaxially stretched optical film.
【과제의 해결 수단】 [Measures of problem]
상기 과제를 해결하기 위하여, 본 발명은, 기재층, 및 상기 기재층 상에 형성된 프라이머층을 포함하는, 2축 연신 광학 필름에 있어서, 상기 기재층은 아크릴계 수지, 및 자외선 흡수제를 포함하고, 상기 프라이머층은 폴리에스테르계 수지 70 내지 95 중량부 및 폴리우레탄계 수지 5 내지 30 중량부를 포함하는, 2축 연신 광학 필름을 제공한다.
아크릴계 수지는 투명성이 우수하여 광학용 필름, 특히 편광판 보호용 필름으로 사용할 수 있다. 그러나, 아크릴계 수지를 필름으로 제조할 경우 기계적 강도를 높이기 위하여 연신 공정을 사용하여야 하는데, 아크릴계 수지는 유리전이온도가 낮기 때문에 연신하여 제조한 광학용 필름은 고온에서 연신 이력이 풀려 치수 안정성이 나빠지는 문제가 있다. 이를 개선하기 위하여, 아크릴계 수지의 주쇄에 고리 구조를 도입하는 방법이 있으나, 제조 공정이 복잡하고, 원료의 단가가 높아질 뿐만 아니라, 보다 고온에서의 가공을 하여야 하는 문제가 있다. 또한, 아크릴계 수지를 연신하게 되면, 연신 조건에 따라 편광판인In order to solve the said subject, this invention is a biaxially stretched optical film containing a base material layer and the primer layer formed on the said base material layer, The said base material layer contains an acrylic resin and a ultraviolet absorber, The primer layer provides a biaxially stretched optical film including 70 to 95 parts by weight of polyester resin and 5 to 30 parts by weight of polyurethane resin. Acrylic resin is excellent in transparency and can be used as an optical film, especially a polarizing plate protective film. However, when the acrylic resin is made into a film, the stretching process should be used to increase the mechanical strength. Since the acrylic resin has a low glass transition temperature, the optical film produced by stretching is released at high temperature, resulting in poor dimensional stability. there is a problem. In order to improve this, there is a method of introducing a ring structure into the main chain of the acrylic resin, but the manufacturing process is complicated, the cost of the raw material is not only high, there is a problem that must be processed at a higher temperature. Moreover, when extending | stretching acrylic resin, it is a polarizing plate according to extending | stretching conditions.
PVA 소자와의 접착력이 달라지게 되는 문제가 있다. 이에, 본 발명에서는 후술할 바와 같은 자외선 흡수제를 사용하고, 프라이머층을 도입함으로써, 접착력 및 자외선 차단 기능이 우수한 광학 필름을 제공한다. 이하, 본 발명을 보다 상세히 설명한다. 아크릴계 수지 There is a problem that the adhesive strength with the PVA device is different. Accordingly, in the present invention, by using a ultraviolet absorber as described later, by introducing a primer layer, to provide an optical film excellent in adhesion and UV blocking function. Hereinafter, the present invention will be described in more detail. Acrylic resin
본 발명에서 사용하는 용어 '아크릴계 수지'는, 아크릴레이트계 단량체를 중합하여 제조되는 수지를 의미하며, 본 발명에서 기재층을 구성하는 주성분이다. 특히, 상기 '아크릴계 수지'는 주쇄에 고리 구조를 포함하지 않는 것을 특징으로 한다. 바람직하게는 상기 아크릴레이트계 단량체로는 주쇄에 고리 구조가 없는 것으로, 메틸 메타크릴레이트, 메틸 아크릴레이트, 에틸 아크릴레이트, 부틸 아크릴레이트, 2-에틸핵실 메타크릴레이트, 라우릴 메타크릴레이트, 및 벤질 메타크릴레이트로 구성되는 군으로부터 선택되는 어느 하나 이상을 사용할 수 있다.
또한, 필요에 따라 상기 아크릴계 수지는 스티렌계 단량체, 예를 들어 스티렌, α -메틸스티렌, Ρ-메틸스티렌, m-메틸스티렌, 또는 벤조일 스티렌, 또는 아크릴로 나이트릴을 추가로 포함할 수 있다. 상기 아크릴계 수지의 유리전이온도는 10CTC 내지 120°C이다. 상기 유리전이온도가 ioo°c 미만인 경우에는 필름으로 제조하였을 때 열적 안정성이 떨어지는 문제가 있다. 또한, 상기 아크릴계 수지의 중량평균분자량은 100, 000 내지 150, 000이다. 상기 중량평균분자량이 100,000 미만인 경우에는 필름으로 제조하였을 때 기계적 물성이 떨어지는 문제가 있고, 상기 중량평균분자량이 150 , 000 초과인 경우에는 압출 가공이 어렵다는 문제가 있다. 특히, 본 발명에서는 상기 아크릴레이트계 단량체로 메틸 메타크릴레이트 및 /또는 메틸 아크릴레이트를 사용할 수 있으며, 바람직하게는 메틸 메타크릴레이트 및 메틸 아크릴레이트의 공중합체인 폴리메틸메타크릴레이트이다. 바람직하게는, 상기 폴리메틸메타크릴레이트는 메틸 메타크릴레이트를 90 내지 99 중량 %로 포함하고, 메틸 아크릴레아트 단량체를 1 내지 10 중량 포함하는 것이 바람직하다. 상기 메틸 아크릴레이트는 공중합체의 분해를 억제하는 역할을 한다. 상기 폴리메틸메타크릴레이트는 메틸 메타크릴레이트 외에 메틸 아크릴레이트가 사용되는 점을 제외하고는, 공지의 방법으로 제조할 수 있다. 예를 들어, 유화 중합법, 유화 -현탁 중합법, 현탁 중합법 등의 방법으로 제조될 수 있다. 또한, 메틸 아크릴레이트 단량체를 폴리메틸메타크릴레이트의 말단에 도입하기 위하여, 폴리메틸메타크릴레이트를 먼저 중합한 후 메틸 아크릴레이트 단량체를 중합할 수 있다.
자외선 흡수제 The term "acrylic resin" used in the present invention means a resin produced by polymerizing an acrylate monomer, and is a main component constituting the base layer in the present invention. In particular, the 'acrylic resin' is characterized in that it does not contain a ring structure in the main chain. Preferably, the acrylate monomer has no ring structure in the main chain, methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylnuclear methacrylate, lauryl methacrylate, and Any one or more selected from the group consisting of benzyl methacrylate can be used. In addition, if necessary, the acrylic resin may further include a styrene monomer, for example, styrene, α -methylstyrene, Ρ-methylstyrene, m-methylstyrene, or benzoyl styrene, or acrylonitrile. The glass transition temperature of the acrylic resin is 10CTC to 120 ° C. If the glass transition temperature is less than ioo ° c there is a problem that the thermal stability is lowered when manufactured with a film. In addition, the weight average molecular weight of the acrylic resin is 100, 000 to 150, 000. When the weight average molecular weight is less than 100,000, there is a problem that the mechanical properties when the film is produced, when the weight average molecular weight is more than 150, 000 has a problem that extrusion processing is difficult. In particular, in the present invention, methyl methacrylate and / or methyl acrylate may be used as the acrylate monomer, and preferably polymethyl methacrylate is a copolymer of methyl methacrylate and methyl acrylate. Preferably, the polymethyl methacrylate comprises 90 to 99% by weight of methyl methacrylate, and preferably contains 1 to 10% by weight of methyl acrylate art monomer. The methyl acrylate serves to suppress decomposition of the copolymer. The polymethyl methacrylate can be produced by a known method, except that methyl acrylate is used in addition to methyl methacrylate. For example, it may be prepared by an emulsion polymerization method, an emulsion-suspension polymerization method, a suspension polymerization method or the like. In addition, in order to introduce the methyl acrylate monomer to the terminal of the polymethyl methacrylate, the polymethyl methacrylate may be polymerized first and then the methyl acrylate monomer may be polymerized. UV absorbers
본 발명에서, 자외선 흡수제는 기재층에 포함되는 것으로, 외부로부터 유입되는 자외선을 효과적으로 차단하기 위하여 포함된다. 본 발명에서 사용할 수 있는 자외선 흡수제로는, 본 발명에 따른 2축 연신 광학 필름이, 후술할 바와 같이, 광학 필름의 두께가 40 urn인 조건에서, 파장 380 nm의 광 투과율을 20% 이하, 바람직하게는 10% 이하로 할 수 있는 자외선 흡수제이면 특별한 제한없이 사용이 가능하다. 예컨대, 상기 자외선 흡수제로는 당해 기술분야에 잘 알려진 벤조페논계 자외선 흡수제, 벤조트리아졸계 자외선 흡수제, 트리아진계 자외선 흡수제, 살리실레이트계 자외선 흡수제 등을 사용할 수 있다. 그 중에서도 트리아진계 자외선 흡수제가 바람직하다. 이 경우 열 안정성과 자외선 흡수 효과가 우수하여 적정량의 함량으로도 층분한 자외선 차단 효과를 가질 수 있으며, 나아가 제막 과정에서 발생할 수 있는 품 ( fume) 현상이나 마이그레이션 (migrat ion) 현상 등을 방지할 수 있다. 상기 트리아진계 자외선 흡수제의 예로는 2 , 4, 6-트리페닐 -1 , 3 , 5-트리아진 골격을 갖는 화합물을 주 성분으로 포함하는 것으로서, 당해 기술분야에서 시판되는 다양한 트리아진계 자외선 흡수제가 특별한 제한 없이 사용될 수 있다. 상기 자외선 흡수제는, 상기 아크릴계 수지 100 중량부 대비 0. 1 내지 5 중량부로 포함되는 것이 바람직하다. 자외선 흡수제가 상기 범위보다 적은 경우에는 층분한 자외선 차단 효과를 가지지 못하며, 자외선 흡수제가 상기 범위를 초과하는 경우에는, 광학 필름 제조과정에서 자외선 흡수제가 분해되면서 필름 밖으로 빠져 나오는 마이그레이션이 발생하는 문제가 있다. 기재충
본 발명에서 기재충은, 상술한 아크릴계 수지를 포함하는 조성물로 제조된다. 일례로, 상기 아크릴계 수지를 미연신 필름으로 제조하여 상기 기재층을 제조할 수 있다. 또한, 상기 기재층은 위상차 조절을 위하여 위상차 조절제를 추가로 포함할 수 있다. 아크릴계 수지를 연신하게 되면, 연신 방향에 대하여 수직인 방향으로 굴절율이 커지는 부의 복굴절 특성을 가지며, 따라서 zero 위상차를 구현하기 위해서는, 연신 방향으로 굴절율이 커지는 정의 복굴절 특성을 가지는 위상차 조절제가 필요하다. 바람직하게는, 상기 위상차 조절제는 폴리카보네이트를 사용할 수 있다. 본 발명에서 사용하는 용어 '폴리카보네이트'란, 방향족 디올 화합물 및 카보네이트 전구체가 반웅하여 형성되는 것으로, 계면 중합 또는 용액 중합으로 제조될 수 있다. 일례로, 비스페놀 A와 포스겐을 계면 중합하여 제조할 수 있다. 특히, 본 발명에서 폴리메틸메타크릴레이트와 함께 기재층을 구성하는 성분이다. 상기 폴리카보네이트를 추가로 포함할 경우, 아크릴계 수지와의 상용성을 고려하여, 상기 폴리카보네이트의 중량평균분자량은 10 , 000 내지 20, 000이 바람직하다. 상기 폴리카보네이트의 중량평균분자량이 20 , 000을 초과하는 경우에는, 아크릴계 수지와의 상용성이 떨어져 전체적으로 불투명한조성물이 되어 광학 필름으로 사용하기에 바람직하지 않다. 또한, 상기 폴리카보네이트는, 상기 기재층에서 10 중량 % 이하로 포함되는 것이 바람직하다. 상기 함량이 10 중량 %를 초과하게 되면, 전체적으로 불투명한 조성물이 되고, 위상차 발현성이 너무 커져 zero 위상차를 구현하는데 바람직하지 않다. 또한 바람직하게는, 상기 폴리카보네이트는, 상기 기재층에서 1 중량 % 이상, 또는 2 증량 % 이상인 것이 바람직하다.
