KR20130000447A - Coating composition for anti-glare, anti-glare film using the coating composition, polarizing plate and display device - Google Patents

Abstract

The present invention relates to a composition for forming an antiglare layer, an antiglare film, a polarizing plate, and an image display device using the same.
The composition for forming an antiglare layer according to the present invention is a urethane (meth) acrylate oligomer (A), a (meth) acrylate monomer (B), silicon particles (C), a photoinitiator (D) and a solvent ( E) is made.
≪ Formula 1 >

(In Formula 1, R1 is ethylene or propylene, R2 is hydrogen or methyl, X is an aliphatic hydrocarbon having 1 to 30 carbon atoms, n is an integer of 1 to 10, m is an integer of 1 to 5).
The composition for forming an antiglare layer according to the present invention includes a urethane (meth) acrylate oligomer having a low refractive index, thereby minimizing a difference in refractive index with low refractive silicon particles, thereby maintaining excellent anti-glare property during film formation. Not only can the transmission sharpness be improved, but also the curl prevention effect is shown. Accordingly, the composition for forming the antiglare layer may be usefully used for the production of the antiglare film, and the manufactured antiglare film may be usefully applied to the polarizing plate and the display device.

Description

Anti-glare layer forming composition, anti-glare film, polarizing plate and image display device using the same {Coating Composition for Anti-Glare, Anti-Glare Film using the Coating Composition, Polarizing Plate and Display Device}

The present invention relates to a composition for forming an antiglare layer, an antiglare film, a polarizing plate, and an image display device using the same.

The anti-glare film has a function of reducing reflection of external light by using diffuse reflection by surface protrusions, and various display panels such as liquid crystal display (LCD), plasma display (PDP), CRT, and electroluminescent display (EL). It is used for the purpose of preventing the reduction of the contrast due to the reflection of external light or the deterioration of the visibility of the display due to the reflection of the image.

The anti-glare film described above can be produced by various methods. Typically, the antiglare film is produced by applying a UV curable resin in which fine particles having a predetermined particle size are dispersed on a transparent substrate, drying the film, and irradiating UV rays to cure the unevenness to form irregularities on the surface thereof. have.

Various techniques are known in this regard. In Korean Patent No. 1999-0057941, transmissive fine particles having a refractive index of 1.53 to 1.62 or more and a transmissive resin having a refractive index of 1.49 to 1.53 are used, but the transparence fineness is improved by setting the difference in refractive index between the transparent fine particles and the transparent resin to 0.03 or more and 0.20 or less. Disclosed is a technique to make. However, the technique disclosed in Korean Patent No. 1999-0057941 makes it difficult to lower the refractive index of the translucent resin, so that when the silicon particles having a low refractive index (for example, a refractive index of 1.43) are applied to the translucent particles, the refractive index difference from the transparent resin is different. Is largely generated and there is a problem in that the transmission sharpness cannot be improved.

An object of the present invention is to include the silicon particles as the light-transmitting fine particles while lowering the refractive index of the light-transmissive resin to reduce the difference in refractive index between the silicon particles and the transparent resin to maintain the excellent anti-glare when manufacturing the anti-glare film while improving the transmission sharpness, It is to provide a composition for forming an antiglare layer having excellent curl prevention properties.

Another object of the present invention is to provide an antiglare film having excellent antiglare property and transmittance sharpness formed using the antiglare layer forming composition.

Still another object of the present invention is to provide a polarizing plate provided with the antiglare film.

Still another object of the present invention is to provide a display device provided with the antiglare film.

In order to achieve the above object, the present invention provides a composition for forming an antiglare layer comprising a urethane (meth) acrylate oligomer (A) and a (meth) acrylate monomer (B) represented by the following Chemical Formula 1. .

≪ Formula 1 >

(In Formula 1, R1 is ethylene or propylene, R2 is hydrogen or methyl, X is an aliphatic hydrocarbon having 1 to 30 carbon atoms, n is an integer of 1 to 10, m is an integer of 1 to 5).

It is preferable that the refractive index of the urethane (meth) acrylate oligomer (A) represented by the said Formula (1) is 1.45-1.48.

