KR101620998B1 - Antistatic coating composition and antistatic film using the same - Google Patents

Abstract

The present invention relates to an antistatic coating composition comprising an inorganic or organic hybrid type ionic liquid copolymer prepared by using silica particles containing an unsaturated functional group on the surface thereof and an organic salt copolymer containing an unsaturated functional group, The antistatic film thus produced is provided.

Description

TECHNICAL FIELD [0001] The present invention relates to an antistatic coating composition and an antistatic film using the antistatic coating composition.

The present invention relates to an antistatic coating composition comprising an inorganic hybrid type ionic liquid copolymer excellent in antistatic function and an antistatic film using the same.

The demand for plastic molded articles is increasing steadily as a substitute for glass and metal products because it is light, has excellent resistance to rupture, is inexpensive, and is easy to mold. In recent years, such plastic molded articles have been used for decorative purposes such as signboards and displays, and in particular, transparent plastic has been applied to public transportation means such as trains, taxis, airplanes, and transparent plates used in large buildings . In addition, application of such a transparent plastic as a soundproofing wall material of a high-speed train which has recently become a subject of interest is being investigated.

Many plastics molded articles having various excellent properties have been commercially developed, but plastics are electroconductive in nature, so they are easily charged by friction or the like to generate static electricity, adsorb dust or the like in the air, and the appearance of appearance is lowered . Also, this characteristic of plastics can impair product value by lowering the light transmittance.

In addition, the front panel used in a cathode-ray tube, a plasma display panel, or a liquid crystal display device is likely to attract foreign substances such as dust around the front panel due to the charging phenomenon of the surface during operation of the image display device. When the viewer's body touches the front panel, static electricity causes discomfort, and sometimes such static electricity causes damage or malfunction of the IC circuit in the apparatus.

In order to solve the above problems, it is desirable to use a transparent plastic having antistatic properties in an electrostatic sensitive electronic or electronic material manufacturer or a hospital, or to form a transparent conductive film panel on the transparent conductive film panel, There was an attempt to solve the problem.

Particularly, as such a charged film, a three-layer structure in which a hard coating layer, a high refractive index layer and a low refractive index layer are laminated on a light transmitting base film is mainly used. Further, in order to simplify the manufacturing process, a hard coat layer or a two-layer structure in which a high refractive index layer and a low refractive index layer are laminated on a base film has been commercialized.

Such an antistatic film is produced by a dry method or a wet method.

Among them, the dry method is a method in which a low refractive index material (for example, MgF ₂ , SiO ₂ or the like) is laminated on a substrate film by vapor deposition, sputtering or the like, or a high refractive index material (for example, ITO Indium), ATO (tin doped antimony oxide), ZnO, TiO _2, etc.) and the low refractive index material are alternately laminated. The dry method has an advantage of being able to produce an antistatic film having high inter-layer adhesion, but it has a high manufacturing cost and is rarely commercially used.

On the other hand, the wet method is a method of applying a composition including a polymer resin, an organic solvent, and the like onto a substrate film, drying and curing the composition, and its manufacturing cost is lower than that of the dry method.

However, the above-mentioned wet process has a disadvantage in that the adhesion between each layer is weak and the scratch resistance is poor, since the steps of forming the respective layers such as the hard coat layer, the high refractive index layer and the low refractive index layer included in the antistatic film are separately performed. In addition, the antistatic film may cause whitening due to environmental changes such as temperature and humidity.

In particular, as a main method of exhibiting the antistatic function by the wet method, a method of adding an inorganic particle or organic salt type polymer having conductivity to the hard coating liquid composition is widely used. When the inorganic conductive nanoparticles are used in the high refractive index layer having a general three-layer structure, the antistatic function is satisfied, but the transmissivity is lowered when the film is used as a clear type low reflection coating film (transmittance> 95%). As described above, in order to simplify the manufacturing process and reduce the cost, a low reflection film having a two-layer structure is currently commercialized. In order to realize a two-layer structure, the hard coating layer must contain a conductive material having antistatic function. In this method, an organic salt type polymer is used. The introduction of the organic salt type ionic liquid has a disadvantage that whitening occurs due to bleeding out of the organic salt due to moisture in the air after coating, although the antistatic function, the transmittance and the haze characteristics are good. To solve this problem, a method using a copolymer of an organic salt having a reactive coupler (acrylate) may be used.

Accordingly, various studies have been made on a method for solving the above problems at the same time, but the degree of such research is insufficient.

An object of the present invention is to provide an antistatic coating composition which is excellent in antistatic property of a hard coat layer and can produce a film which does not cause whitening even under high-temperature and high-humidity environmental conditions, exhibits excellent optical characteristics and improved scratch resistance .

The present invention also provides an antistatic film produced using the coating composition.

The present invention also provides a display device including the antistatic film.

The present invention provides an antistatic coating composition comprising an organic liquid hybrid type ionic liquid copolymer comprising a functional group to which silica particles are bonded.

The present invention also provides an antistatic film produced using the coating composition.

The present invention also provides a display device comprising the antistatic film.