또한, 상기 조성물은, 필요에 따라 열 안정화제, 윤활제 등의 첨가제를 포함할 수 있다. 이때, 상기 첨가제들은 조성물의 물성을 해하지 않는 범위 내에서 적절한 함량으로 포함될 수 있으며, 예를 들면, 전체 조성물 100 중량부를 기준으로 0. 1 내지 5 중량부로 포함될 수 있다. 또한, 상기 조성물로 필름을 제조하는 방법으로는, 당해 기술분야에 알려진 어떠한 방법, 예를 들면, 용액 캐스터법이나 압출법 등을 이용할 수 있고, 일례로 용융 압출 성형법을 이용할 수 있다. 구체적으로, 상기 광학 재료용 수지 조성물을 건조하여 수분을 제거한 후, 원료 호퍼 (hopper )로부터 압출기를 싱글 또는 트윈 압출기에 공급하고, 고온에서 용융하여 원료 펠렛을 얻고, 얻어진 원료 펠렛을 건조하고, 원료 호퍼로부터 압출기까지를 싱글 압출기로 용융한 후, 코트 행거 타입의 T-다이에 통과시키고, 크롬 도금 캐스팅 를 및 넁각 를 등을 거쳐 필름을 제조할 수 있다. 이때, 필름 성형 은도는 바람직하게는 150°C 내지 350 °C , 보다 바람직하게는 200°C 내지 300°C이다. 한편, 상기와 같이, T 다이법으로 필름을 성형하는 경우에는, 공지된 단축 압출기나 2축 압출기의 선단부에 T-다이를 장착하고, 필름 형상으로 압출된 필름을 권취하여 를 형상의 필름을 얻을 수 있다. 또한, 필름 성형시 이물질을 제거하기 위하여 폴리머 필터를 사용할 수 있다. 프라이머층 In the present invention, the ultraviolet absorber is included in the base layer, it is included to effectively block the ultraviolet rays introduced from the outside. As the ultraviolet absorber that can be used in the present invention, the biaxially stretched optical film according to the present invention, as described below, has a light transmittance of 20% or less at a wavelength of 380 nm under a condition that the thickness of the optical film is 40 urn, preferably Preferably, UV absorbers that can be up to 10% can be used without particular limitations. For example, as the ultraviolet absorber, a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a triazine ultraviolet absorber, a salicylate ultraviolet absorber, and the like, which are well known in the art, may be used. Especially, a triazine type ultraviolet absorber is preferable. In this case, it has excellent thermal stability and UV absorption effect, so it can have a sufficient UV blocking effect even at an appropriate amount of content, and can also prevent fume phenomenon and migration phenomenon that may occur during the film forming process. have. Examples of the triazine-based UV absorber include a compound having a 2, 4, 6-triphenyl-1, 3, 5-triazine skeleton as a main component, and various triazine-based UV absorbers commercially available in the art are It can be used without limitation. The ultraviolet absorber is preferably contained in 0.1 to 5 parts by weight based on 100 parts by weight of the acrylic resin. If the UV absorber is less than the above range does not have a sufficient UV blocking effect, if the UV absorber exceeds the above range, there is a problem that migration occurs out of the film as the UV absorber decomposes during the optical film manufacturing process. . Equipment In the present invention, the base worm is made of a composition containing the acrylic resin described above. For example, the base layer may be manufactured by manufacturing the acrylic resin into an unstretched film. In addition, the base layer may further include a phase difference regulator for phase difference control. When the acrylic resin is stretched, it has a negative birefringence characteristic in which the refractive index increases in a direction perpendicular to the stretching direction. Therefore, in order to realize zero phase difference, a phase difference regulator having a positive birefringence characteristic in which the refractive index increases in the stretching direction is required. Preferably, the phase difference regulator may be a polycarbonate. The term 'polycarbonate' used in the present invention is formed by reacting an aromatic diol compound and a carbonate precursor, and may be prepared by interfacial polymerization or solution polymerization. For example, bisphenol A and phosgene can be produced by interfacial polymerization. In particular, in the present invention, it is a component constituting the base layer together with the polymethyl methacrylate. When the polycarbonate is further included, in consideration of compatibility with the acrylic resin, the weight average molecular weight of the polycarbonate is preferably 10, 000 to 20, 000. When the weight average molecular weight of the polycarbonate is more than 20, 000, the compatibility with the acrylic resin is poor, which becomes a totally opaque composition, which is not preferable for use as an optical film. In addition, the polycarbonate is preferably contained in 10% by weight or less in the base layer. When the content exceeds 10% by weight, it becomes an opaque composition as a whole, and the phase difference expression property is too large, which is not preferable to implement zero phase difference. Also preferably, the polycarbonate is preferably 1% by weight or more, or 2% by weight or more in the substrate layer. In addition, the composition may include additives such as heat stabilizers, lubricants, if necessary. In this case, the additives may be included in an appropriate amount within a range that does not impair the physical properties of the composition, for example, may be included in 0.1 to 5 parts by weight based on 100 parts by weight of the total composition. In addition, as a method for producing a film from the composition, any method known in the art, for example, a solution caster method, an extrusion method, or the like may be used, and for example, a melt extrusion method may be used. Specifically, after drying the resin composition for the optical material to remove moisture, supply the extruder to a single or twin extruder from the raw material hopper, melt at high temperature to obtain raw material pellets, dry the obtained raw material pellets, After melting from the hopper to the extruder with a single extruder, it can be passed through a coat hanger type T-die, and the film can be produced via chrome plating casting, engraving, and the like. At this time, the film forming silver degree is preferably 150 ° C to 350 ° C, more preferably 200 ° C to 300 ° C. On the other hand, as described above, in the case of forming a film by the T-die method, a T-die is attached to the tip of a known single screw extruder or twin screw extruder, and the film extruded in a film shape is obtained to obtain a film having a shape of. Can be. In addition, a polymer filter may be used to remove foreign substances in film forming. Primer layer
본 발명에서 프라이머층은, 상기 기재층 상에 형성되는 것으로 필요에 따라 기재층의 일면 또는 양면에 형성될 수 있다. 특히, 본 발명의 프라이머층은 후술할 바와 같이 2축 연신하여 광학 필름을 제조하였을 때, 편광판, 예를 들어 PVA 소자와의 접착력을 향상시킬 수 있다. 상기 프라이머층은 폴리에스테르계 수지 및 폴리우레탄계 수지를 각각 70 내지 95 중량부 및 5 내지 30 증량부 포함한다. 보다 바람직하게는, 상기 프라이머층은 폴리에스테르계 수지 및 폴리우레탄계 수지를 각각 75
내지 90 중량부 및 10 내지 25 중량부 포함한다. 상기 폴리에스테르계 수지는 주쇄에 카르복시산과 알코올의 반웅에 의해 형성되는 에스테르기를 포함하는 수지를 의미하는 것으로, 바람직하게는 수분산성 폴리에스레트 수지일 수 있으며, 더 바람직하게는, 다염기간 (polybasi c acid)과 폴리올 (polyol )의 반응에 의해 형성되는 폴리에스테르 글리콜을 포함한다. 이때, 상기 다염기산 성분으로는, 예를 들어 오쏘 (ortho)-프탈산, 이소프탈산, 테레프탈산, 1 ,4-나프탈렌디카르복시산, 2, 5- 나프탈렌디카르복시산, 2, 6-나프탈렌디카르복시산, 비페닐디카르복시산, 테트라히드로프탈산 등의 방향족 디카르복시산; 옥살산, 숙신산, 말론산, 글루타르산, 아디프산, 피멜산, 수베르산, 아젤라인산, 세바스산, 리놀레산, 말레산, 푸마르산, 메사콘산, 이타콘산 등의 지방족 디카르복시산; 핵사히드로프탈산, 테트라히드로프탈산, 1 , 3-시클로핵산디카르복시산, 1,4_ 시클로핵산디카르복시산 등의 지환식 디카르복시산; 또는 이들의 산 무수물, 알킬 에스테르, 산 할라이드 등의 반웅성 유도체 등이 있으나, 이에 한정되는 것은 아니며, 이들로 이루어진 군으로부터 1종 또는 2종 이상을 포함하는 것일 수 있다. 이 중에서도 테레프탈산, 이소프탈산, 숙신상 등이 특히 바람직하다. 또한, 술폰산 염으로 치환된 이소프탈산을 염시간으로 사용할 경우, 수분산성 측면에서 특히 바람직하다. 상기 폴리올은 분자 중에 히드록시기를 2개 이상 갖는 것이면 특별히 한정되지 않으며, 예를 들면, 상기 폴리올로는, 에틸렌글리콜, 1ᅳ 2ᅳ 프로판온디올, 1,3-프로판디올, 1 ,3-부탄디올, 1 , 4-부탄디올, 네오펜틸글리콜, 펜탄디올, 1 ,6-핵산디을, 1 ,8-옥탄디올, 1,10-데칸디올, 4,4' -디히드록시페닐프로판, 4,4' -디히드톡시메틸메탄, 디에틸렌글리콜, 트리에틸렌글리콜, 폴리에틸렌글리콜 (PEG) , 디프로필렌글리콜, 폴리테트라메틸렌글리콜 (PTMG) , 폴리프로필렌글리콜 (PPG) , 1 ,4- 시클로핵산디메탄올 1,4-시클로핵산디올, 비스페놀 A, 비스페놀 F ,