The antiglare layer forming composition may further include a silicon particle (C), a photoinitiator (D) and a solvent (E).

It is preferable that the refractive index of the said silicon particle (C) is 1.42-1.45.

The average particle diameter of the silicon particles (C) is preferably 2.0um to 5,0um.

It is preferable that the refractive index of the composition except the said silicon particle (C), a photoinitiator (D), and a solvent (E) is less than 1.49.

The composition for forming an antiglare layer is 1.5 to 45 parts by weight of the urethane (meth) acrylate oligomer (A), 0.1 to 30 parts by weight of the (meth) acrylate monomer (B), and the silicon particles based on 100 parts by weight of the total. (C) 0.1 to 2.5 parts by weight, 0.05 to 5 parts by weight of the photoinitiator (D) and 50 to 95 parts by weight of the solvent (E).

In order to achieve another object of the present invention, the present invention provides an anti-glare film comprising an anti-glare layer formed by using the composition for forming an anti-glare layer according to the present invention on one or both surfaces of the transparent substrate.

In order to achieve another object of the present invention, the present invention provides a polarizing plate characterized in that the anti-glare film is provided.

In order to achieve the another object of the present invention, the present invention provides a display device characterized in that the anti-glare film is provided.

As described above, the composition for forming the antiglare layer according to the present invention is excellent in forming the film by minimizing the refractive index difference with the low refractive silicon particles by the light-transmitting resin comprises a urethane (meth) acrylate having a low refractive index characteristics While maintaining the anti-glare property, it is possible not only to improve the transmission sharpness but also to exhibit a curl prevention effect. Accordingly, the composition for forming the antiglare layer may be usefully used for the production of the antiglare film, and the manufactured antiglare film may be usefully applied to the polarizing plate and the display device.

Hereinafter, the present invention will be described in more detail.

The composition for antiglare layer formation according to the present invention comprises a urethane (meth) acrylate oligomer (A), a (meth) acrylate monomer (B), silicon particles (C), a photoinitiator (D) and a solvent (E). . For reference, in the following description, the light transmissive resin refers to the remaining composition except for the silicon particles (C), the photoinitiator (D), and the solvent (E).

Urethane (meth) acrylate Oligomer (A)

The urethane (meth) acrylate oligomer is included to reduce the refractive index of the composition except the particles, it is represented by the following formula (1). Particularly, in the case of the composition for forming an antiglare layer including the urethane (meth) acrylate oligomer represented by the following Chemical Formula 1, excellent anti-curling effect is produced during film production.

≪ Formula 1 >

(In Formula 1, R1 is ethylene or propylene, R2 is hydrogen or methyl, X is an aliphatic hydrocarbon having 1 to 30 carbon atoms, n is an integer of 1 to 10, m is an integer of 1 to 5).

In Formula 1, R1 is ethylene or propylene, and the propylene may be preferably isopropylene. The repeating unit including the ethylene or propylene may be made of a repeating unit of ethylene oxide and / or propylene oxide ring opening, and these repeating units may be in the form of a single or a mixture of two or more kinds.

The urethane (meth) acrylate oligomer represented by Chemical Formula 1 may be prepared by reacting a (meth) acrylate monomer including a hydroxyl group and an ethylene oxide / propylene oxide ring opening with an aliphatic hydrocarbon compound having two or more isocyanate groups in a molecule. have.

Specific examples of the aliphatic hydrocarbon compound having two or more isocyanate groups in the molecule include 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,12-diisocyanato Decane, 1,5-diisocyanato-2-methylpentane, trimethyl-1,6-diisocyanatohexane, 1,3-bis (isocyanatomethyl) cyclohexane, trans-1,4-cyclohexene diisocyanate And 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, trifunctional isocyanate derived from hexamethylene diisocyanate, trifunctional isocyanate derived from isophorone diisocyanate, and the like. The compound which has the said isocyanate group can be used individually or in combination of 2 types or more, respectively.