Hereinafter, an antistatic coating composition according to a specific embodiment of the present invention, an antistatic film produced using the antistatic coating composition, and a display device including the film will be described in detail.

The inventors of the present invention have been studying a low reflection film having a low reflectance and excellent antistatic property while using a hybrid type ionic liquid copolymer containing silica, it has a low reflectance and excellent antistatic property , A film having excellent light transmittance and haze characteristics and exhibiting high scratch resistance and low reflectance can be produced, thereby completing the present invention.

Particularly, since the antistatic coating composition of the present invention contains a copolymer of an inorganic particle / organic salt type which is prepared by polymerization using a surface-initiated polymerization method, the coating film has a low reflectance and excellent antistatic properties.

The antistatic coating composition according to one embodiment of the present invention includes an organic hybrid type ionic liquid copolymer containing a functional group to which silica particles are bonded.

In the present invention, the organic / inorganic hybrid type ionic liquid copolymer containing the functional group to which the silica particles are bonded is prepared by using silica particles containing an unsaturated functional group on the surface and an organic salt copolymer containing an unsaturated functional group . In particular, the inorganic particles / organic salt type copolymer may be prepared by using an organic salt copolymer and quaternary ammonium-based conductive monomer and a (meth) acrylic-based inorganic particle and a surface-initiated polymerization method.

In particular, the organic hybrid type ionic liquid copolymer containing the functional group to which the silica particles are bonded may comprise a first functional group to which an organic salt is bonded and a second functional group to which a silica particle is bonded. The first functional group may be at least one selected from the group consisting of a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a pyrroline skeleton, a pyrrole skeleton, an imidazolium cation, a tetrahydropyrimidinium cation, And may include one selected from the group consisting of a cation, a pyrazolium cation, a pyrazolinium cation, a tetraalkylammonium cation, a trialkylsulfonium cation, and a tetraalkylphosphonium cation.

Specific examples of the cation of the first functional group to which the organic salt is bonded in the ionic liquid copolymer include 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl- Butyl-4-methylpyridinium cation, a 1-butyl-3-methylpyridinium cation, a 1-butyl-3,4-dimethylpyridinium cation, a 1,1-dimethylpyrrolidinium cation, Methyl-1-propylpyrrolidinium cation, a 1-ethyl-2-phenylindole cation, a 1-ethyl-1-methylpyrrolidinium cation, Ethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-ethylimidazolium cation, Methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, Zolium cations, Dimethylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethyl Imidazolium cation, 1-hexyl-2,3-dimethylimidazolium cation, 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3-trimethyl- Tetrahydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,5-tetramethyl- 1,4,5,6-tetrahydropyrimidinium cation, 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1 , 2,3-trimethyl-1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl- Dihydropyrimidinium cation, a 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cation, a 1-methylpyrazolium cation, a 3-methylpyrazolium cation, - methylpiperazine A tetraethylammonium cation, a tetraethylammonium cation, a tetrapropylammonium cation, a tetrapropylammonium cation, a tetrahexylammonium cation, a tetraheptylammonium cation, a triethylmethylammonium cation, a tributylethylammonium cation, a tetramethylammonium cation, , Trimethyldecylammonium cation, trioctylmethylammonium cation, tripentylbutylammonium cation, trihexylmethylammonium cation, trihexylpentylammonium cation, triheptylmethylammonium cation, triheptylhexylammonium cation, N, N-diethyl-N N-dimethyl-N, N-dipropylammonium cation, N, N-dimethyl-N (2-methoxyethyl) ammonium cation, glycidyltrimethylammonium cation, diallyldimethylammonium cation, N-dimethylamino-N-ethyl-N-propylammonium cation, N, N-dimethyl- An N, N-dimethyl-N-ethyl-N-butylammonium cation, an N, N-dimethyl- Ethyl-N-heptylammonium cation, an N, N-dimethyl-N-propyl-N-butylammonium cation, N-dimethyl-N-butyl-N-heptylammonium cation, N, N-dimethyl- N-dimethyl-N-heptylammonium cation, N, N-diethyl-N-heptylammonium cation, N, Methyl-N-propylammonium cation, N, N-diethyl-N-methyl-N-pentylammonium cation, N, -Propyl-N-pentylammonium cation, triethylmethylammonium cation, triethylpropylammonium cation, triethylpentylammonium cation, N-dipropyl-N-methyl-N-ethylammonium cation, N, N-dipropyl-N-methyl-N-pentylammonium cation, N, An N, N-dibutyl-N-methyl-N-hexylammonium cation, a trioctylmethylammonium cation, an N, N-dibutyl- Ethyl-N-propyl-N-pentylammonium cation, trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexylsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation Tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraheptylphosphonium cation, tetraoctylphosphonium cation, tetrabutylphosphonium cation, tetrabutylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraheptylphosphonium cation, tetrabutylphosphonium cation, tetrabutylphosphonium cation, tetrabutylphosphonium cation, Ethyl methylphosphonium cation, tributylethylphosphonium cation, trimethyl And a t-decylphosphonium cation.