글리세린, 1,1,1-트리메틸올프로판, 1,2 , 5-핵사트리올, 펜타에리트리올, 글루코오스, 수크로오스, 및 소르비를로 이루어진 군으로부터 선택된 1종 이상을 포함하는 것이 바람직하다. 또한 폴리올로서 카르복시기를 함유한 디메틸올알칸산, 디메틸올아세트산, 디메틸올프로피온산, 디메틸를부틸산으로 이루어진 군으로부터 선택된 1종 또는 2종 이상을 포함하는 경우, 수분산성 측면에서 특히 바람직하다. 상기 폴리에스테르 글리콜은 다염시간과 폴리올을 2.5 : 1 내지 1 :2.5의 몰비, 바람직하게는 2.3 : 1 내지 1 : 2.3의 몰비, 더 바람직하게는 2 : 1 내지 1 : 2의 몰비로 반응시켜 형성되는 것이 바람직하다. 다염시간과 폴리올의 반웅 몰비를 벗어나는 경우, 미반웅 단량체에 의해 냄새가 발생하거나, 코팅 블량을 유발할 수 있기 때문이다. 상기 폴리에스테르 수지의 제조 방법은 당해 기술 분야에 잘 알려져 있는, 예를 들면, 다염기산과 폴리올의 에스테르화 반웅 후 중축하는 방법, 또는 다염기산 무수물과 폴리을의 에스테르화 반웅 후 축중합 하는 방법 등에 의해 수행될 수 있다. 구체적으로, 상기 방법들은 (1) 폴리에스테르의 중합을 위한 중합 원료를 흔합하여 원료 흔합물을 수득하는 원료 흔합 단계, (2) 상기 원료 흔합물을 에스테르화시키는 에스테르화 반웅 단계, 및 (3) 에스테르화된 원료 흔합물을 중축합시켜 폴리에스테르를 수득하는 중축합 단계를 포함할 수 있다. 한편, 상기와 같은 방법을 통해 제조되는 폴리에스테르계 수지는, 하기 화학식 1로 표시되는 반복단위를 포함할 수 있다: In the present invention, the primer layer is formed on the base layer, and may be formed on one side or both sides of the base layer as necessary. In particular, the primer layer of the present invention can improve the adhesive force with a polarizing plate, for example, a PVA device, when biaxially stretched to produce an optical film as described below. The primer layer contains 70 to 95 parts by weight and 5 to 30 parts by weight of a polyester resin and a polyurethane resin, respectively. More preferably, the primer layer is a polyester resin and a polyurethane resin, respectively 75 To 90 parts by weight and 10 to 25 parts by weight. The polyester-based resin refers to a resin containing an ester group formed by reaction of carboxylic acid and alcohol in the main chain, preferably a water-dispersible polyester resin, more preferably, polybasi c acid) and polyester glycols formed by the reaction of polyols. At this time, as the polybasic acid component, for example, ortho-phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, biphenyldi Aromatic dicarboxylic acids such as carboxylic acid and tetrahydrophthalic acid; Aliphatic dicarboxylic acids such as oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelline acid, sebacic acid, linoleic acid, maleic acid, fumaric acid, mesaconic acid and itaconic acid; Hex tetrahydro phthalic acid, tetrahydrophthalic acid, 1,3-cyclohexane dicarboxylic acid, 1, 4 _ cyclo aliphatic di-acid, such as dicarboxylic acids; Or semi-ungung derivatives such as acid anhydrides, alkyl esters and acid halides thereof, and the like, but are not limited thereto, and may include one or two or more kinds from the group consisting of these. Among these, terephthalic acid, isophthalic acid, and succinic phase are particularly preferable. Moreover, when isophthalic acid substituted by sulfonic acid salt is used for salt time, it is especially preferable at the point of water dispersibility. The polyol is not particularly limited as long as it has two or more hydroxy groups in the molecule. For example, the polyol may be ethylene glycol, 1'2 'propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentylglycol, pentanediol, 1,6-nucleic acid di, 1,8-octanediol, 1,10-decanediol, 4,4'-dihydroxyphenylpropane, 4,4'- Dihydrotoxymethylmethane, Diethylene glycol, Triethylene glycol, Polyethylene glycol (PEG), Dipropylene glycol, Polytetramethylene glycol (PTMG), Polypropylene glycol (PPG), 1,4-cyclonucleodimethanol 1,4 -Cyclonucleodiol diol, bisphenol A, bisphenol F, It is preferable to include at least one member selected from the group consisting of glycerin, 1,1,1-trimethylolpropane, 1,2,5-nuxatriol, pentaerytriol, glucose, sucrose, and sorbitol. Moreover, when polyol contains 1 type (s) or 2 or more types selected from the group which consists of dimethylol alkanoic acid, dimethylol acetic acid, dimethylol propionic acid, and dimethyl which contains a carboxyl group, it is especially preferable at the point of water dispersibility. The polyester glycol is formed by reacting polysalt time with a polyol in a molar ratio of 2.5: 1 to 1: 2.5, preferably in a molar ratio of 2.3: 1 to 1: 2.3, more preferably in a molar ratio of 2: 1 to 1: 2. It is preferable to be. This is because when the salting out of the reaction time between the polysalt time and the polyol, the odor may be generated by the uncoupling monomer or the coating may be caused. The production method of the polyester resin is well known in the art, for example, by the method of condensation after the esterification reaction of polybasic acid and polyol, or the method of condensation polymerization after the esterification reaction of polybasic anhydride and poly, etc. Can be. Specifically, the methods include (1) a raw material mixing step of mixing a polymerization raw material for polymerization of polyester to obtain a raw material mixture, (2) an esterification reaction step of esterifying the raw material mixture, and (3) an ester A polycondensation step may be obtained by polycondensing the pulverized raw material mixture to obtain a polyester. On the other hand, the polyester-based resin produced by the above method, may include a repeating unit represented by the following formula (1):
화학식 1에서, In Formula 1,
Ri 및 ¾는 각각 독립적으로 ( 20 알킬렌기, C6-20 아릴렌기, 또는 C5_And Ri are each independently a ¾ (20 alkylene group, C 6 - 20 aryl group, or a C 5 _
20 시클로알킬렌기이고, 20 cycloalkylene group,
R3 및 ¾는 각각 ¾ 및 ¾에 치환된 치환기로서, 각각 독립적으로 수소, 카르복시, 히드록시 , 술폰산염기, ( 20 알킬, C6-20 아릴, 또는 C5-20 시클로알킬이고, 단, R3 및 ¾ 중 적어도 하나는 카르복시, 히드록시, 또는 술폰산염기이다. 바람직하게는, ¾ 또는 ¾는 카르복시, 또는 술폰산염기이다. 보다 바람직하게는, 상기 폴리에 수지는 하기 화학식 2로 표시되는 반복 단위를 포함할 수 있다: R 3 and ¾ are each ¾ and as the substituent substituted to ¾, each independently selected from hydrogen, carboxy, hydroxy, sulfonic acid base, (20 alkyl, C 6 - 20 aryl, or C 5 - and 20 cycloalkyl, with the proviso that, R At least one of 3 and ¾ is a carboxy, hydroxy, or sulfonate group, Preferably, ¾ or ¾ is a carboxy, or sulfonate group More preferably, the poly resin is a repeating unit represented by the following formula (2): May include:
[화학식 2] [Formula 2]
상기 화학식 2에서, In Chemical Formula 2,
, R ' 및 R"는 각각 독립적으로 d-20 알킬렌, C6— 20 아릴렌, 또는 C5-20 사이클로알킬렌이고, S03Na는 R' '에 치환된 치환기를 의미한다. 한편, 상기 폴리에스테르 수지는, 본 명세서의 물성을 해하지 범위에서 상기 성분들 이외에 추가적인 성분들이 더 포함될 수 있다. 상기 폴리우레탄계 수지는 주쇄에 이소시아네이트와 폴리을의 반웅에
의해 형성된 우레탄 반복 단위를 포함하는 수지를 의미하는 것으로, 이때 상기 이소시아네이트는 2 이상의 NC0 기를 가지는 화합물이며, 상기 폴리올은 2 이상의 수산기를 가지는 화합물로서, 예를 들면, 폴리에스테르계 폴리올, 폴리카보네이트계 폴리올, 폴리에테르 폴리올 등이 있으나, 이에 한정되는 것은 아니다. 구체적으로, 상기 디오시아네이트의 예로는, 를루엔이소시아네이트 (TDI), 4,4-디페닐메탄디이소시아네이트 (MDI), 1,5- 나프탈렌 디이소시아네이트 (NDI), 를리딘 디이소시아네이트 (T0DI), 핵사메틸렌디이소시아네이트 (HMDI), 이소프론디이소시아네이트 (IPDI), p- 페닐렌 디이소시아네이트, 트랜스시클로핵산, 1,4-디이소시아네이트, 및 자이렌디이소시아네이트 (XDI) 등이 있으나, 이에 한정되지 않으며, 이들은 1종 또는 2종 이상을 포함하는 것일 수 있다. 상기 폴리에스테르계 폴리올은 다염기산 성분과 폴리을 성분을 반웅시켜 얻을 수 있으며, 이때 상기 다염기산 성분의 예로는 오쏘 (ortho)- 프탈산, 이소프탈산, 테레프탈산, 1,4-나프탈렌디카르복시산, 2,5- 나프탈렌디카르복시산, 2,6-나프탈렌디카르복시산, 비페닐디카르복시산, 테트라히드로프탈산 등의 방향족 디카르복시산; 옥살산, 숙신산, 말론산, 글루타르산 아디프산, 피멜산, 수베르산, 아젤라인산, 세바스산, 리놀레산, 말레산, 푸마르산, 메사콘산, 이타콘산 등의 지방족 디카르복시산; 핵사히드로프탈산, 테트라히드로프탈산, 1, 3-시클로핵산디카르복시산, 1,4- 시클로핵산디카르복시산 등의 지환식 디카르복시산; 또는 이들의 산 무수물, 알킬 에스테르, 산 할라이드 등의 반웅성 유도체 등이 있으나, 이에 한정되는 것은 아니며, 이들로 이루어진 군으로부터 1종 또는 2종 이상을 포함하는 것일 수 있다. 또한, 상기 폴리카보네이트계 폴리올은 카보네이트기를 갖는 화합물과 폴리올 성분을 반웅시켜 얻을 수 있으며, 이때, 상기 카보네이트기를 갖는 화합물의 예로는, 디페닐카보네이트,
디알킬카보네이트, 알킬렌 카보네이트 등이 있으나, 이에 한정되는 것은 아니다. 한편, 상기 폴리에테르 폴리.올은 폴리을 성분에 알킬렌옥사이드를 개환 중합하여 부가시킴으로써 얻을 수 있다. 상기 폴리올 성분은 분자 중에 히드록시기를 2개 이상 갖는 것이면 특별히 한정되지 않느다. 예를 들면, 상기 폴리을로는, 에틸렌글리콜, 1,2- 프로판온디올, 1,3-프로판디올, 1,3-부탄디올, 1,4-부탄디올, 네오펜틸글리콜, 펜탄디을, 1,6-핵산디올, 1,8-옥탄디올, 1,10-데칸디올, 4,4'-디히드록시페닐프로판, 4, 4'-디히드록시메틸메탄, 디에틸렌글리콜, 트리에틸렌글리콜, 폴리에틸렌글리콜 (PEG), 디프로필렌글리콜, 폴리테트라메틸렌글리콜 (PTMG), 폴리프로필렌글리콜 (PPG), 1,4- 시클로핵산디메탄을, 1,4-시클로핵산디올, 비스페놀 A, 비스페놀 F, 글리세린, 1,1,1—트리메틸올프로판, 1,2,5-핵사트리올, 펜타에리트리을, 글루코오스, 수크로오스, 및 소르비를로 이루어진 군으로부터 선택된 1종 이상을 포함하는 것이 바람직하다. 이 중에서도 특히, 폴리테트라메틸렌글리콜 (PTMG), 폴리프로필렌글리콜 (PPG) 및 폴리에틸렌글리콜 (PEG)로 이루어진 군으로부터 선택된 적어도 1종인 것이 바람직하다. 한편, 상기 폴리우레탄계 수지는 본 명세서의 물성을 해하지 않는 범위에서 상가성분들에 다른 폴리올이나 사슬 연장제를 더 포함할 수 있다. 상기의 다른 폴리올은, 예를 들면, 소르비를, 글리세린, 트리메틸올에탄, 트리메틸올프로판, 펜타에리트리올 등의 수산기 수가 3개 '이상인 폴리올 등이 있으나, 이에 한정되는 것은 아니다. 상기 다른 사슬 연장제는, 예를 들면, 에틸렌글리콜, 디에틸렌글리콜, 트리에틸렌글리콜, 1,3-프로판디을, 1,3-부탄디을, 1,4-부탄디을,
