KR20140084760A - Optical multilayer film and polarizing plate using the same - Google Patents

Abstract

The present invention relates to a laminated optical film and a polarizing plate including the laminated optical film. More specifically, the laminated optical film has a surface processing layer formed on a base film and a surface protection film laminated on the surface processing layer. The equation of surface energy of the surface processing layer X (adhesive energy of the surface protection film / surface energy of the surface protection film) is in a range higher than 2.0×106mN/m or lower than 5.0×106mN/m to ensure excellent adhesion properties between the surface processing layer and the surface protection film to enable the surface protection film to be easily peeled off.

Description

TECHNICAL FIELD [0001] The present invention relates to a polarizing plate,

The present invention relates to an optical layer film and a polarizing plate comprising the optical layer film, wherein no peeling and no peeling occur between the surface treatment layer and the surface protective film.

A liquid crystal display device (LCD) includes a liquid crystal cell and a polarizer laminated on both surfaces of the liquid crystal cell.

Generally, the polarizing plate is composed of iodine-based polyvinyl alcohol (PVA) polarizer and a protective film for protecting both surfaces of the polarizer. Specifically, it is a multilayer structure in which a protective film is laminated on one surface of a polarizer, and a protective film, a pressure-sensitive adhesive layer for bonding with a liquid crystal cell, and a release film are laminated in order on the other surface.

In addition to the polarizing plate, the liquid crystal display further includes various surface-treated films such as an antiglare film, a low reflection film, a hard coating film and the like in order to improve the display quality.

Such a surface-treated film is subjected to surface treatment so as to prevent defects such as scratches and scratches on the surface of the surface-treated film during handling processes such as processing, transport, transportation, manufacture, A surface protective film may be adhered to the surface protective film.

The surface-treated film on which the surface-protective film is adhered is usually a structure in which a surface-treatment layer and a surface-protective film are laminated on one surface of a base film in this order, and no lifting between the surface- At the same time, the surface protective film must be easily peeled off from the surface treatment layer.

Korean Patent Laid-Open Publication No. 2011-0096503 discloses a technique of improving the adhesion and releasability of a surface protective film by specifying the press-fitting distortion and peeling force of a surface protective film having a support and a pressure-sensitive adhesive layer on one side of the support Lt; / RTI > However, since the above technique requires the use of a pressure-sensitive adhesive layer made of an acrylic polymer in order to improve the adhesiveness and peelability of the surface protective film, application to various pressure-sensitive adhesive layers is limited.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems of the prior art, and it is an object of the present invention to provide a surface protective film and a surface protective film, And to provide an optical layer film in which no peeling and no peeling occur between the surface treatment layer and the surface protective film.

Another object of the present invention is to provide a polarizing plate comprising the optical layer film.

In order to achieve the above object, the present invention provides an optical layer film in which a surface treatment layer is formed on a base film and a surface protective film is laminated on the surface treatment layer, It provides an optical laminate film that satisfies 10 ⁶ mN / m to more than 5.0 × 10 less than ⁶ mN / m range.

(Wherein, the surface energy of the surface treatment layer and the surface protective film were measured by the OWRK (Owen, Wendt, Rabel and Kaelble) method after measuring the water contact angle and the oil contact angle under a constant temperature / humidity condition of 23 ° C. and 60 RH% The adhesive energy of the surface protective film was obtained by bonding a surface protective film to a steel sheet and then folding a part of the surface protective film at an angle of 180 ° and measuring the load when pulling off at a pulling rate of 30 m / .

Also, preferably, the above formula (1) can satisfy the range of 2.4 x 10 ⁶ mN / m to 4.0 x 10 ⁶ mN / m.

The surface treatment layer may be at least one selected from the group consisting of an antiglare layer, a low refractive layer and a hard coat layer.

In addition, the surface treatment layer may be a coating layer on which a composition for forming a surface treatment layer is coated on a base film.

Further, the present invention provides a polarizing plate comprising the optical layer film.

The optical layer film according to the present invention has a correlation between the surface energy of the surface treatment layer and the surface energy and the adhesive energy of the surface protective film and defines the range thereof so that the adhesion property between the surface treatment layer and the surface protective film is excellent And the surface protective film can be easily peeled off.

The present invention relates to an optical layer film and a polarizing plate comprising the optical layer film, wherein no peeling and no peeling occur between the surface treatment layer and the surface protective film.

Hereinafter, the present invention will be described in more detail, but it is for the purpose of illustrating the present invention and is not intended to limit the scope of the present invention.

The optical layer film of the present invention is a structure in which a surface treatment layer is formed on a base film and a surface protective film is laminated on the surface treatment layer, and the optical layer film has a refractive index of 2.0 x 10 ⁶ mN / m And less than 5.0 x 10 < ⁶ > mN / m.

[Equation 1]

Surface energy of surface treatment layer x (adhesion energy of surface protective film / surface energy of surface protective film)

(Wherein, the surface energy of the surface treatment layer and the surface protective film were measured by the OWRK (Owen, Wendt, Rabel and Kaelble) method after measuring the water contact angle and the oil contact angle under a constant temperature / humidity condition of 23 ° C. and 60 RH% The adhesive energy of the surface protective film was obtained by bonding a surface protective film to a steel sheet and then folding a part of the surface protective film at an angle of 180 ° and measuring the load when pulling off at a pulling rate of 30 m / .