Specific examples of the (meth) acrylate monomer including the hydroxy group and the ethylene oxide / propylene oxide ring opening are ethylene oxide ring-opened hydroxy mono (meth) acrylate having a repeating unit of 1 to 10, and having a repeating unit of 1 to 10. Propylene oxide ring-opened hydroxy mono (meth) acrylate, caprolactone ring-opened hydroxy acrylate, and the like, wherein the (meth) acrylate monomer containing the above-described hydroxy group and ethylene oxide / propylene oxide ring opening each It can be used or mixed two or more kinds.

The urethane (meth) acrylate oligomer represented by Chemical Formula 1 has a low refractive index of 1.45 to 1.48 to lower the refractive index of the translucent resin including the same. Accordingly, even when the composition for forming an antiglare layer including the light transmissive resin includes silicon particles having a low refractive index, the difference in refractive index between the silicon particles and the translucent resin is minimized. Therefore, when the film is formed using the composition for forming the antiglare layer, it is possible to improve the transmission sharpness while maintaining the excellent antiglare property. In addition, the urethane (meth) acrylate oligomer represented by the formula (1) is mixed with other (meth) acrylate monomers have a low shrinkage during photocuring, thereby exhibiting the effect of preventing curl generation. .

The amount of the urethane (meth) acrylate oligomer (A) represented by Formula 1 is preferably 1.5 to 45 parts by weight based on 100 parts by weight of the total composition for forming an antiglare layer. When the content of the urethane (meth) acrylate oligomer (A) is less than 1.5 parts by weight, the refractive index of the translucent resin may not be sufficiently reduced, and when the content of the urethane (meth) acrylate oligomer (A) exceeds 45 parts by weight, curling may occur in the produced antiglare film. There are disadvantages.

( Meta ) Acrylate Monomer (B)

The (meth) acrylate monomer (B) is added to improve the hardness of the antiglare layer.

The (meth) acrylate monomer (B) is, for example, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate , Propylene glycol (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, neopentyl glycoldi (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate Di (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, At least one selected from the group consisting of stearyl (meth) acrylate, tetrahydroperfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, and isobornol (meth) acrylate can be used.

Although the usage-amount of the said (meth) acrylate monomer (B) is not restrict | limited, It is preferable that 0.1-30 weight part is included with respect to 100 weight part of whole compositions for anti-glare layer formation. If the added amount of the (meth) acrylate monomer (B) is less than 0.1 parts by weight based on the above standard, it is difficult to obtain a sufficient hardness improvement effect, if it exceeds 30 parts by weight problem that may cause cracks and curl of the anti-glare film on the coating surface There is this.

Silicon particle (C)

The silicon particles (C) form an unevenness on the surface of the antiglare film to impart antiglare properties to the film.

The silicon particles (C) may be applied without limitation as long as they are generally used in the art. Preferably, the silicon particles (C) may use a refractive index of 1.42 ~ 1.45.

In addition, the silicon particles (C) preferably have an average particle diameter of 2.0um or more and 5,0um or less. If the average particle diameter of the silicon particles (C) is less than 2.0um, irregularities are difficult to form on the surface of the antiglare layer, and thus the antiglare effect does not appear. If the average particle diameter exceeds 5.0um, the irregularities on the surface of the antiglare layer become rough, causing visibility problems.

In addition, it is preferable that the usage-amount of the said silicon particle (C) contains 0.1-2.5 weight part with respect to 100 weight part of whole compositions for anti-glare layer formation. The content of the silicon particles is less than 0.1 parts by weight based on the above standard and the number of irregularities on the surface of the antiglare layer is less anti-glare effect, if the content of silicon particles exceeds 2.5 parts by weight has a problem that whitening occurs in the anti-glare film .

Photoinitiator (D)

The photoinitiator (D) may be applied without limitation as long as it is generally used in the art.

Specifically, the photoinitiator (D) is 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1, diphenylketonebenzyldimethylketal, 2-hydroxy-2-methyl-1 -Phenyl-1-one, 4-hydroxycyclophenylketone, dimethoxy-2-phenylatetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-knoloacetophenone , 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenylketone, benzophenone and the like can be selected and used. However, the present invention is not limited thereto.