네오펜틸글리콜, 펜탄디올, 1 , 6-핵산디올, 프로필렌글리콜 등의 글리콜류 등이 있으나, 이에 한정되는 것은 아니다. 한편, 상기 폴리우레탄계 수지는, 필요에 따라, 중화제를 더 포함할 수 있다. 중화제를 포함할 경우, 수정에 있어서의 우레탄 수지의 안정성이 향상된다. 상기 중화제는, 예를 들면, 암모니아 N—메틸모르폴린, 트리에틸아민, 디메틸에탄올아민, 메틸디에탄올아민, 트리에탄올알킨, 모르폴린, 트리프로필아민, 에탄을 아민, 트리이소프로판올아민으로 이루어진 군으로부터 선택된 1종 또는 2종 이상을 포함하는 것일 수 있다. 상기 폴리우레탄계 수지의 제조는 상기 이소시아네이트에 대하여 불활성이고 물에 대해 상용성을 갖는 유기 용제에서 수행되는 것이 바람직하다. 당해 유기 용제로는 아세트산에틸, 에틸셀로솔브아세테이트 등의 에스테르계 용제, 아세톤, 메탄에틸케톤, 메틸이소부틸케톤 등의 케톤계 용제, 디옥산 테트라히드로푸란 등의 에테르계 용제로 이루어진 군으로부터 선택된 1종 또는 2종 이상을 포함하는 것일 수 있다. 또한, 상기 폴리우레탄계 수지는 당해 기술 분야에서 잘 알려진 원샷법 및 다단법 등을 통해 제조할 수 있다. 구체적으로, 원샷법은 상기 각 성분을 한번에 반웅시키는 방법이며, 다단법은 상기 각 성분을 단계적으로 반웅시키는 방법이다. 또한, 상기 폴리우레탄계 수지의 제조시 우레탄 반웅 촉매를 추가로 포함할 수 있다. 한편, 이로서 제한되는 것은 아니나, 분산성과 투명도의 관점에서, 상기 폴리우레탄 수지는 폴리카보네이트계 폴리올을 반응물로 사용하는 카보네이트계 폴리우레탄 수지 또는 폴리에스테르계 폴리을을 반웅물로 사용하는 에스테르계 폴리우레탄 수지인 것이 특히 바람직하다. 또한, 상기 폴리우레탄계 수지의 증량평균분자량은 10 , 000 내지 1 , 000, 000인 것이 바람직하다. 상기 수치 범위를 만족하는 경우 층분한
접착력을 구현할 수 있고, 수분산성이 우수한 효과가 있다. 본 명세서의 일 실시상태에 따르면 상기 폴리우레탄계 수지는 카르복시, 히드록시, 술폰산염기, 및 3급 아민기로 구성되는 군으로부터 선택되는 1종 이상의 작용기를 포함하는 것이 바람직하다. 폴리우레탄계 수지에 상기 작용기들이 포함될 경우, 접착층에 대한 접착력 및 수분산성이 크게 향상된다. 한편, 상기와 같은 작용기를 포함하는 폴리우레탄계 수지는, 폴리올 및 /또는 이소시아네이트로 상기 작용기들을 포함하는 화합물을 사용하거나, 폴리을과 이소시아네이트 반웅시 상기 작용기들을 포함하는 사슬 연장제를 첨가하는 방법으로 제조할 수 있다. 예를 들면, 카르복시기 또는 3급 아민기를 포함하는 폴이우레탄계 수지는 폴리에스테르 폴리올과 이소시아네이트 반웅시 유리 카르복시기 또는 유리 아민기를 갖는 사슬 연장제를 첨가하여 반웅시킴으로써 제조될 수 있다. 이때, 상기 유리 카르복시기를 갖는 사슬 연장제로는, 예를 들어, 디히드록시 카르복시산, 디히드록시 숙신산 등이 있으나, 이에 한정되지 않는다. 디히드록시 카르복시산으로는, 예를 들면 디메틸올아세트산, 디메틸올부탄산, 디메틸올프로피온산, 디메틸올부틸산, 디메틸올펜탄산 등의 디메틸올알칸산을 포함하는 디알킬올알칸산으로' 이루어진 군으로부터 선택된 1종 또는 2종 이상을 포함하는 것일 수 있다. 한편, 상기 유리 아민기를 갖는 사슬 연장제로는, 예를 들면, 에틸렌디아민 프로필렌디아님, 핵사메틸렌디아민, 1 , 4-부탄디아민, 아미노에틸에탄올아민 등의 지방족 디아민 ; 이소포론디아민 , 4,4 ' - 디시클로핵실메탄디아민 등의 지환족 디아민; 자일릴렌디아민, 를릴렌디아민 등의 방향족 디아민 등이 있으나, 이에 한정되는 것은 아니며, 이들로 이루어진 군으로부터 선택된 1종 또는 2종 이상을 포함하는 것일 수 있다. 한편, 상기 폴리우레탄 수지는, 본 명세서의 물성을 해하지 않는 범위에서 상기 성분들 이외에 추가적인 성분들이 더 포함될 수 있다.
또한, 상기 프라이머층은 필요에 따라 수분상성 미립자 및 수분산성 가교제를 추가로 포함할 수 있다. 상기 수분산성 미립자로는, 실리카, 티타니아, 알루미나, 지르코니아, 및 안티몬계 미립자로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있으며, 바람직하게는 실리카를 사용할 수 있다. 실리카를 사용할 경우, 콜로이달 실리카로 사용하는 것이 바람직하다. 상기 수분산성 미립자의 직경은 50 nm 내지 500 nm , 바람직하게는 70 nm 내지 300 nm이다. 상기 프라이머층은, 폴리에스테르계 수지 및 폴리우레탄계 수지를 포함하는 프라이머 용액을 코팅하여 제조할 수 있으며, 코팅 방법은 특별히 제한되지 않는다. 일례로, 바 (bar ) 코팅, 마이크로그라비어 코팅, 슬롯 다이 코팅, 콤마 코팅 등의 방법을 사용할 수 있다. 또한, 필요에 따라 상기 프라이머층은 대전방지 특성을 가질 수 있으며, 이를 위하여 상기 프라이머층은 계면활성제, 유기염, 무기염, 전도성 필러, 전도성 고분자, 블록 공중합체, 금속 산화물 등을 0. 1 내지 10 중량 ¾»로 포함할 수 있다. 또한, 필요에 따라 상기 프라이머층은 자외선 차단 특성을 가질 수 있으며, 이를 위하여 상기 프라이머층은 자외선 흡수제를 0. 1 내지 10 중량 %로 포함할 수 있다. 상기 자외선 흡수제로는 광학 필름에 사용되는 것이면 특별히 제한되지 않으며, 예를 들어 트리아진계, 벤조트리아졸계 벤조페놀계 자외선 흡수제를 사용할 수 있다. 또한, 필요에 따라 상기 프라이머층은 ant i -blocking 특성을 가질 수 있으며, 이를 위하여 상기 프라이머층은 유기 비드 또는 무기 비드를 포함할 수 있다. 상기와 같은 프라이머층을 사용할 경우, 기재층에 s l ip 성을 부여하여 ant i-block의 효과가 있으며, 또한 코팅시 코팅 용액으로부터 기재층의 침식을 방지할 수 있는 효과가 있다. 또한, 후술할 바와 같이 기재층과 프라이머층의 2축 연신에서도 각 충의 특성을 유지하면서도
프라이머층의 접착력을 향상시킬 수 있다 . , R. The 'and R "are each independently selected from d- 20 alkylene, C 6 - - 20 arylene, or C 5 20 cycloalkyl alkylene, S0 3 Na is R' means a substituent substituted on 'the other hand, The polyester resin may further include additional components in addition to the above components in the range of not impairing the physical properties of the present specification. Means a resin comprising a urethane repeating unit formed by, wherein the isocyanate is a compound having two or more NC0 groups, the polyol is a compound having two or more hydroxyl groups, for example, polyester-based polyols, polycarbonate-based polyols And polyether polyols, but are not limited thereto. Specifically, examples of the diocyanate include toluene isocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), toldine diisocyanate (T0DI), Nuxamethylene diisocyanate (HMDI), isopron diisocyanate (IPDI), p-phenylene diisocyanate, transcyclonucleic acid, 1,4-diisocyanate, and xylene diisocyanate (XDI), but are not limited thereto, These may be those containing one kind or two or more kinds. The polyester-based polyol may be obtained by reacting a polybasic acid component and a poly component, and examples of the polybasic acid component include ortho-phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, and 2,5-naphthalene. Aromatic dicarboxylic acids such as dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid and tetrahydrophthalic acid; Aliphatic dicarboxylic acids such as oxalic acid, succinic acid, malonic acid, glutaric acid adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, linoleic acid, maleic acid, fumaric acid, mesaconic acid and itaconic acid; Alicyclic dicarboxylic acids such as nucleated hydrophthalic acid, tetrahydrophthalic acid, 1,3-cyclonucleic acid dicarboxylic acid, and 1,4-cyclonucleic acid dicarboxylic acid; Or semi-ungung derivatives such as acid anhydrides, alkyl esters, and acid halides thereof, and the like, but are not limited thereto, and may include one or two or more kinds from these groups. In addition, the polycarbonate-based polyol may be obtained by reacting a compound having a carbonate group and a polyol component. In this case, examples of the compound having the carbonate group include diphenyl carbonate, Dialkyl carbonate, alkylene carbonate, and the like, but is not limited thereto. On the other hand, the polyether poly.ol can be obtained by adding a poly ring-opening polymerization of alkylene oxide to the component. The polyol component is not particularly limited as long as it has two or more hydroxyl groups in the molecule. For example, as the poly olefin, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentylglycol, pentanedi, 1,6- Nucleic acid diols, 1,8-octanediol, 1,10-decanediol, 4,4'-dihydroxyphenylpropane, 4,4'-dihydroxymethylmethane, diethylene glycol, triethylene glycol, polyethylene glycol ( PEG), dipropylene glycol, polytetramethylene glycol (PTMG), polypropylene glycol (PPG), 1,4-cyclonucleodimethane, 1,4-cyclonucleodiol, bisphenol A, bisphenol F, glycerin, 1, It is preferable to include at least one member selected from the group consisting of 1,1—trimethylolpropane, 1,2,5-nuxatriol, pentaerythritol, glucose, sucrose, and sorbitol. Especially, it is preferable that it is at least 1 sort (s) chosen from the group which consists of polytetramethylene glycol (PTMG), polypropylene glycol (PPG), and polyethylene glycol (PEG). On the other hand, the polyurethane-based resin may further include other polyols or chain extenders in the additive components in a range that does not impair the physical properties of the present specification. Other polyols of the, for example, a non-sorbitan, glycerin, trimethylolethane, trimethylolpropane, pentaerythrityl, but the hydroxyl number, such as three, or higher polyols such as triols, and the like. The other chain extender, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanedi, 1,3-butanedi, 1,4-butanedi, Glycols such as neopentyl glycol, pentanediol, 1, 6-nucleic acid diol, propylene glycol, and the like, but are not limited thereto. On the other hand, the polyurethane-based resin may further include a neutralizing agent, if necessary. When it contains a neutralizing agent, the stability of the urethane resin in a crystal | crystallization improves. The neutralizing agent is selected from the group consisting of, for example, ammonia N—methylmorpholine, triethylamine, dimethylethanolamine, methyldiethanolamine, triethanolalkyne, morpholine, tripropylamine, ethane, amine and triisopropanolamine. It may be one or two or more. Preparation of the polyurethane-based resin is preferably carried out in an organic solvent inert to the isocyanate and compatible with water. The organic solvent is selected from the group consisting of ester solvents such as ethyl acetate, ethyl cellosolve acetate, ketone solvents such as acetone, methane ethyl ketone and methyl isobutyl ketone, and ether solvents such as dioxane tetrahydrofuran. It may be one or two or more. In addition, the polyurethane-based resin can be prepared through a one-shot method and a multi-stage method well known in the art. Specifically, the one-shot method is a method