The present invention is characterized in that the correlation between the surface energy of the surface treatment layer and the surface energy and the adhesive energy of the surface protective film is determined by the equation 1, and limits the range of the expression (1).

In order to derive Equation (1) and its range, the surface energy and the tacky energy can be determined by the following method.

First, the surface energy of the surface treatment layer and the surface protective film is measured using a contact angle meter.

Specifically, the water contact angle and oil contact angle of the surface treatment layer and the surface protective film are measured using a contact angle meter manufactured by KSV.

The water contact angle and oil contact angle are preferably measured under constant temperature / humidity conditions of 23 DEG C and 60RH%.

The surface energy of the surface treatment layer and the surface protective film can be derived using the water contact angle and the oil contact angle measured under the constant temperature / humidity conditions.

At this time, a method of deriving the surface energy from the contact angle can be OWRK (Owen, Wendt, Rabel and Kaelble) method, and the expression of OWRK is as follows.

The adhesive energy of the surface protective film is measured using a tensile strength machine.

Specifically, a surface protective film having a width of 25 mm and a length of 250 mm is stuck on a stainless steel plate, and then pressed using a pressing roller. Then, the surface protective film is folded at an angle of 180 °, the surface protective film is peeled off by a predetermined length, and the adhesive energy is derived by fixing the surface protective film to the clip of the tensile strength machine have.

The tensile speed at which the surface protective film is pulled off is preferably 30 m / min.

By deriving the surface energy of the surface-treated layer and the surface energy and the adhesive energy of the surface-protective film by the above-described method, the optical layer film has the above-mentioned formula 1 in the range of more than 2.0 x 10 ⁶ mN / m to 5.0 x 10 ⁶ mN / m Or less. And more preferably in the range of 2.4 x 10 ⁶ mN / m to 4.0 x 10 ⁶ mN / m.

When the numerical value of Equation 1 is 2.0 x 10 < ⁶ > mN / m or less, the surface protective film floats from the surface treatment layer. When the surface treatment layer receives external force or temperature change, The appearance of the optical layer film is changed by bubbles existing between the films. Therefore, there is a difference in apparent difference between the portion receiving the external force and the portion not receiving the external force, which causes a reduction in the precision of the visual inspection and a reduction in the yield of the optical layer film produced.

When the numerical value of Equation (1) is 5.0 x 10 ⁶ mN / m or more, a pressure-sensitive adhesive may be present on the surface treatment layer or the surface protective film may not easily peel off when the surface protective film is peeled off.

Hereinafter, each of the base film, the surface treatment layer and the surface protective film constituting the optical layer film of the present invention will be described in detail.

The base film may be a film excellent in transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, and the like. Specific examples include polyester resins such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate and polybutylene terephthalate; Cellulose-based resins such as diacetylcellulose and triacetylcellulose; Polycarbonate resin; Acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene resins such as polystyrene and acrylonitrile-styrene copolymer; Polyolefin resins such as polyethylene, polypropylene, cyclo- or norbornene-structured polyolefins, ethylene-propylene copolymers; Vinyl chloride resin; Amide resins such as nylon and aromatic polyamide; Imide resin; Sulfone based resin; Polyether sulfone type resin; Polyether ether ketone resin; A sulfided polyphenylene resin; Vinyl alcohol type resin; Vinylidene chloride resins; Vinyl butyral resin; Allylate series resin; Polyoxymethylene type resin; Epoxy resin, and the like, and a film composed of the blend of the thermoplastic resin may also be used. Further, a film made of a thermosetting resin such as (meth) acrylic, urethane, acrylic urethane, epoxy, or silicone or a film made of an ultraviolet curable resin may be used.

The surface treatment layer may be a coating layer on which a composition for forming a surface treatment layer is coated on a base film. Such a surface treatment layer serves to impart functions such as antistatic property and antistatic property.

 The surface treatment layer may be at least one selected from the group consisting of an antiglare layer, a low refractive layer and a hard coat layer.

In addition, the surface treatment layer may be a coating layer on which a composition for forming a surface treatment layer is coated on a base film.

The present invention will be described with respect to the surface-treated layer by way of example of the antiglare layer, but the present invention is not limited thereto.

The antiglare layer may be formed using a composition for forming an antiglare layer comprising a light transmitting resin, a light transmitting particle, a photoinitiator, and a solvent for imparting antistatic properties to the base film.

The light transmitting resin is a photocurable resin, and the photocurable resin may include a photocurable (meth) acrylate oligomer and / or a photocurable monomer.

The photocurable (meth) acrylate oligomer may be, for example, epoxy (meth) acrylate, urethane (meth) acrylate or the like, and urethane (meth) acrylate may more preferably be used.

The urethane (meth) acrylate can be produced in the presence of a catalyst having a polyfunctional (meth) acrylate having a hydroxyl group in the molecule and an isocyanate group.

Specific examples of the (meth) acrylate having a hydroxy group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxyisopropyl (meth) acrylate, 4-hydroxybutyl A mixture of pentaerythritol tetra (meth) acrylate, and a mixture of dipentaerythritol penta / hexa (meth) acrylate.