The photoinitiator (D) may be used in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the total composition for forming an antiglare layer. When the content of the photoinitiator (D) is less than 0.05 parts by weight based on the above criteria, when the curing rate of the antiglare layer forming composition is slow and exceeds 5 parts by weight, cracking of the antiglare layer may occur due to over curing.

Solvent (E)

The solvent (E) is applied to improve the coating property when the antiglare layer forming composition is applied to a transparent substrate. The solvent (E) can be used without limitation so long as it is known in the art.

Specific examples of the solvent (E) include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, isobutyl alcohol, methyl glycol, methyl glycol acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, acetone, Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diacetone alcohol; esters such as methyl formate, methyl acetate, ethyl acetate, ethyl lactate and butyl acetate; nitromethane, N-methylpyrrolidone, N Nitrogen-containing compounds such as N-dimethylformamide; ethers such as propylene glycol monomethyl ether, diisopropyl ether, tetrahydrofuran, dioxane and dioxolane; methylene chloride, chloroform, trichloroethane, tetrachloroethane and the like Halogenated hydrocarbons; and other substances such as dimethyl sulfoxide and propylene carbonate. The solvents (E) exemplified above may be used alone or in combination of two or more thereof.

The solvent (E) is not necessarily limited, but the solvent (E) is preferably included 50 to 95 parts by weight based on 100 parts by weight of the composition for forming an antiglare layer. If the content of the solvent (E) is less than 50 parts by weight based on the above standards, the viscosity is high and workability is lowered, if it exceeds 95 parts by weight has a disadvantage that takes a lot of time in the drying and curing process.

In the case of the composition for forming an antiglare layer according to the present invention including the above-described components and components, the refractive index of the composition excluding the silicon particles (C), the photoinitiator (D) and the solvent (E), that is, the translucent resin, is preferably less than 1.49. When the refractive index of the light-transmissive resin exceeds 1.49, there is a problem in that the transmission sharpness of the coating film is decreased by increasing the difference in refractive index between the light-transmissive resin and the silicon particles.

In addition to the above components, the composition for forming an antiglare layer according to the present invention may be used with photo-stimulating agents, antioxidants, UV absorbers, light stabilizers, thermal polymerization inhibitors, leveling agents, surfactants, lubricants and the like.

The present invention provides an antiglare film prepared using the composition for forming an antiglare layer described above.

The anti-glare film according to the present invention includes an anti-glare layer formed by applying the above-described composition for forming an anti-glare layer on one side or both sides of a transparent substrate and then curing.

The anti-glare film produced using the composition according to the present invention has excellent anti-glare property while having excellent anti-glare property and high transmission sharpness.

Any film can be used as long as the transparent substrate is a transparent film. For example, as the transparent substrate, a cycloolefin derivative having a unit of a monomer containing a cycloolefin such as norbornene or a polycyclic norbornene monomer, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, isobutyl Cellulose selected from ester cellulose, propionyl cellulose, butyryl cellulose or acetyl propionyl cellulose, ethylene-vinyl acetate copolymer, polyester, polystyrene, polyamide, polyetherimide, polyacryl, polyimide, polyether sulfone, poly Sulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether sulfone, polymethyl methacrylate, polyethylene terephthalate , Polybutyl Terephthalate, may be used polyethylene naphthalate, polycarbonate, polyurethane, may be used one selected from among epoxy, non-stretched uniaxially or biaxially stretched film. Of these, preferred are monoaxially or biaxially oriented polyester films which are excellent in transparency and heat resistance, cycloolefin-based derivative films which are excellent in transparency and heat resistance and capable of coping with the enlargement of the film, transparency and optical anisotropy, An acetylcellulose film may suitably be used.

The thickness of the transparent base material is not necessarily limited, but is preferably 8 to 1000 μm, more preferably 40 to 100 μm.

Application of the composition for forming the antiglare layer can be easily performed by applying a method known in the art, for example, coating such as die coater, air knife, reverse roll, spray, blade, casting, gravure and spin coating The method can be applied.