of reacting each component at a time, and the multi-stage method is a method of reacting each component in steps. In addition, the production of the polyurethane-based resin may further include a urethane reaction catalyst. On the other hand, but not limited thereto, in view of dispersibility and transparency, the polyurethane resin is a carbonate-based polyurethane resin using a polycarbonate polyol as a reactant or an ester-based polyurethane resin using a polyester-based poly as a reaction product Is particularly preferred. In addition, the increase average molecular weight of the polyurethane-based resin is preferably from 10,000 to 1,000, 000. If the above numerical range is satisfied Adhesion can be achieved, and water dispersibility is excellent. According to an exemplary embodiment of the present specification, the polyurethane resin preferably includes one or more functional groups selected from the group consisting of carboxy, hydroxy, sulfonate groups, and tertiary amine groups. When the functional groups are included in the polyurethane-based resin, adhesion to the adhesive layer and water dispersibility are greatly improved. On the other hand, the polyurethane-based resin containing the functional group can be prepared by using a compound containing the functional groups as the polyol and / or isocyanate, or by adding a chain extender containing the functional groups to the poly and isocyanate reaction. Can be. For example, a polyurethane-based resin containing a carboxyl or tertiary amine group may be prepared by adding a chain extender having a polyester polyol and an isocyanate half-oxygen free carboxyl group or free amine group. At this time, as the chain extender having the free carboxyl group, for example, dihydroxy carboxylic acid, dihydroxy succinic acid and the like, but is not limited thereto. Dihydroxy carboxylic acid with, for example, dimethylolpropionic acid, dimethyl olbu acid, dimethylol propionic acid, dimethylol butyric acid, dimethyl olpen a dialkyl all acids including a dimethylol alkanoic acid such as carbonic acid, selected from the group consisting of It may be one or two or more. On the other hand, as a chain extender which has the said free amine group, For example, Aliphatic diamines, such as ethylenediamine propylene dinime, nuxa methylenediamine, 1, 4- butanediamine, aminoethylethanolamine; Alicyclic diamines such as isophorone diamine and 4,4'-dicyclonucleosilmethanediamine; Aromatic diamines such as xylylenediamine, rylenediamine, and the like, but are not limited thereto, and may include one or two or more selected from the group consisting of these. Meanwhile, the polyurethane resin may further include additional components in addition to the components within a range that does not impair the physical properties of the present specification. In addition, the primer layer may further include a water-soluble fine particles and a water-dispersible crosslinking agent as necessary. As the water-dispersible fine particles, one or more selected from the group consisting of silica, titania, alumina, zirconia, and antimony-based fine particles can be used, and preferably silica can be used. When using silica, it is preferable to use it as colloidal silica. The diameter of the water dispersible fine particles is 50 nm to 500 nm, preferably 70 nm to 300 nm. The primer layer may be prepared by coating a primer solution containing a polyester resin and a polyurethane resin, and the coating method is not particularly limited. For example, bar coating, microgravure coating, slot die coating, comma coating, or the like may be used. In addition, if necessary, the primer layer may have an antistatic property. For this purpose, the primer layer may contain a surfactant, an organic salt, an inorganic salt, a conductive filler, a conductive polymer, a block copolymer, a metal oxide, or the like. 10 weight ¾ ". In addition, if necessary, the primer layer may have ultraviolet ray blocking properties, and for this purpose, the primer layer may include 0.1 to 10 wt% of an ultraviolet absorber. The ultraviolet absorber is not particularly limited as long as it is used in an optical film, and for example, a triazine-based, benzotriazole-based benzophenol-based ultraviolet absorber can be used. In addition, if necessary, the primer layer may have an ant i-blocking property, and for this purpose, the primer layer may include organic beads or inorganic beads. When using the primer layer as described above, by giving the slip property to the base layer has the effect of ant i-block, and also has the effect of preventing the erosion of the base layer from the coating solution during coating. In addition, as will be described later, even in the biaxial stretching of the base layer and the primer layer, The adhesion of the primer layer can be improved.
2축 연신 광학필름 Biaxially oriented optical film
본 발명에 따른 2축 연신 광학 필름은, 상술한 기재층, 및 상기 기재층 상에 형성된 프라이머층을 포함한다. 상기의 2축 연신이란, 기재층 및 프라이머층을 포함하는 미연신 필름을 2축 연신한 것을 의미하거나, 또는 기재층을 종방향으로 일축 연신한 다음, 프라이머층을 형성하고, 이를 횡방향으로 연신한 것을 의미한다. 구체적으로, 상술한 기재층, 및 상기 기재층 상에 프라이머층을 형성하여 미연신 필름을 제조하는 단계; 및 상기 미연신 필름을 2축 연신하는 단계를 포함하는 제조 방법으로, 2축 연신 광학 필름을 제조한다. 또는 본 발명에 따른 2축 연신 광학 필름은 상술한 기재층을 종방향으로 일축 연신하는 단계 ; 상기 기재층 상에 프라이머층을 형성하는 단계 ; 및 상기 기재층과 프라이머층을 횡방향으로 연신하는 단계를 포함하는 제조 방법으로, 2축 연신 광학 필름을 제조한다. 바람직하게는, 상기 연신 배율은 MD 방향으로 1.2배 내지 3.0배 및 TD 방향으로 1.5배 내지 4.0배가 바람직하다. 상기 연신은 고분자를 정렬하는 것으로, 연신 정도에 따라 제조되는 2축 연신 광학 필름의 특성에 영향을 미친다. 보다 바람직하게는, 상기 MD 방향의 연신 배율과 TD 방향의 연신 배율의 비 (TD 연신 배율 /MD 연신 배율)이 1.0 내지 2.5이다. 또한, 상기 연신 은도는 상기 아크릴계 수지의 유리전이온도를 기준으로 -10°C 내지 +2CTC의 온도 범위에서 수행하는 것이 바람직하다. 상기 연신 온도는 2축 연신 광학 필름의 접착력에 영향을 주며, 상기 온도 범위 외에서는 접착력이 충분하지 않다는 문제가 있다. 또한, 본 발명에 따른 2축 연신 광학 필름은 치수 안정성이 우수하며, 이러한 열적 치수 안정성을 평가하기 위하여 TTS(Temperature of Thermal
Shr inkage)라는 변수를 도입하였다. The biaxially stretched optical film according to the present invention includes the base layer described above and a primer layer formed on the base layer. Said biaxial stretching means biaxial stretching of the unstretched film containing a base material layer and a primer layer, or uniaxially stretches a base material layer to a longitudinal direction, forms a primer layer, and extends this to a horizontal direction. I mean. Specifically, forming a primer layer on the above-described substrate layer, and the substrate layer to produce an unstretched film; And biaxially stretching the non-stretched film to produce a biaxially stretched optical film. Or the biaxially stretched optical film according to the present invention comprises the steps of uniaxially stretching the substrate layer described above in the longitudinal direction; Forming a primer layer on the substrate layer; And a step of stretching the substrate layer and the primer layer in the transverse direction, to prepare a biaxially stretched optical film. Preferably, the draw ratio is preferably 1.2 times to 3.0 times in the MD direction and 1.5 times to 4.0 times in the TD direction. The stretching is to align the polymer, affecting the properties of the biaxially stretched optical film produced according to the degree of stretching. More preferably, ratio (TD draw ratio / MD draw ratio) of the draw ratio of the said MD direction and the draw ratio of a TD direction is 1.0-2.5. In addition, the stretching silver is preferably carried out in a temperature range of -10 ° C to +2 CTC based on the glass transition temperature of the acrylic resin. The stretching temperature affects the adhesive force of the biaxially stretched optical film, and there is a problem that the adhesive force is not sufficient outside the temperature range. In addition, the biaxially stretched optical film according to the present invention has excellent dimensional stability, and in order to evaluate such thermal dimensional stability, TTS (Temperature of Thermal) Shr inkage) is introduced.