Specific examples of the compound having an isocyanate group include 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,12-diisocyanatododecane, Diisocyanato-2-methylpentane, trimethyl-1,6-diisocyanatohexane, 1,3-bis (isocyanatomethyl) cyclohexane, trans-1,4-cyclohexane diisocyanate, Diisocyanate, toluene-2,6-diisocyanate, xylene-1,4-diisocyanate, tetramethyl xylene-1, Diisocyanate, 1-chloromethyl-2,4-diisocyanate, 4,4'-methylenebis (2,6-dimethylphenyl isocyanate), 4,4'-oxybis (phenylisocyanate), hexamethylene diisocyanate And trifunctional isocyanate derived from trimethylene propanol adduct toluene diisocyanate Ah it may be at least one member selected from the group consisting of carbonate.

The photocurable monomer specifically has an unsaturated group such as a (meth) acryloyl group, a vinyl group, a styryl group or an allyl group as a photocurable functional group in the molecule, and among these, a (meth) acryloyl group is more preferable.

Specific examples of the monomer having a (meth) acryloyl group include neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate, triethylene glycol di (meth) (Meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipropylene glycol di (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra , Dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate (Meth) acrylate such as tripentaerythritol hexa (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, hydroxyethyl , Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, iso-decyl (meth) acrylate, stearyl (meth) acrylate, tetrahydroperfuryl ) Acrylate, phenoxyethyl (meth) acrylate, and isobonole (meth) acrylate.

The photocurable (meth) acrylate oligomers and / or photocurable monomers exemplified above may be used alone or in combination of two or more.

The content of the light-transmitting resin is not particularly limited, but is preferably 1 to 80 parts by weight based on 100 parts by weight of the whole composition for forming an antiglare layer. If the content of the light-transmitting resin is less than 1 part by weight, it may be difficult to achieve sufficient hardness improvement. If the content of the light-transmitting resin exceeds 80 parts by weight, curling may become severe.

The translucent particle is not particularly limited as long as it is a particle capable of imparting a dispersibility in general.

Examples of the translucent particles include silica particles, silicone resin particles, melamine resin particles, acrylic resin particles, styrene resin particles, acryl-styrene resin particles, polycarbonate resin particles, polyethylene resin particles, Resin particles or the like can be used. The light-transmitting particles exemplified above may be used alone or in combination of two or more.

The average particle diameter of the light transmitting particles is preferably 1 to 10 mu m. When the average particle diameter of the light transmitting particles is less than 1 占 퐉, it is difficult to form irregularities on the surface of the antiglare layer, so that the antiglare property may be lowered, and in the case of more than 10 占 퐉, the surface of the antiglare layer may become coarse,

It is preferable that such translucent particles are contained in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the composition for forming an antiglare layer. If the content of the light-transmitting particles is less than 0.5 parts by weight, the antiglare property may be lowered. If the amount is more than 20 parts by weight, whitening of the antiglare layer may be increased.

The photoinitiator is a component for curing the antiglare layer, and the kind thereof is not particularly limited. Examples thereof include acetophenone, benzoin, benzophenone, taoxanthone, triazine, benzylketal, phosphine oxide and alkylphenylketone compounds. Specific examples of the diethoxyacetophenone, dimethoxyacetophenone, 4-quinolone acetophenone, 2-hydroxy-2-methyl-1-phenylpropan- Propan-1-one and its oligomers, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propane 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, dimethoxy-2-phenylacetophenone and 3-methylacetophenone; Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (t- butylperoxycarbonyl) benzophenone , 2,4,6-trimethylbenzophenone, 4,4-diaminobenzophenone; Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Oxantone; (Trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) ) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran- (Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis 2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- ( 3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine; Diphenyl ketone benzyl dimethyl ketal; Trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,9-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -Phenylphosphine oxide; 1-hydroxycyclohexyl phenyl ketone, 4-hydroxycyclophenyl ketone, and the like. Further, anthraquinone, fluorene, triphenylamine, carbazole, titanocene compounds and the like can be given. These may be used alone or in combination of two or more.

Such a photoinitiator may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the composition for forming an antiglare layer. If the content of the photoinitiator is less than 0.1 parts by weight, the curing rate may be slower, and if it exceeds 10 parts by weight, cracking may occur in the antiglare layer due to overcuring.

The solvent can be used without limitation as long as it is known as a solvent for the composition for forming an antiglare layer in the technical field.

Examples of the solvent include alcohols such as methanol, ethanol, isopropanol, butanol, methylcellulose, ethylsorbox, etc., ketones such as methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, Cyclohexanone, etc.), hexane (hexane, heptane, octane etc.), benzene (benzene, toluene, xylene and the like) The solvents exemplified above may be used alone or in combination of two or more.

The solvent may be included in an amount of 10 to 95 parts by weight based on 100 parts by weight of the composition for forming an antiglare layer. When the content of the solvent is less than 10 parts by weight, the viscosity is high and workability is poor. When the content of the solvent is more than 95 parts by weight, the curing process takes a long time and the economical efficiency may be decreased.

The composition for forming an antiglare layer according to the present invention may contain, in addition to the above-mentioned components, additives generally used in the art within the range not to impair the effect of the present invention.

The additive may further include one or more selected from the group consisting of an antioxidant, a UV absorber, a light stabilizer, a leveling agent, a surfactant, an antifouling agent, and a nonionic compound.