The preferable coating thickness of the said anti-glare layer forming composition is 3-10 micrometers. After application, the composition is dried by evaporation of the volatiles for 10 seconds to 1 hour, preferably 30 seconds to 10 minutes at a temperature of 30 ~ 150 ℃. After curing by irradiation with UV light. The irradiation amount of said UV light is about 0.01-10 J / cm <2>, Preferably it is 0.1-2 J / cm <2>.

The thickness of the antiglare layer is not limited but is preferably in the range of 1.5-5 μm.

The present invention provides a polarizing plate provided with the anti-glare film described above. That is, the polarizing plate according to the present invention is formed by laminating the antiglare film according to the present invention on the other side of the polarizer in which the protective film is laminated on at least one side or one side of the polarizer.

The polarizer may be used without particular limitation that is generally used in the art.

For example, the polarizer is a film polyvinyl alcohol obtained by uniaxial stretching by adsorbing a dichroic substance such as iodine or a dichroic dye to a hydrophilic polymer film such as a polyvinyl alcohol film or an ethylene-vinyl acetate copolymerized partial saponified film. And polyene-based alignment films such as dehydration of polyvinyl chloride and dehydrochlorination of polyvinyl chloride. Among these, the polarizer which consists of dichroic substances, such as a polyvinyl alcohol-type film and iodine, can be used preferably. Although the thickness of these polarizers is not specifically limited, Generally, it is about 5-80 micrometers.

The protective film may be preferably applied excellent in transparency, mechanical strength, thermal stability, moisture shielding, isotropy and the like.

For example, the protective film may be a polyester film such as polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate or the like; Cellulose films such as diacetyl cellulose and triacetyl cellulose; Polycarbonate film; Acrylic films such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene films such as polystyrene and acrylonitrile-styrene copolymers; Polyolefin-based films such as polyethylene, polypropylene, cyclo- or polyolefin-based films having a norbornene structure, and ethylene propylene copolymers; Polyimide film; Polyether sulfone-based film; Sulfone type films and the like can be used. Among the protective films exemplified above, a triacetyl cellulose film may be preferably used in view of excellent transparency and no optically anisotropy. The thickness of the protective film is not particularly limited, and is preferably 8 to 1000 µm, more preferably 40 to 100 µm.

The present invention also provides a display device to which the above-described antiglare film is applied.

For example, the display device according to the present invention can be manufactured by incorporating a polarizing plate on which at least one antiglare film of the present invention is laminated on a display device. In addition, the anti-glare film of this invention can also be made to adhere to the window of a display apparatus. The anti-glare film of the present invention can be preferably used in reflective, transmissive, semi-transmissive LCD or LCD of various driving methods such as TN type, STN type, OCB type, HAN type, VA type, and IPS type. In addition, the anti-glare film of the present invention can be preferably used for various display devices such as plasma displays, field emission displays, organic EL displays, inorganic EL displays, electronic papers, and the like.

The present invention will be further illustrated by the following examples, which are only specific examples of the present invention, and are not intended to limit or limit the protection scope of the present invention.

[ Synthetic example  1] urethane Acrylate Oligomer  synthesis

100 parts by weight of 4,4'-methylene bis (cyclohexyl isocyanate) (H12MDI, Biomaterials) and ethylene oxide ring opening, 525 parts by weight of hydroxy monoacrylate (PEA6, Cognis) of repeat unit 6, as a reaction catalyst 1.0 part by weight of dibutyl butyl dilaurate (FASCAT 4202, Akema) and 0.4 part by weight of methoxy hydroquinone (HQMME, Eastman) were used as polymerization inhibitors. The reaction was carried out at 80 ° C. for 6 hours, and the reaction was terminated when 2265 cm −1, an isocyanate characteristic peak of the infrared spectrum, disappeared completely. At this time, the refractive index of the synthesized urethane acrylate oligomer was 1.477.