TTS는 연신 공정으로 제조된 광학 필름이 연신 이력이 완화되면서 급격하게 수축하기 시작하는 온도를 의미한다. 구체적으로, 광학 필름에 온도를 가하였을 때, 온도가 증가함에 따라 팽창 후 수축이 시작되는 온도를 의미한다. 바람직하게는, 본 발명에 따른 2축 연신 광학 필름의 MD 방향의 TTS 및 TD 방향의 TTS가 각각 95 °C 이상이고, 바람직하게는 100 °C 내지 120 °C이다. 또한, 본 발명에 따른 광학 필름은 자외선 차단 기능이 우수하며, 구체적으로 광학 필름의 두께가 40 um인 조건에서, 파장 380 nm의 광 투과율이 20% 이하, 바람직하게는 10% 이하라는 특징이 있다. 이는 상기 기재층에 자외선 흡수제가 포함된 것에 기인한다. 바람직하게는, 상기 380 nm 투과도는 9% 이하, > 이하, Ί 이하, 6% 이하, 또는 5%이하이다. 또한, 상기 380 nm 투과도는 그 값이 작을수록 우수한 것이어서 그 하한은 이론상 0%이며, 일례로 그 하한은 0.5% , 1% , 또는 2%일 수 있다. 한편, 본 발명에 따른 2축 연신 광학 필름의 두께는 필요에 따라 적절히 조절할 수 있으며, 일례로 10 um 내지 100 um인 것이 바람직하다. 편광판 TTS refers to the temperature at which the optical film produced by the stretching process begins to shrink rapidly as the stretching history is relaxed. Specifically, when the temperature is applied to the optical film, it means the temperature at which shrinkage starts after expansion as the temperature increases. Preferably, the TTS in the MD direction and the TTS in the TD direction of the biaxially stretched optical film according to the present invention are each 95 ° C. or more, preferably 100 ° C. to 120 ° C. In addition, the optical film according to the present invention is excellent in UV blocking function, specifically, under the condition that the thickness of the optical film is 40 um, the light transmittance having a wavelength of 380 nm is 20% or less, preferably 10% or less. . This is due to the inclusion of an ultraviolet absorber in the substrate layer. Preferably, the 380 nm transmittance is 9% or less,> or less, Ί or less, 6% or less, or 5% or less. In addition, the smaller the value of the 380 nm transmittance is excellent, the lower limit is theoretically 0%, for example, the lower limit may be 0.5%, 1%, or 2%. On the other hand, the thickness of the biaxially stretched optical film according to the present invention can be appropriately adjusted as needed, for example, it is preferably 10um to 100um. Polarizer
또한, 본 발명은 상기 2축 연신 광학 필름을 포함하는 편광판을 제공한다. 상술한 바와 같이 본 발명에 따른 2축 연신 광학 필름은 편광판의 보호 필름으로 사용할 수 있으며, 이에 따라 편광판의 기계적 특성을 보완하고, 외부 환경, 예를 들어 은도나 습도의 영향으로부터 편광판을 보호할 수 있다. 본 명세서에 있어서, 편광판은 편광자와 보호 필름을 포함하는 상태를 의미한다. 이때 본 발명에 따른 보호필름의 프라이머층이 편광자와 접하거나, 또는 본 발명에 따른 보호필름의 기재층이 편광자와 접할 수
있다. 상기 편광자로는 요오드 또는 이색성 염료를 포함하는 폴리비닐알콜 (PVA)로 이루어진 필름을 사용할 수 있다. 상기 편광자는 PVA 필름에 요오드 또는 이색성 염료를 염착시켜서 제조될 수 있으나, 이의 제조방법은 특별히 한정되지 않는다. 또한, 본 발명에 따른 보호 필름은 편광자의 양면에 구비될 수도 있고, 일면에만 구비될 수도 있다. 본 발명의 광학 필름이 편광자의 일면에 구비될 경우, 다른 한 면에는, 당해 기술 분야에 잘 알려진 편광자 보호 필름, 예를 들면, 아크릴 필름, TAC 필름, PET 필름, COP필름, PC 필름, 노보넨계 필름 등이 제한 없이 사용될 수 있다. 한편, 본 발명에 따른 보호 필름을 편광자에 구비할 접착제를 사용할 수 있다. 상기 접착제로는 비수계 접착제를 사용하는 것이 바람직하며, 자외선 경화형을 사용하는 것이 보다 바람직하다. 상기 접착제의 예로, (메타)아크릴레이트계 접착제, 엔 /티올계 접착제, 불포화 폴리에스테르계 접착제 등의 광 라디칼 중합반응을 이용하는 접착제 ; 또는 에폭시계 접착제 , 옥세탄계 접착제, 에폭시 /옥세탄계 접착제, 비닐에테르계 접착제 둥의 광 양이온 중합반웅을 이용하는 접착제를 사용할 수 있으나, 이에 한정되는 것은 아니다. 상기 비수계 접착제를 이용할 경우, 편광자 또는 보호 필름의 일면에 비수계 접착제를 도포하여 접착층을 형성한 다음, 편광자와 보호필름을 합판하고 광 조사를 통하여 접착층을 경화시키는 방법으로 수행할 수 있다. 또한, 본 발명은 상기 편광판을 포함하는 화상 표시 장치를 제공하며, 더욱 바람직하게는 액정 표시 장치일 수 있다. 예컨대, 본 발명에 따른 액정 표시 장치는 액정 셀 및 이 액정 셀의 양면에 각각 구비된 제 1 편광판 및 게 2 편광판을 포함하는 액정 표시 장치로서, 상기 제 1 편광판 및 상기 제 2 편광판 중 적어도 하나가 본 발명에 따른 편광판인 것을 특징으로 한다. 즉, 게 1 편광판을 기준으로 액정셀 면과 반대측 면, 게 2 편광판을 기준으로 액절셀 면과 반대측 면, 또는 상기 모두에 본 발명에 따른 광학 필름이
구비될 수 있다. 상기 편광판의 액정셀과 반대측에 구비된 광학 필름 또는 편광자 보호 필름은 AG , LR과 같은 표면 코팅할 수도 있다. Moreover, this invention provides the polarizing plate containing the said biaxially stretched optical film. As described above, the biaxially stretched optical film according to the present invention can be used as a protective film of a polarizing plate, thereby compensating the mechanical properties of the polarizing plate and protecting the polarizing plate from the influence of external environment, for example, silver or humidity. have. In this specification, a polarizing plate means the state containing a polarizer and a protective film. At this time, the primer layer of the protective film according to the present invention may be in contact with the polarizer, or the base layer of the protective film according to the present invention may be in contact with the polarizer. have. As the polarizer, a film made of polyvinyl alcohol (PVA) containing iodine or dichroic dye may be used. The polarizer may be prepared by dyeing iodine or dichroic dye on the PVA film, but a method of manufacturing the polarizer is not particularly limited. In addition, the protective film according to the present invention may be provided on both sides of the polarizer, or may be provided only on one surface. When the optical film of the present invention is provided on one side of the polarizer, on the other side, a polarizer protective film well known in the art, for example, acrylic film, TAC film, PET film, COP film, PC film, norbornene-based Films and the like can be used without limitation. On the other hand, the adhesive agent which is equipped with the protective film which concerns on this invention to a polarizer can be used. It is preferable to use a non-aqueous adhesive as said adhesive agent, and it is more preferable to use an ultraviolet curing type. As an example of the said adhesive agent, the adhesive agent which uses radical photopolymerization reaction, such as a (meth) acrylate type adhesive agent, an N / thiol type adhesive agent, an unsaturated polyester type adhesive agent; Or an adhesive using an optical cationic polymerization reaction of an epoxy adhesive, an oxetane adhesive, an epoxy / oxetane adhesive, or a vinyl ether adhesive, but is not limited thereto. In the case of using the non-aqueous adhesive, a non-aqueous adhesive may be applied to one surface of the polarizer or the protective film to form an adhesive layer, and then, the polarizer and the protective film may be laminated, and the adhesive layer may be cured through light irradiation. In addition, the present invention provides an image display device including the polarizing plate, more preferably may be a liquid crystal display device. For example, the liquid crystal display device according to the present invention is a liquid crystal display device comprising a liquid crystal cell and a first polarizing plate and a second polarizing plate respectively provided on both sides of the liquid crystal cell, wherein at least one of the first polarizing plate and the second polarizing plate is It is characterized in that the polarizing plate according to the present invention. That is, the optical film according to the present invention has a surface opposite to the liquid crystal cell surface based on the C1 polarizing plate, the surface opposite to the axel cell surface based on the C2 polarizing plate, or both. It may be provided. The optical film or polarizer protective film provided on the side opposite to the liquid crystal cell of the polarizing plate may be surface coated such as AG, LR.
【발명의 효과】 【Effects of the Invention】
상술한 바와 같이, 본 발명에 따른 2축 연신 광학 필름은, 고리 구조의 단량체를 포함하지 않는 아크릴계 수지를 사용하면서도 접착력이 우수하고 자외선 차단 기능이 우수하다는 특징이 있다. As described above, the biaxially stretched optical film according to the present invention is characterized in that it is excellent in adhesive strength and excellent in UV blocking function while using an acrylic resin that does not contain a monomer having a ring structure.