It is preferable to compound the compound (nonionic compound) having an HLB value in the predetermined range by the Griffin method. For example, a nonionic compound having an HLB value of not less than 2, preferably not less than 5, more preferably not less than 10, such as not more than 18, preferably not more than 15, by the Griffin method. It is easy to adjust the contact angle of the hard coat film with respect to water, the contact angle with respect to the diiodomethane, and the surface energy to the above-mentioned predetermined range by blending the nonionic compound having an appropriately adjusted HLB value. Nonionic compounds are collectively referred to as compounds that do not exhibit ionic properties due to their dissolution in water, but they are composed of a combination of a hydrophilic group and a hydrophilic group.

Examples of such a compound include at least one kind or more of a hydrophilic group (for example, a polyalkylene oxide, a hydroxyl group, a carboxyl group, a sulfonyl group, a phosphate group, an amino group, an isocyanate group, a glycidyl group, an alkoxysilyl group, Examples of the compound having a hydroxyl group include ethoxylated glycerin triacrylate, ethoxylated bisphenol A diacrylate, polyethylene glycol diacrylate, polyether-modified acrylate and polyhydroxy-modified acrylate. Among them, it is preferable to use polyethylene glycol diacrylate from the viewpoint of solubility as a solvent and handleability. As non-ionic compounds, fatty acid esters and polyethers can also be used.

Examples of fatty acid esters include fatty acid esters obtained by condensation of monohydric alcohols or polyhydric alcohols having two or more valences with fatty acids, and examples thereof include propylene glycol monostearic acid esters, propylene glycol monolauric acid esters, diethylene glycol monostearate Sorbitan monooleate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan monostearate, sorbitan monostearate, sorbitan monostearate, sorbitan monostearate, sorbitan monostearate, sorbitan monostearate, Uric acid esters and the like. The fatty acid ester may be a polyoxyalkylene-added fatty acid ester. Further, a nonionic compound obtained by addition polymerization of an alkylene oxide to a fatty acid ester may be added. As the alkylene oxide to be subjected to the addition polymerization, ethylene oxide or propylene oxide is suitable. The ethylene oxide or the propylene oxide may be added either singly or in a copolymerized state. Examples of the polyoxyalkylene-added fatty acid esters include polyoxyethylene hydrogenated castor oil, polyoxyethylene glycerin monostearate, polyoxyethylene, sorbitan monostearate, polyoxyethylene, sorbitan monostearate, Polyoxyethylene, sorbitan tristearate, polyoxyethylene, sorbitan monooleate, polyoxyethylene, sorbitan monooleate, polyoxyethylene, sorbitan trioleate, polyoxyethylene, sorbitan monolaurate Acid esters, polyoxyethylene glycol 400 monooleic acid esters, polyoxyethylene glycol 400 monomonostearic acid esters, polyethylene glycol 400 monolauric acid esters, polyoxyethylene, and sorbitan monolauric acid esters.

In this example, polyoxyethylene cholesteryl ether, polyoxyethylene decyltetradecyl ether, or the like may be used as a compound other than a fatty acid ester or a polyether. The compound having an HLB value in a predetermined range by the Griffin method is preferably 0.05 to 60 parts by weight, preferably 0.1 to 15 parts by weight, more preferably 1 to 10 parts by weight based on 100 parts by weight of the composition for forming an antiglare layer.

The composition for forming an antiglare layer provides an antiglare film coated on at least one side of a base film to form an antiglare layer. The coating method is not limited, and examples thereof include a die coater, an air knife, a reverse roll, a spray, and a blade. Casting, gravure, spin coating, and the like.

The thickness of the antiglare layer is usually about 0.1 탆 to 200 탆, preferably about 1 탆 to 50 탆, and most preferably 3 탆 to 30 탆.

After the composition for forming an antiglare layer is applied, it is dried by evaporation of volatiles at a temperature of 30 to 150 DEG C for 10 seconds to 1 hour, preferably 30 seconds to 10 minutes. When the drying is completed, the composition for forming an antiglare layer is cured. In the case of photocuring, UV light is irradiated in a nitrogen or air atmosphere to cure the composition for forming an antiglare layer to form an antiglare layer. The irradiation amount of the UV light is about 0.01 to 10 J / cm ² , preferably 0.1 to 2 J / cm ² .

The antiglare film may be subjected to a saponification step with a saponifying solution to facilitate bonding with a surface protective film to be described later.

The above-mentioned saponifying solution is a solution containing an alkali agent. Specifically, examples of the alkaline agent include inorganic alkaline agents such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide; Monoethylamine, diethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, diethanolamine, Organic alkaline agents such as triethanolamine, monoisopropanolamine, and diisopropanolamine; Or their halogenated salts may be used. These may be used alone or in combination of two or more. Of these, sodium hydroxide and potassium hydroxide are preferable in that the pH can be adjusted over a wide range according to the content. The concentration of the alkali agent is preferably 1.0 to 5.0N. If the concentration of the alkali agent is less than 1.0 N or exceeds 5.0 N, the saponification rate may be lowered and non-uniformity of saponification degree may be caused.

The temperature (T) of the saponifying solution is preferably 30 to 70 ° C, more preferably 30 to 60 ° C.

In addition, the saponification process can be carried out using an immersion or coating method, and it is more preferable to apply the saponification solution for about 40 to 50 seconds to activate the saponification.

The surface protective film is the same as the base film described above.