[ Synthetic example  2] urethane Acrylate Oligomer  synthesis

620 parts by weight of 100 parts by weight of isophorone diisocyanate (IPDI, BASF) and ethylene monoacrylate (PEA6, Cognis, Inc.) with repeating unit 6, 1.0 part by weight of dibutyl butyl dilaurate as a reaction catalyst (FASCAT 4202, Akema Co., Ltd.) and 0.4 parts by weight of methoxy hydroquinone (HQMME, Eastman Co., Ltd.) were used as polymerization inhibitors. The reaction was carried out at 80 ° C. for 6 hours, and the reaction was terminated when 2265 cm −1, an isocyanate characteristic peak of the infrared spectrum, disappeared completely. At this time, the refractive index of the synthesized urethane acrylate oligomer was 1.475.

[ Synthetic example  3] urethane Acrylate Oligomer  synthesis

100 parts by weight of hexamethylene diisocyanate (HMDI, Tokyo Kasei Co., Ltd.) and propylene oxide ring opening, 655 parts by weight of hydroxy monoacrylate (PPA6, Cognis Co., Ltd.) as repeating unit 6, 1.0 parts by weight of dibutyl butyl dilaurate as a reaction catalyst. (FASCAT 4202, Akema Co., Ltd.) and 0.4 parts by weight of methoxy hydroquinone (HQMME, Eastman Co., Ltd.) were used as polymerization inhibitors. The reaction was carried out at 80 ° C. for 6 hours, and the reaction was terminated when 2265 cm −1, an isocyanate characteristic peak of the infrared spectrum, disappeared completely. In this case, the refractive index of the synthesized urethane acrylate oligomer was 1.471.

[ Synthetic example  4] urethane Acrylate Oligomer  synthesis

100 parts by weight of 4,4'-methylenebis (cyclohexyl isocyanate) (H12MDI, Biomaterials) and propylene oxide ring-opening agent 655 parts by weight of hydroxymonoacrylate (PPA6, Cognis) of repeating unit 6, as a reaction catalyst 1.0 part by weight of dibutyl butyl dilaurate (FASCAT 4202, Akema) and 0.4 part by weight of methoxy hydroquinone (HQMME, Eastman) were used as polymerization inhibitors. The reaction was carried out at 80 ° C. for 6 hours, and the reaction was terminated when 2265 cm −1, an isocyanate characteristic peak of the infrared spectrum, disappeared completely. At this time, the refractive index of the synthesized urethane acrylate oligomer was 1.463.

[ Synthetic example  5] urethane Acrylate Oligomer  synthesis

100 parts by weight of 4,4'-methylenebis (cyclohexyl isocyanate) (H12MDI, Biomaterials) and 525 parts by weight of dipentaerythritol penta / hexaacrylate (DPHA, Japan Synthetic), 1.0 part by weight of dibutyl butyl di 0.4 parts by weight of methoxy hydroquinone (HQMME, Eastman) was used as laurate (FASCAT 4202, Akema) and polymerization inhibitor. The reaction was carried out at 80 ° C. for 6 hours, and the reaction was terminated when 2265 cm −1, an isocyanate characteristic peak of the infrared spectrum, disappeared completely. At this time, the refractive index of the synthesized urethane acrylate oligomer was 1.495.

[ Synthetic example  6] urethane Acrylate Oligomer  synthesis

100 parts by weight of 2,4-toluene diisocyanate (TDI, Tokyo Kasei Co., Ltd.) and ethylene monocyclic ring-opening agent, 620 parts by weight of hydroxy monoacrylate (PEA6, Cognis), repeating unit 6, 1.0 part by weight of reaction catalyst Butyl tin dilaurate (FASCAT 4202, Akema) and 0.4 parts by weight of methoxy hydroquinone (HQMME, Eastman) were used as polymerization inhibitor. The reaction was carried out at 80 ° C. for 6 hours, and the reaction was terminated when 2265 cm −1, an isocyanate characteristic peak of the infrared spectrum, disappeared completely. At this time, the refractive index of the synthesized urethane acrylate oligomer was 1.504.

Antiglare layer  Preparation of the composition for formation: Example  1-7 and Comparative example  1-4

Each component was mixed at a ratio as shown in Tables 1 and 2 to prepare a composition for forming an antiglare layer.