【발명을 실시하기 위한 구체적인 내용】 [Specific contents to carry out invention]
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 이에 의해 본 발명의 내용이 한정되는 것은 아니다. 제조예 1: 폴리메틸메타크릴레이트 Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto. Preparation Example 1 Polymethylmethacrylate
5리터 반응기에, 메틸 메타크릴레이트 98 wt% 및 메틸 아크릴레이트 2 wt%의 단량체 흔합물 1000 g을 넣고, 증류수 2000 g, 5% 폴리비닐알코올 용액 8.4 g(P0VAL PVA217 , kuraray 사), 및 분산 조력제로 붕산 0. 1 g을 투입하고 용해하였다. 여기에, 사슬이동제로 n—옥틸머캡탄 2 5 g , 중합개시제로 2,2 ' -아조비스이소부티로니트릴 1.5 g을 투입하고 400 rpm으로 교반하면서 수상에 분산시켜 현탁액을 제조하였다. 80°C로 승온하여 90분 동안 중합시킨 후, 30°C로 냉각시켰다. 얻어진 비드를 증류수로 세척 및 탈수한 후에 건조하여 폴리메틸메타크릴레이트 수지를 제조하였다. 상기 제조된 수지의 유리전이온도와 분자량을 측정한 결과, 유리전이온도 115°C , 중량평균분자량 120 , 000이었다. 상기 유리전이온도는, Met t ier Toledo 사의 시차주사열량계 (DSC)를 이용하여, 10°C /min의 승온 조건으로 측정하였다. 제조예 2: 폴리카보네이트 In a 5 liter reactor, 1000 g of a monomer mixture of 98 wt% methyl methacrylate and 2 wt% methyl acrylate were added, 2000 g of distilled water, 8.4 g of a 5% polyvinyl alcohol solution (P0VAL PVA217, kuraray), and dispersion 0.1 g of boric acid was added and dissolved as adjuvants. Here, n —octylmercaptan 2 5 g as a chain transfer agent and 1.5 g of 2,2′-azobisisobutyronitrile were added as a polymerization initiator and dispersed in an aqueous phase while stirring at 400 rpm to prepare a suspension. After heating to 80 ° C. for 90 minutes, the mixture was cooled to 30 ° C. The obtained beads were washed with distilled water, dehydrated, and dried to prepare a polymethylmethacrylate resin. As a result of measuring the glass transition temperature and molecular weight of the resin thus prepared, the glass transition temperature was 115 ° C, the weight average molecular weight was 120,000. The glass transition temperature was measured using a differential scanning calorimeter (DSC) manufactured by Met Tier Toledo under a temperature rising condition of 10 ° C./min. Preparation Example 2 Polycarbonate
폴리카보네이트로는, 유리전이온도가 134°C이고 중량평균분자량이 16 , 000인 폴리카보네이트 수지 F 1004A , 주식회사 엘지화학)를 사용하였다. 제조예 3 : 프라이머 용액
폴리에스테르계 수지 (A-645GH; Takamatsu oi l & fat ; 물을 제외한 전체 고형분의 함량은 30 중량? 0와 폴리우레탄계 수지 (CK-PUD-PF; 조광페인트사; 물을 제외한 전체 고형분의 함량은 30 중량 ¾)를 고형분 80 :20의 중량비로 흔합하였다. 여기에, 수성 실리카를 5 중량 %로 흔합하여 프라이머 용액을 제조하였다. 제조예 4: 프라이머 용액 As the polycarbonate, a polycarbonate resin F 1004A, LG Chemical Co., Ltd. having a glass transition temperature of 134 ° C. and a weight average molecular weight of 16, 000 was used. Preparation Example 3 Primer Solution Polyester-based resin (A-645GH; Takamatsu oil &fat; total solid content except water is 30 wt%? 0 and polyurethane-based resin (CK-PUD-PF; light-glow paint yarn; total solid except water) 30 weight ¾) was mixed at a weight ratio of solid content of 80:20, and aqueous silica was mixed at 5 weight% to prepare a primer solution Preparation Example 4: Primer solution
상기 제조예 3과 동일한 방법으로 제조하되, 폴리에스테르계 수지와 폴리우레탄계 수지를 고형분 기준으로 20 : 80의 중량비로 흔합하여, 프라이머 용액을 제조하였다. 제조예 5: 프라이머 용액 Prepared in the same manner as in Preparation Example 3, by mixing a polyester-based resin and a polyurethane-based resin in a weight ratio of 20: 80 on a solid basis, to prepare a primer solution. Preparation Example 5 Primer Solution
상기 제조예 3과 동일한 방법으로 제조하되, 폴리우레탄계 수지만 사용하여, 프라이머 용액을 제조하였다. 제조예 6: 프라이머 용액 Prepared in the same manner as in Preparation Example 3, using only a polyurethane-based resin, to prepare a primer solution. Preparation Example 6 Primer Solution
상기 제조예 3과 동일한 방법으로 제조하되, 폴리에스테르계 수지와 폴리우레탄계 수지를 고형분 기준으로 65 : 35의 중량비로 흔합하여, 프라이머 용액을 제조하였다. 제조예 7: 프라이머 용액 Prepared in the same manner as in Preparation Example 3, by mixing a polyester-based resin and polyurethane-based resin in a weight ratio of 65: 35 based on the solid content, to prepare a primer solution. Preparation Example 7 Primer Solution
상기 제조예 3과 동일한 방법으로 제조하되, 폴리에스테르계 수지만 사용하여, 프라이머 용액을 제조하였다. 실시예 1 내지 3 및 비교예 1 내지 3 Prepared in the same manner as in Preparation Example 3, using only a polyester resin, to prepare a primer solution. Examples 1 to 3 and Comparative Examples 1 to 3
제조예 1에서 제조한 폴리메틸메타크릴레이트, 제조예 2의 폴리카보네이트, 및 를 자외선 흡수제 (LAF70 , 아데카 사)를 하기 표 1에 기재된 바와 같이 각각 첨가하고, 산화방지제 ( Irganox 1010, BASF 사)를 0.4 phr 함량으로 처방하여 드라이 블렌드하고, 트원 압출기로 컴파운딩하여 수지 조성물을 제조하였다. 상기 수지 조성물을 265°C에서
용융시키고, T-Die를 통하여 시트 형태로 압출 캐스팅하여 두게 180 urn의 시트를 얻었다. 상기 시트를 MD 방향으로 일축 연신한 후, 바코터를 이용하여 상기 제조예 3에서 제조한 프라이머 용액으로 프라이머층을 형성하였으며, 이를 TD 방향으로 연신하여 2축 연신 필름을 제조하였다. 상기 연신온도와 연신배율은 하기 표 1과 같았다. 비교예 4 Polymethyl methacrylate prepared in Preparation Example 1, polycarbonate of Preparation Example 2, and UV absorbers (LAF70, Adeka Co., Ltd.) were respectively added as shown in Table 1 below, and an antioxidant (Irganox 1010, BASF Corporation) was added. ) Was formulated in a 0.4 phr content, dry blended, and compounded with a twin extruder to prepare a resin composition. The resin composition at 265 ° C. The sheet was melted and extrusion cast in the form of a sheet through T-Die to obtain a sheet of 180 urn. After the sheet was uniaxially stretched in the MD direction, a primer layer was formed from the primer solution prepared in Preparation Example 3 using a bar coater, and the sheet was stretched in the TD direction to prepare a biaxially stretched film. The draw temperature and draw ratio were as shown in Table 1 below. Comparative Example 4
상기 실시예 1과 동일한 방법으로 제조하되, 제조예 3의 프라이머 용액 대신 제조예 4의 프라이머 용액을 사용하여, 광학 필름을 제조하였다. 비교예 5 Prepared in the same manner as in Example 1, using the primer solution of Preparation Example 4 instead of the primer solution of Preparation Example 3, an optical film was prepared. Comparative Example 5
상기 실시예 1과 동일한 방법으로 제조하되, 제조예 3의 프라이머 용액 대신 제조예 5의 프라이머 용액을 사용하여, 광학 필름을 제조하였다. 비교예 6 Prepared in the same manner as in Example 1, using the primer solution of Preparation Example 5 instead of the primer solution of Preparation Example 3, an optical film was prepared. Comparative Example 6
상기 실시예 1과 동일한 방법으로 제조하되, 제조예 3의 프라이머 용액 대신 제조예 6의 프라이머 용액을 사용하여, 광학 필름을 제조하였다. 비교예 7 Prepared in the same manner as in Example 1, using the primer solution of Preparation Example 6 instead of the primer solution of Preparation Example 3, an optical film was prepared. Comparative Example 7
상기 실시예 1과 동일한 방법으로 제조하되, 제조예 3의 프라이머 용액 대신 제조예 7의 프라이머 용액을 사용하여, 광학 필름을 제조하였다. 실험예 Prepared in the same manner as in Example 1, using the primer solution of Preparation Example 7 instead of the primer solution of Preparation Example 3, an optical film was prepared. Experimental Example
상기 실시예 및 비교예에서 제조한 광학 필름을 이하의 방법으로 평가하였다. , The optical film manufactured by the said Example and the comparative example was evaluated by the following method. ,
1) 380 nm 투과도: Hi tachi U-3310을 이용하여 380 nm에서의 투과도를 측정하였다. 이때 광학 필름의 두께는 40 um이었다. 1) 380 nm transmittance: The transmittance at 380 nm was measured using Hi tachi U-3310. At this time, the thickness of the optical film was 40 um.
2) TTS(Temperature of Thermal Shr inkage) : 광학용 필름을 10 x 4.5 mm의 치수로 샘플을 제조한 후, TMA(Q400) 장비를 이용하여 측정하였다.
구체적으로, 승온 속도 10 °C /min 및 하증 0.02 N의 조건으로 온도를 가하였을 때, 상기 샘플이 腸 및 TD 방향으로 각각 팽창 후 수축이 시작되는 변곡점의 온도 (접선 기울기가 0)를 TTS 값으로 하였다. 3) 위상차: 복굴절 측정기 (AxoScan , Axometr i cs 사)를 이용하여 550 nm의 파장에서 위상차를 측정하였다. X축 방향의 굴절율 (nx) 및 y축 방향의 굴절율 (ny) , z축 방향의 굴절를 (nz)의 측정값으로, 이하 수학식으로 면내 위상차 (Rin) 및 두께 방향 위상차 (Rth) 값을 계산하였다. 2) TTS (Temperature of Thermal Shr inkage): After preparing a sample of the optical film to the dimensions of 10 x 4.5 mm, it was measured using a TMA (Q400) equipment. Specifically, when the temperature is applied under conditions of a temperature increase rate of 10 ° C / min and a descent 0.02 N, the TTS value of the inflection point (the tangent slope is 0) at which the sample starts to contract after expansion in the 腸 and TD directions, respectively It was made. 3) Phase difference: The phase difference was measured at a wavelength of 550 nm using a birefringence measuring instrument (AxoScan, Axometr i cs). The in-plane phase difference (Rin) and the thickness direction phase difference (Rth) are calculated using the measured values of the refractive index ( nx ) in the X-axis direction, the refractive index (ny) in the y- axis direction, and the refraction in the z-axis direction (nz). It was.
Rin(nm) = (ηχ-ny) d Rin (nm) = (ηχ-ny) d
Rth = (nz-ny) x d Rth = (nz-ny) x d
상기에서, nx는 광학 필름의 면내에서 굴절율이 가장 큰 방향의 굴절율을 나타내며, ny는 nx와 수직인 방향의 굴절율을 나타내고, nz는 광학 필름의 두께 방향의 굴절율을 나타내고, In the above, nx represents the refractive index of the direction of the largest refractive index in the plane of the optical film, ny represents the refractive index of the direction perpendicular to nx, nz represents the refractive index of the thickness direction of the optical film,
d는 광학 필름의 두께 (nm)를 의미한다. d means the thickness (nm) of an optical film.