An adhesive layer is attached to one surface of the surface protective film and bonded to the antiglare film to produce an optical layer film.

At this time, the adhesive surface of the surface protective film can be pressed onto the antiglare film at a pressure of 25 MPa at a rate of 0.3 m / min to produce an optical layer film.

The present invention provides a polarizing plate comprising the above optical layer film according to the present invention.

That is, the polarizing plate of the present invention may be formed by bonding the above-described optical layer film according to the present invention to one surface or both surfaces of a conventional polarizer. The polarizer may have a protective film on at least one side thereof.

Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples, but the following examples are only specific examples of the present invention and are not intended to limit or limit the scope of protection of the present invention.

Manufacturing example  One: Anticyclone layer  Composition for forming

Manufacturing example  1-1

20 parts by weight of urethane acrylate (SC2153, Miwon Chemical Co., Ltd.), 20 parts by weight of? Erythritol triacrylate (M340, Miwon Company), light transmitting particles (organosilicon compound coated amorphous particles, surface area 500 m ² / g, 2 parts by weight of methyl ethyl ketone (purified gold), 35 parts by weight of propylene glycol monomethyl ether (purified gold), 2.5 parts by weight of a photoinitiator (I-184, manufactured by Shiba Chemical Co., Ltd.) 0.5 part by weight of BYK3530 (BYK KEMISA) were mixed using a stirrer and filtered using a PP filter to prepare a composition for forming an antiglare layer.

Manufacturing example  1-2

20 parts by weight of urethane acrylate (SC2153, Miwon Chemical Co., Ltd.), 20 parts by weight of? Erythritol triacrylate (M340, Miwon Company), light transmitting particles (organosilicon compound coated amorphous particles, surface area 500 m ² / g, , 20 parts by weight of methyl ethyl ketone (purified water), 35 parts by weight of propylene glycol monomethyl ether (purified water), and 3 parts by weight of a photoinitiator (Cibasia, I-184) , And the mixture was filtered using a PP-made filter to prepare a composition for forming an antiglare layer.

Example : Optical layer film

Example  One

The composition for forming an antiglare layer in Production Example 1-1 was stirred for 1 hour, applied to a side of a transparent substrate film (Fuji Paper, thickness 60um, TAC, surface energy 51.1mN / m) , And dried at 80 DEG C for 2 minutes. Then, the film was cured at a dose of 720 mJ / cm ² in a nitrogen atmosphere to prepare an antiglare film having a surface energy of 34.2 mN / m. Then, the above-mentioned antiglare film was immersed in a saponification solution containing an alkali agent (KOH) having a concentration of 3N for 40 seconds to be saponified. The pressure-sensitive adhesive surface of a surface protective film (Fujimori, FT-PF, surface energy of 31.1 mN / m, adhesive energy of 2.4 x 10 ⁶ mN / m) having a pressure-sensitive adhesive layer was pressed on the saponified antiglare film at a pressure of 0.25 MPa, 0.3 m / min to produce an optical layer film.

Example  2

(Surface energy: 31.1 mN / m, adhesive energy: 2.4 × 10 ⁶ mN / m) as Fujimori's FT-PF (surface energy: 23 mN / m , Adhesive energy: 1.9 × 10 ⁶ mN / m) was used to produce an optical layer film.

Example  3

PF (surface energy: 18 mN / m) of FT-PF (surface energy: 31.1 mN / m, adhesive energy: 2.4 x 10 ⁶ mN / m) was used instead of Fujimori's surface protective film, m, an adhesive energy of 1.3 x 10 ⁶ mN / m).

Example  4

The procedure of Example 1 was repeated except that the surface treatment layer was cured in an air atmosphere in place of the nitrogen atmosphere to prepare an antiglare film having a surface energy of 53.94 mN / m. Then, the above-mentioned antiglare film was immersed in a saponification solution containing an alkali agent (KOH) having a concentration of 3N for 40 seconds to be saponified. The pressure-sensitive adhesive surface of a surface protective film (Fujimori, FT-PF, surface energy of 31.1 mN / m, adhesive energy of 2.4 x 10 ⁶ mN / m) having a pressure-sensitive adhesive layer was pressed on the saponified antiglare film at a pressure of 0.25 MPa, 0.3 m / min to produce an optical layer film.

Example  5

(Surface energy: 31.1 mN / m, adhesive energy: 2.4 × 10 ⁶ mN / m) as Fujimori's FT-PF (surface energy: 23 mN / m , Adhesive energy: 1.9 × 10 ⁶ mN / m) was used to produce an optical layer film.

Example  6

PF (surface energy of 18 mN / m) instead of FT-PF (surface energy of 31.1 mN / m, adhesive energy of 2.4 x 10 ⁶ mN / m) of Fujimori as surface protective film, m, an adhesive energy of 1.3 x 10 ⁶ mN / m).

Example  7

An antiglare film having a surface energy of 44.19 mN / m was prepared by performing the same procedure as in Example 1 except that the surface treatment layer was cured in an air atmosphere in place of the nitrogen atmosphere. (FT-PF, surface energy of 31.1 mN / m, adhesive energy of 2.4 x ¹⁰ < ⁶ > mN / m) having a pressure-sensitive adhesive layer on the antiglare film was omitted, Was pressed at a pressure of 0.25 MPa and a speed of 0.3 m / min to prepare an optical layer film.