Composition Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 urethane
Acrylate
Oligomer Synthesis Example 1 25.25 10.25 24.76 Synthesis Example 2 25.25 10.25 Synthesis Example 3 25.25 10.25 Synthesis Example 4 25.25 10.25 Synthesis Example 5 Synthesis Example 6 Acrylate
Monomer M340 5 5 5 5 20 20 20 20 5 Silicon particles Tospearl 130 0.875 0.875 0.875 0.875 0.875 0.875 0.875 0.875 1.12 Tospearl 145 0.875 0.875 0.875 0.875 0.875 0.875 0.875 0.875 1.12 solvent PGME 65 65 65 65 65 65 65 65 65 Photoinitiator I-184 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 additive BYK-3550 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Refractive index ^* 1.479 1.477 1.474 1.467 1.481 1.483 1.482 1.479 1.480

Composition Example 10 Example 11 Example 12 Example 13 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 urethane
Acrylate
Oligomer Synthesis Example 1 9.76 Synthesis Example 2 24.76 Synthesis Example 3 Synthesis Example 4 24.76 9.76 Synthesis Example 5 25.25 10.25 24.76 Synthesis Example 6 25.25 10.25 Acrylate
Monomer M340 5 5 20 20 5 5 20 20 5 Silicon particles Tospearl 130 1.12 1.12 1.12 1.12 0.875 0.875 0.875 0.875 1.12 Tospearl 145 1.12 1.12 1.12 1.12 0.875 0.875 0.875 0.875 1.12 solvent PGME 65 65 65 65 65 65 65 65 65 Photoinitiator I-184 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 additive BYK-3550 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Refractive index 1.477 1.467 1.482 1.480 1.493 1.501 1.490 1.493 1.493

In Tables 1 and 2, the refractive index ^* is the refractive index of the remaining composition excluding the solvent, silicon particles, photoinitiator. In addition, each component used is as follows.

M340: Pentaerythritol tri / tetra acrylate (Miwon Corporation)

Tospearl 130: 3um diameter silicon particles (refractive index 1.43, momentary)

Tospearl 130: 4.5um diameter silicon particles (refractive index 1.43, momentary)

PGME: 1-methoxy-2-propanol (Samjeon Pure Pharmaceutical Co., Ltd.)

Igacure 184: 1-hydroxycyclohexylphenyl ketone (Ciba company)

BYK 3550: Silicone Modified Oil (BYK)

< Experimental Example >

After stirring the composition prepared in Example and Comparative Example for 6 hours, and then applied to the triacetyl cellulose film (40㎛, TAC) with a meyer bar, dried at 70 ℃ for 2 minutes, and then cured to 700mJ / cm2 thickness 2.5㎛ An antiglare film having a phosphorus antiglare layer was prepared. The physical properties of the antiglare film were measured as follows, and the results are shown in Tables 3 and 4 below.

(1) Total light transmittance and haze measurement

The total light transmittance and Haze of each anti-glare film were measured using the spectrophotometer (HZ-1 Haze Meter of Suga Corporation).

(2) anti-glare evaluation

The anti-glare film was bonded to the black acrylic plate using a pressure-sensitive adhesive and then reflected by a three-wavelength stand light to evaluate the anti-glare property to the extent that the shape of the stand light was clearly seen as follows.

Anti-glare ◎: The shape of the stand light is crushed and not recognized

Anti-glare ○: The shape of the stand light is blurred

Anti-glare X: The shape of the stand light is clearly visible

(3) Measurement of transmission sharpness

The transmission sharpness of each film was measured using the sharpness measuring instrument (ICM-1T, Suga Corporation). In measuring the transmission sharpness, the transmission sharpness value was determined by the sum of the transmission sharpness values of slit intervals of 0.001 mm, 0.5 mm, 1.0 mm, and 2.0 mm.

(4) Measurement of reflection sharpness

The reflection sharpness value of the antiglare film has a correlation with the antiglare value, and the smaller the reflection sharpness value, the higher the antiglare property.