4) 접착력 (90° 필 (peel ) 박리력) : 물성 분석기 (TA . XT. plus Texture Analyser ; Stable Mi cro Systems)를 이용하여 접착력을 측정하였다. 구체적으로, 일반 아크릴계 광학 필름 /PVA 소자 /상기 제조한 광학 필름 순으로 적층하였다. 이때, 상기 광학 필름의 프라이머 면이 PVA 소자에 면하도록 한 것과, 상기 광학 필름의 프라이머 면의 반대면 (기재면)이 PVA 소자에 면하도록 한 것, 두 종류를 제조하였다. 각 필름 사이에 자외선 경화형 접착제를 도포한 후, 최종 접착층의 두께가 1 내지 2 um이 되도록 조건을 설정하여, 라미네이터를 통과시켰다. 이어, 자외선을 일반 아크릴계 광학 필름 면으로 조사하였다. 이를 폭 2 cm의 시편을 제조하고, 시편 일부를 물성 분석기를 이용하여 PVA 소자로부터 광학 필름을 속도 300 mm/min, 90° 로 박리하여 박리력을 측정하였다. 또한, 상기 시편의 나머지 일부를 80°C에 500시간 보관한 후 동일한 방법으로 박리력을 측정하였다. 상기 결과를 하기 표 1 및 2에 나타내었다. 4) Adhesion (90 ° peel peel): The adhesion was measured using a physical property analyzer (TA.XT.plus Texture Analyser; Stable Micro Systems). Specifically, it was laminated in the order of the general acrylic optical film / PVA device / the optical film prepared above. At this time, the primer surface of the optical film was faced to the PVA device, and the opposite surface (substrate surface) of the primer surface of the optical film to face the PVA device, two types were prepared. After apply | coating UV cure adhesive between each film, conditions were set so that the thickness of a final adhesive layer might be 1-2 micrometers, and the laminator passed through. Subsequently, ultraviolet rays were irradiated onto the normal acrylic optical film side. The specimen was prepared with a width of 2 cm, and the peeling force was measured by peeling an optical film from the PVA device at a speed of 300 mm / min and 90 ° using a property analyzer. In addition, after the rest of the specimen was stored at 80 ° C. for 500 hours, the peel force was measured in the same manner. The results are shown in Tables 1 and 2 below.
위하여 실시예 1의 값을 재차 기재하였다.
【표 1] The value of Example 1 was described again for this purpose. [Table 1]
【표 2] [Table 2]
상기 표 1에 나타난 바와 같이, 본 발명에 따른 실시예 1 내지 3은 모두 380 nm 투과도가 5% 미만으로 나타났으며 , 접착력 또한 1 N/20 隱 이상으로 우수하였다. 반면, 비교예 1및 2은 연신온도가 너무 높아 접착력이 0.5 N/20 隱 미만으로 낮게 나타났다. 또한, 기재면 접착시 실시예 1 내지 3은 모두 접착력 우수하나, 비교예 1 및 2 연신 온도가 너무 높아 접착력이 0.5 N/20 隱 미만으로 낮게 나타났다. 또한, 비교예 3은 자외선 흡수제를 포함하지 않아 380 nm 투과도가 높게 나타나 실질적으로 자외선을 흡수하지 못하였다,
또한, 상기 표 2에 나타난 바와 같이 , 본 발명에 따른 실시예 1에 비하여 비교예 4 내지 7은 프라이머층의 조성이 본 발명에 만족하지 않아 효과적인 접착력이 구현되지 않음을 확인할 수 있었으며, 비교예 7의 경우에는 초기 접착력은 구현되나, 고온에 장시간 노출 후에는 접착력이 저하됨을 확인할 수 있었다. 따라서, 본 발명에 따른 광학 필름은 접착력이 우수하면서도 자외선 흡수 기능이 우수함을 확인할 수 있었다.
As shown in Table 1, Examples 1 to 3 according to the present invention all showed a 380 nm transmittance of less than 5%, the adhesion was also excellent in more than 1 N / 20 kPa. On the other hand, in Comparative Examples 1 and 2, the drawing temperature was too high, and the adhesive strength was lower than 0.5 N / 20 Pa. In addition, in Examples 1 to 3, when the substrate surface is bonded, all of the excellent adhesion, Comparative Examples 1 and 2 stretching temperature is too high, the adhesion was lower than 0.5 N / 20 Pa. In addition, Comparative Example 3 does not include a UV absorber, so the transmittance of 380 nm was high, and thus, the UV absorber could not be absorbed substantially. In addition, as shown in Table 2, Comparative Examples 4 to 7 compared to Example 1 according to the present invention was confirmed that the composition of the primer layer is not satisfied with the present invention, the effective adhesion is not implemented, Comparative Example 7 In the case of the initial adhesive strength is implemented, after a long time exposure to high temperature was confirmed that the adhesive strength is lowered. Therefore, the optical film according to the present invention was confirmed that the excellent ultraviolet absorption function while excellent adhesion.
Claims
【특허청구범위】 [Patent Claims]
【청구항 11 [Claim 11
기재층, 및 상기 기재층 상에 형성된 프라이머층을 포함하는, 2축 연신 광학 필름에 있어서, In the biaxially stretched optical film containing a base material layer and the primer layer formed on the said base material layer,
상기 기재층은 아크릴계 수지 및 자외선 흡수제를 포함하고, 상기 프라이머층은 폴리에스테르계 수지 70 내지 95 중량부 및 폴리우레탄계 수지 5 내지 30 중량부를 포함하는, The base layer includes an acrylic resin and an ultraviolet absorber, and the primer layer includes 70 to 95 parts by weight of polyester resin and 5 to 30 parts by weight of polyurethane resin,
2축 연신 광학 필름. Biaxially stretched optical film.
【청구항 2】 [Claim 2]
게 1항에 있어서, According to claim 1,
상기 아크릴계 수지는 주쇄에 고리 구조를 포함하지 않는, The acrylic resin does not include a ring structure in the main chain,
2축 연신 광학 필름. Biaxially stretched optical film.
【청구항 3】 [Claim 3]
제 1항에 있어서, The method of claim 1,
상기 아크릴계 수지의 유리전이온도는 100 내지 120°C인, The glass transition temperature of the acrylic resin is 100 to 120 ° C,
2축 연신 광학 필름. Biaxially stretched optical film.
【청구항 4】 [Claim 4]
제 1항에 있어서, The method of claim 1,
상기 아크릴계 수지의 중량평균분자량은 100, 000 내지 150 , 000인, 2축 연신 광학 필름. The weight average molecular weight of the acrylic resin is 100, 000 to 150, 000, biaxially stretched optical film.
【청구항 5】 [Claim 5]
게 1항에 있어서, According to claim 1,
상기 아크릴계 수지는 메틸 메타크릴레이트 및 메틸 아크릴레이트의 공중합체인, The acrylic resin is a copolymer of methyl methacrylate and methyl acrylate,
2축 연신 광학 필름.
Biaxially stretched optical film.
【청구항 6] [Claim 6]
제 5항에 있어서, The method of claim 5,
상기 아크릴계 수지는 메틸 메타크릴레이트를 90 내지 99 중량 %로 포함하고, 메틸 아크릴레이트 단량체를 1 내지 10 중량 % 포함하는, The acrylic resin includes 90 to 99% by weight of methyl methacrylate, 1 to 10% by weight of methyl acrylate monomer,
2축 연신 광학 필름. Biaxially stretched optical film.
【청구항 7】 [Claim 7]
제 1항에 있어서, The method of claim 1,
상기 자외선 흡수제는, 상기 아크릴계 수지 100 중량부 대비 0. 1 내지 5 중량부로 포함되는 것을 특징으로 하는, Wherein the ultraviolet absorber, characterized in that contained in 0.1 to 5 parts by weight relative to 100 parts by weight of the acrylic resin,
2축 연신 광학 필름. Biaxially stretched optical film.
【청구항 8] [Claim 8]
제 1항에 있어서, The method of claim 1,
상기 기재층은 폴리카보네이트를 추가로 포함하는 것올 특징으로 하는, The substrate layer is characterized in that it further comprises a polycarbonate,
2축 연신 광학 필름. Biaxially stretched optical film.
【청구항 9】 [Claim 9]
게 8항에 있어서, According to claim 8,
상기 폴리카보네이트의 중량평균분자량은 10 , 000 내지 20 , 000인, 2축 연신 광학 필름. The weight average molecular weight of the polycarbonate is 10, 000 to 20, 000, biaxially stretched optical film.
【청구항 10] [Claim 10]
제 8항에 있어서, The method of claim 8,
상기 기재층은 상기 폴리카보네이트를 10 중량 ¾> 이하로 포함하는, 2축 연신 광학 필름. The base layer is biaxially stretched optical film containing less than 10 weight ¾> polycarbonate.
【청구항 11】 [Claim 11]
제 1항에 있어서,
상기 프라이머층은 폴리에스테르계 수지 및 폴리우레탄계 수지를 각각 75 내지 90 중량부 및 10 내지 25 중량부 포함하는, The method of claim 1, The primer layer comprises 75 to 90 parts by weight and 10 to 25 parts by weight of polyester resin and polyurethane resin, respectively,
2축 연신 광학 필름. Biaxially stretched optical film.
【청구항 12】 [Claim 12]
제 1항에 있어서, The method of claim 1,
상기 2축 연신의 배율은 MD 방향으로 1.2배 내지 3.0배 및 TD 방향으로 1.5배 내지 4.0배인, The magnification of the biaxial stretching is 1.2 times to 3.0 times in the MD direction and 1.5 times to 4.0 times in the TD direction,
2축 연신 광학 필름. Biaxially stretched optical film.
【청구항 13】 [Claim 13]
제 10항에 있어서, The method of claim 10,
상기 MD 방향의 연신 배율과 TD 방향의 연신 배율의 비 (TD 연신 배율 /MD 연신 배율)이 1.0 내지 2.5인, Ratio of the draw ratio in the MD direction and the draw ratio in the TD direction (TD draw ratio / MD draw ratio) is 1.0 to 2.5,
2축 연신 광학 필름. Biaxially stretched optical film.
【청구항 14】 [Claim 14]
제 1항에 있어서, The method of claim 1,
상기 2축 연신 광학 필름은, 필름의 두께가 40 urn인 조건에서, 380 nm투과도가 20% 이하인 , The biaxially stretched optical film has a 380 nm transmittance of 20% or less under the condition that the film thickness is 40 urn.
2축 연신 광학 필름. Biaxially stretched optical film.
【청구항 15】 [Claim 15]
제 1항 내지 제 14항 중 어느 한 항의 2축 연신 광학 필름을 포함하는, 편광판.
The polarizing plate containing the biaxially stretched optical film of any one of Claims 1-14.
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CN201780011999.1A CN108700691A (en) | 2016-09-20 | 2017-09-19 | The optical film of characteristic with high adhesiveness and excellent blocking UV light and including its polarizer |
JP2018546854A JP2019507909A (en) | 2016-09-20 | 2017-09-19 | Optical film excellent in adhesion and ultraviolet blocking function, and polarizing plate including the same |
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KR20160038324A (en) * | 2014-09-30 | 2016-04-07 | 주식회사 엘지화학 | Optical film comprising primer layer comprising polyester-resin, and polarizing plate using the same |
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