Example  8

(Surface energy: 31.1 mN / m, adhesion energy: 2.4 x 10 ⁶ mN / m) as Fujimori's FT-PF (surface energy: 23 mN / m , Adhesive energy: 1.9 × 10 ⁶ mN / m) was used to produce an optical layer film.

Example  9

PF (surface energy of 18 mN / m) of Nitto Denso was used instead of FT-PF (surface energy of 31.1 mN / m, adhesive energy of 2.4 x 10 ⁶ mN / m) of Fujimori Co., m, an adhesive energy of 1.3 x 10 ⁶ mN / m).

Example  10

The composition for forming an antiglare layer of Production Example 1-2 was stirred for 1 hour, applied to a side of a transparent substrate film (Fuji Paper, thickness 60um, TAC, surface energy 51.1mN / m) , And dried at 80 DEG C for 2 minutes. Then, the film was cured in a nitrogen atmosphere at an irradiation dose of 720 mJ / cm ² to prepare an antiglare film having a surface energy of 47.77 mN / m. (FT-PF, surface energy of 31.1 mN / m, adhesive energy of 2.4 x ¹⁰ < ⁶ > mN / m) on the antiglare film was applied on the antiglare film Surface was pressed at a pressure of 0.25 MPa and a speed of 0.3 m / min to produce an optical layer film.

Example  11

(Surface energy: 31.1 mN / m, adhesive energy: 2.4 × 10 ⁶ mN / m) as Fujimori's FT-PF (surface energy: 23 mN / m , Adhesive energy: 1.9 × 10 ⁶ mN / m) was used to produce an optical layer film.

Example  12

PF (surface energy of 18 mN / m) of Nitto Denso was used instead of FT-PF (surface energy of 31.1 mN / m, adhesive energy of 2.4 x 10 ⁶ mN / m) of Fujimori as surface protective film, m, an adhesive energy of 1.3 x 10 ⁶ mN / m).

Example  13

The composition for forming an antiglare layer of Production Example 1-2 was stirred for 1 hour, applied to a side of a transparent substrate film (Fuji Paper, thickness 60um, TAC, surface energy 51.1mN / m) , And dried at 80 DEG C for 2 minutes. Then, the film was cured in an air atmosphere at an irradiation dose of 720 mJ / cm ² to prepare an antiglare film having a surface energy of 48.39 mN / m. (FT-PF, surface energy of 31.1 mN / m, adhesive energy of 2.4 x ¹⁰ < ⁶ > mN / m) having a pressure-sensitive adhesive layer on the antiglare film was omitted, Was pressed at a pressure of 0.25 MPa and a speed of 0.3 m / min to prepare an optical layer film.

Example  14

(Surface energy: 31.1 mN / m, adhesive energy: 2.4 × 10 ⁶ mN / m) as Fujimori's FT-PF (surface energy: 23 mN / m , Adhesive energy: 1.9 × 10 ⁶ mN / m) was used to produce an optical layer film.

Example  15

PF (surface energy of 18 mN / m) of Nitto Denso was used instead of FT-PF (surface energy of 31.1 mN / m, adhesive energy of 2.4 x 10 ⁶ mN / m) of Fujimori as surface protective film, m, an adhesive energy of 1.3 x 10 ⁶ mN / m).

Comparative Example  One

An antiglare film having a surface energy of 27.3 mN / m was prepared in the same manner as in Example 1, except that the surface treatment layer had a surface energy of 27.3 mN / m. (FT-PF, surface energy of 31.1 mN / m, adhesive energy of 2.4 x ¹⁰ < ⁶ > mN / m) having a pressure-sensitive adhesive layer on the antiglare film was omitted, Was pressed at a pressure of 0.25 MPa and a speed of 0.3 m / min to prepare an optical layer film.

Comparative Example  2

(Surface energy: 31.1 mN / m, adhesive energy: 2.4 × 10 ⁶ mN / m) of Fujimori FT-PF (surface energy: 23 mN / m , Adhesive energy: 1.9 × 10 ⁶ mN / m) was used to produce an optical layer film.

Comparative Example  3

(Surface energy of 18.1 mN / m, adhesive energy of 2.4 x 10 ⁶ mN / m) instead of Fujimori's FT-PF (surface energy of 31.1 mN / m) m, an adhesive energy of 1.3 x 10 ⁶ mN / m).

Comparative Example  4

The composition for forming an antiglare layer of Production Example 1-2 was stirred for 1 hour, applied to a side of a transparent substrate film (Fuji Paper, thickness 60um, TAC, surface energy 51.1mN / m) , And dried at 80 DEG C for 2 minutes. Then, the film was cured at a dose of 720 mJ / cm ² in a nitrogen atmosphere to prepare an antiglare film having a surface energy of 71.26 mN / m. (FT-PF, surface energy of 31.1 mN / m, adhesive energy of 2.4 x ¹⁰ < ⁶ > mN / m) having a pressure-sensitive adhesive layer on the antiglare film was omitted, Was pressed at a pressure of 0.25 MPa and a speed of 0.3 m / min to prepare an optical layer film.

Comparative Example  5

(Surface energy: 31.1 mN / m, adhesive energy: 2.4 × 10 ⁶ mN / m) as Fujimori's FT-PF (surface energy: 23 mN / m , Adhesive energy: 1.9 × 10 ⁶ mN / m) was used to produce an optical layer film.