The anti-glare film was bonded to a black acrylic plate using an adhesive and then measured by using a sharpness measuring instrument (ICM-1T, Sugasa) to measure the reflection sharpness at an angle of 60 degrees. The reflection sharpness values were 0.5 mm and 1.0 mm. , The values at 2.0 mm were added together.

 (5) curling measurement

After cutting the antiglare film to 10cm x 10 cm, and left in a constant temperature and humidity chamber with a temperature of 25 ℃, 50% humidity for one day was evaluated as a phenomenon that the four corners of the antiglare film falling from the bottom surface.

○: When one of the four corners of the film is not separated from the bottom

△: When one of the four edges of the film is separated from the bottom surface

X: Four corners of the four corners of the film are separated from the floor

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Total light transmittance (%) 92.4 92.3 92.3 92.1 91.6 91.6 91.7 91.9 92.1 Haze (%) 10.2 10.3 10.1 10.9 16.9 16.8 16.5 16.1 14 Anti-glare ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Transmission sharpness 254.7 258.4 261.3 221.9 114.9 112.6 121.5 288.2 181.9 Reflection 27.6 26.9 26.3 23.8 22.2 22.6 21.7 35.3 24.6 curl O O O O O O O O O

Example 10 Example 11 Example 12 Example 13 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Total light transmittance (%) 91.9 91.7 91.6 91.4 91.7 91.4 91.4 91.3 91.3 Haze (%) 14.2 13.9 19.6 19.4 18.9 19.8 18.3 21.1 22.4 Anti-glare ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Transmission sharpness 175.8 177.6 105.7 198.6 60.0 51.0 85.7 74.3 43.7 Reflection 24.1 22.1 21.7 27.5 19.0 18.9 25.0 24.3 17.6 curl O O O O X O X △ X

As shown in Tables 3 and 4, in the embodiment of the present invention including the urethane (meth) acrylate oligomer represented by the formula (1) while containing silicon particles of low refractive index, it includes a urethane (meth) acrylate oligomer of another structure Compared with the comparative example, the difference in refractive index between the silicon particles and the light-transmissive resin is small, so that not only the transparency of transparency is excellent but also the excellent anti-glare property can be confirmed.

Claims (10)

A composition for forming an antiglare layer comprising a urethane (meth) acrylate oligomer (A) and a (meth) acrylate monomer (B) represented by the following formula (1).
&Lt; Formula 1 >

(In Formula 1, R1 is ethylene or propylene, R2 is hydrogen or methyl, X is an aliphatic hydrocarbon having 1 to 30 carbon atoms, n is an integer of 1 to 10, m is an integer of 1 to 5). The refractive index of the urethane (meth) acrylate oligomer (A) represented by the said Formula (1) is 1.45-1.48, The composition for anti-glare layer formation of Claim 1 characterized by the above-mentioned. The composition for forming an antiglare layer according to claim 1, wherein the composition for forming an antiglare layer further comprises silicon particles (C), a photoinitiator (D), and a solvent (E). The composition for forming an antiglare layer according to claim 4, wherein the refractive index of the silicon particles (C) is 1.42 to 1.45. The composition for forming an antiglare layer according to claim 4, wherein the average particle diameter of the silicon particles (C) is 2.0 um to 5,0 um. The composition for forming an antiglare layer according to claim 1, wherein the refractive index of the composition excluding the silicon particles (C), the photoinitiator (D), and the solvent (E) is less than 1.49. The method according to claim 4, 1.5 to 45 parts by weight of the urethane (meth) acrylate oligomer represented by the formula (1) relative to 100 parts by weight of the total composition for forming the antiglare layer, 0.1 to 30 parts by weight of the (meth) acrylate monomers, 0.1 to 2.5 parts by weight of silicon particles, 0.05 to 5 parts by weight of the photoinitiator, characterized in that the composition for forming an antiglare layer. An anti-glare film comprising the anti-glare layer formed by applying the composition for forming the anti-glare layer of any one of claims 1 to 7 on one or both surfaces of the transparent substrate and then curing. The antiglare film of Claim 8 was provided, The polarizing plate characterized by the above-mentioned. Display device characterized in that the anti-glare film of claim 8.