Comparative Example  6

PF (surface energy of 18 mN / m) instead of FT-PF (surface energy of 31.1 mN / m, adhesive energy of 2.4 x 10 ⁶ mN / m) of Fujimori as a surface protective film, m, an adhesive energy of 1.3 x 10 ⁶ mN / m).

Comparative Example  7

The composition for forming an antiglare layer of Production Example 1-2 was stirred for 1 hour, applied to a side of a transparent substrate film (Fuji Paper, thickness 60um, TAC, surface energy 51.1mN / m) , And dried at 80 DEG C for 2 minutes. Then, the film was cured in an air atmosphere at an irradiation dose of 720 mJ / cm ² to prepare an antiglare film having a surface energy of 76.09 mN / m. Then, the above-mentioned antiglare film was immersed in a saponification solution containing an alkali agent (KOH) having a concentration of 3N for 40 seconds to be saponified. The pressure-sensitive adhesive surface of a surface protective film (Fujimori, FT-PF, surface energy of 31.1 mN / m, adhesive energy of 2.4 x 10 ⁶ mN / m) having a pressure-sensitive adhesive layer was pressed on the saponified antiglare film at a pressure of 0.25 MPa, 0.3 m / min to produce an optical layer film.

Comparative Example  8

(Surface energy: 31.1 mN / m, adhesion energy: 2.4 × 10 ⁶ mN / m) as Fujimori's FT-PF (surface energy: 23 mN / m , Adhesive energy: 1.9 × 10 ⁶ mN / m) was used to produce an optical layer film.

Comparative Example  9

(Surface energy of 18.1 mN / m, adhesion energy of 2.4 x 10 ⁶ mN / m) instead of Fujimori's FT-PF (surface energy of 31.1 mN / m) as a surface protective film, m, an adhesive energy of 1.3 x 10 ⁶ mN / m).

<Measurement method>

The surface energy of the surface treatment layer and the surface protective film of the examples and the comparative examples and the adhesive energy of the surface protective film were measured by the following methods, and the results are shown in Table 1.

1) Surface energy

1. Water contact angle

After dropping water droplets onto the surface of the antiglare film at room temperature (25 ° C), the contact angle with respect to water droplets was measured using a contact angle meter (KSV, CAM100) after 1 minute. The contact angle was measured three times using the same sample of the left and right contact angle of the water droplet, and the average value was used.

2. oil contact angle

Diiodomethane droplets were dropped onto the surface of the antiglare film at room temperature (25 DEG C), and contact angle with respect to diiodomethane droplets was measured using a contact angle meter (KSV, CAM100) after 1 minute. The contact angle was measured three times using the same sample of the left and right contact angle of the diiodomethane drop, and the average value was used.

The measured values of the water contact angle and the oil contact angle were measured using the following OWRK (Owen, Wendt, Rabel and Kaelble) equations.

2) Adhesion energy

Adhesive force measurement was performed by attaching a surface protecting film (FT-PF, LG Chem GT-PF, Nitto Denso NT-PF) having a width of 25 mm and a length of 250 mm to a SUS # 304 stainless steel plate, And reciprocated once at a speed of 300 mm / min. After the lapse of 24 hours, the surface protective film was folded at an angle of 180 °, and the steel plate was fixed on the lower clip of the tensile strength machine (SJTA-034HSD) / min &lt; / RTI &gt; at the pulling rate.

division Surface treatment layer
Surface energy
(mN / m) Surface protective film surface energy (mN / m) Surface protective film adhesive energy
(mN / m) Equation 1
Surface energy of the surface treatment layer x
(The adhesive energy of the surface protective film /
Surface energy of surface protective film
(mN / m) Example 1 34.2 31.1 2.4 × 10 ⁶ 2.6 x 10 ⁶ Example 2 34.2 23 1.9 × 10 ⁶ 2.8 × 10 ⁶ Example 3 34.2 18 1.3 × 10 ⁶ 2.4 × 10 ⁶ Example 4 53.94 31.1 2.4 × 10 ⁶ 4.2 × 10 ⁶ Example 5 53.94 23 1.9 × 10 ⁶ 4.4 × 10 ⁶ Example 6 53.94 18 1.3 × 10 ⁶ 3.8 × 10 ⁶ Example 7 44.19 31.1 2.4 × 10 ⁶ 3.4 × 10 ⁶ Example 8 44.19 23 1.9 × 10 ⁶ 3.6 × 10 ⁶ Example 9 44.19 18 1.3 × 10 ⁶ 3.1 × 10 ⁶ Example 10 47.77 31.1 2.4 × 10 ⁶ 3.7 × 10 ⁶ Example 11 47.77 23 1.9 × 10 ⁶ 3.9 × 10 ⁶ Example 12 47.77 18 1.3 × 10 ⁶ 3.4 × 10 ⁶ Example 13 48.39 31.1 2.4 × 10 ⁶ 3.7 × 10 ⁶ Example 14 48.39 23 1.9 × 10 ⁶ 4.0 × 10 ⁶ Example 15 48.39 18 1.3 × 10 ⁶ 3.4 × 10 ⁶ Comparative Example 1 25.3 31.1 2.3 × 10 ⁶ 1.8 × 10 ⁶ Comparative Example 2 23.3 23 1.9 × 10 ⁶ 1.9 × 10 ⁶ Comparative Example 3 27.3 18 1.3 × 10 ⁶ 1.9 × 10 ⁶ Comparative Example 4 71.26 31.1 2.4 × 10 ⁶ 5.5 × 10 ⁶ Comparative Example 5 71.26 23 1.9 × 10 ⁶ 5.8 × 10 ⁶ Comparative Example 6 71.26 18 1.3 × 10 ⁶ 5.1 × 10 ⁶ Comparative Example 7 76.09 31.1 2.4 × 10 ⁶ 5.9 × 10 ⁶ Comparative Example 8 76.09 23 1.9 × 10 ⁶ 6.2 × 10 ⁶ Comparative Example 9 76.09 18 1.3 × 10 ⁶ 5.4 × 10 ⁶

Test Example

The physical properties of the optical layer films of the examples and comparative examples were measured by the following methods, and the results are shown in Table 2.

1) Excavation evaluation

The optical layer film was allowed to stand under the environment of 25 DEG C and 50 RH for 24 hours to visually observe whether floating between the surface treatment layer and the surface protective film of the antiglare film occurred and then evaluated according to the following criteria.

<Evaluation Criteria>

○: Lift

×: Not excited

2) Peel evaluation

The optical layer film was allowed to stand under the environment of 25 占 폚 and 50 RH% for 24 hours, and then the adhesive tape of the surface protective film was peeled at a peeling speed of 0.3 m / min, And peeled off at the peeling angle. The peeling between the surface treatment layer of the antiglare film and the surface protective film was evaluated according to the following criteria.

<Evaluation Criteria>

○: Peeled off

X: Not peeled off

division Equation 1
Surface energy of the surface treatment layer x
(The adhesive energy of the surface protective film /
Surface energy of surface protective film
(mN / m) Domestic consumption
Contact angle
(°) Oil
Contact angle
(°) Lifting Exfoliation Example 1 2.6 x 10 ⁶ 80.36 61 × ○ Example 2 2.8 × 10 ⁶ 80.36 61 × ○ Example 3 2.4 × 10 ⁶ 80.36 61 × ○ Example 4 4.2 × 10 ⁶ 58.76 36.17 × ○ Example 5 4.4 × 10 ⁶ 58.76 36.17 × ○ Example 6 3.8 × 10 ⁶ 58.76 36.17 × ○ Example 7 3.4 × 10 ⁶ 86.05 33.25 × ○ Example 8 3.6 × 10 ⁶ 86.05 33.25 × ○ Example 9 3.1 × 10 ⁶ 86.05 33.25 × ○ Example 10 3.7 × 10 ⁶ 70.59 37.22 × ○ Example 11 3.9 × 10 ⁶ 70.59 37.22 × ○ Example 12 3.4 × 10 ⁶ 70.59 37.22 × ○ Example 13 3.7 × 10 ⁶ 69.08 37.35 × ○ Example 14 4.0 × 10 ⁶ 69.08 37.35 × ○ Example 15 3.4 × 10 ⁶ 69.08 37.35 × ○ Comparative Example 1 1.8 × 10 ⁶ 97.96 64.11 ○ ○ Comparative Example 2 1.9 × 10 ⁶ 97.96 64.11 ○ ○ Comparative Example 3 1.9 × 10 ⁶ 97.96 64.11 ○ ○ Comparative Example 4 5.5 × 10 ⁶ 23.87 40.92 × × Comparative Example 5 5.8 × 10 ⁶ 23.87 40.92 × × Comparative Example 6 5.1 × 10 ⁶ 23.87 40.92 × × Comparative Example 7 5.9 × 10 ⁶ 6.36 40.52 × × Comparative Example 8 6.2 × 10 ⁶ 6.36 40.52 × × Comparative Example 9 5.4 × 10 ⁶ 6.36 40.52 × ×

As shown in Table 2, it was confirmed that the optical laminated films of Examples 1 to 15 satisfying the range of the formula (1) did not cause lifting and peeling between the surface treatment layer and the surface protective film.

On the other hand, the optical layer films of Comparative Examples 1 to 3 were peelable between the surface treatment layer and the surface protective film, but lifting occurred, and the optical layer films of Comparative Examples 4 to 9 were peeled off between the surface treatment layer and the surface protective film It was confirmed that no peeling occurred but peeling occurred.

Claims (5)

An optical layer film in which a surface treatment layer is formed on a base film and a surface protective film is laminated on the surface treatment layer,
The optical laminate film to equation (1) is 2.0 × 10 ⁶ mN / m to 5.0 greater than the optical layer, characterized by satisfying the range of less than × 10 ⁶ mN / m loaded
[Equation 1]
Surface energy of surface treatment layer x (adhesion energy of surface protective film / surface energy of surface protective film)
The optical layer film according to claim 1, wherein the formula (1) satisfies the range of 2.4 x 10 ⁶ mN / m to 4.0 x 10 ⁶ mN / m.
The optical layer film according to claim 1, wherein the surface treatment layer is at least one selected from the group consisting of an antiglare layer, a low refractive layer and a hard coating layer.
4. The optical layer film according to claim 3, wherein the surface treatment layer is a coating layer on which a composition for forming a surface treatment layer is coated on a base film.
A polarizer comprising the optical layer film according to any one of claims 1 to 4.