Further, as the anion component of the first functional groups of the organic salts combined in the ionic liquid copolymer, as long as it is satisfied that the ionic liquid is not particularly limited, and its specific examples, Cl ^-, Br ^-, I ^-, AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , NO ₃ ^- , CH ₃ COO ^- , CF ₃ COO ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^{- _{3 SO 2) 2 N -,}} (CF 3 SO 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, (HF) n -, (CN) 2 N -, C 4 F ₉ SO ₃ ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , C ₃ F ₇ COO ^- , (CF ₃ SO ₂ ) (CF ₃ CO) N ^- and the like. Particularly, anion components such as CH ₃ SO ₃ ^- or CF ₃ SO ₃ ^- are preferably used in terms of dissolution with an organic solvent.

The first functional group to which the organic salt is bonded in the ionic liquid copolymer may be appropriately selected from a combination of the cation component and the anion component. Specific examples thereof include 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl- Methyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) imide, 1-hex Methyl-1-pyrrolin tetrafluoroborate, 1-ethyl-2-phenylindole tetrafluoroborate, 1,2-dimethylindole tetrafluoroborate, 1- ethylcarbazole Ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl- Methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazole Ethyl-3-methylimidazolium pentafluorobutainesulfobate, 1-ethyl-3-methylimidazoliumdithiocyanamide, 1-ethyl-3-methylimidazole Ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethylsulfonyl) imide, 3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoro Butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutyrate, Butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-hexyl-3-methylimidazolium bromide, 1 Hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl- 3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-2,3-dimethylimidazole (Trifluoromethanesulfonyl) imide, 1-methylpyrazolium tetrafluoroborate, 3-methylpyrazolium tetrafluoroborate, 2-dimethyl-3-propylimidazolium bis Tetrahexylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium tetrafluoroborate, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, Diallyl dimethyl ammonium bis (pent N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate, N, (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl- N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, glycidyltrimethylammonium trifluoromethanesulfonate, glycidyltrimethylammonium bis (Trifluoromethanesulfonyl) imide, glycidyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl (Trifluoromethanesulfonyl) trifluoroacetoamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetate (Trifluoromethanesulfonyl) trifluoroacetamide, diallyldimethylammonium (trifluoromethanesulfonyl) amide, N, N-diethyl- N, N-dimethyl-N-ethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide (trifluoromethanesulfonyl) trifluoroacetamide, glycidyltrimethylammonium N, N-dimethyl-N-ethyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, (Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, (Trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl- N, N-dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl- (Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) N, N-dimethyl-N-pentyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, Trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, Imidosulfonyl) imide, N, N-diethyl-N-methyl-N N-diethyl-N-methyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N (Trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, triethylpentylammonium bis (trifluoromethanesulfonyl) imide, , Triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl-N-ethylammonium bis (trifluoromethanesulfonyl) (Trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) N, N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dibutylammonium bis (trifluoromethanesulfonyl) N, N- (Trifluoromethanesulfonyl) imide, trioctylmethylammonium bis (trifluoromethanesulfonyl) imide, N-methyl-N-ethyl-N-propyl N-pentylammonium bis (trifluoromethanesulfonyl) imide, and the like.

In the present invention, the organic or inorganic hybrid type ionic liquid copolymer containing a functional group to which the silica particles are bonded may have a weight average molecular weight of 50,000 to 200,000, preferably 60,000 to 150,000, more preferably 70,000 to 130,000. The organic or inorganic hybrid type ionic liquid copolymer may have an organic solvent dispersibility.

Thus, the antistatic coating composition of the present invention has optical characteristics excellent in light transmittance and haze characteristics, exhibits high abrasion resistance and low reflectance, and has excellent anti-wet heat characteristics.

In general, as a method of imparting an antistatic function to the hard coat layer, there are a method of introducing conductive inorganic particles and a method of applying an organic salt type ionic liquid. When conductive inorganic particles are used, they have good antistatic properties, but they have disadvantages of reduced transmittance. In addition, the introduction of the organic salt type ionic liquid has a good surface resistance, transmittance, and haze characteristics, but has a disadvantage that whitening occurs due to bleeding out of the organic salt in the wet heat resistance test. Thus, recently, a method using a copolymer of an organic salt having a reactive bonding group has been used so as to exhibit good optical characteristics and exhibit antistatic function well.

Coatings using organic salt type copolymers can alleviate the bleed out phenomenon of low molecular weight organic salts themselves, but they have weak strength. Therefore, in order to compensate for this, the present invention attempts to achieve high film strength and antistatic properties by polymerizing a copolymer of a quaternary ammonium salt on the surface of particles using inorganic particles exhibiting good film strength characteristics.

As described above, the organic hybrid type ionic liquid copolymer may be prepared by surface-initiated polymerization. The silica particles as the inorganic particles may be those having a (meth) acrylic group on the surface thereof or a (meth) acrylic group substituted on the surface of the non-surface-treated silica particles, and the organic salt copolymer may be obtained from a quaternary ammonium- Can be made.

The content of the organic hybrid type ionic liquid copolymer in the coating liquid composition may be 1% to 20%, preferably 3% to 15%, more preferably 5% to 10%. If the content of the inorganic particles / organic salt type polymer is less than 1%, the surface resistance increases and it may be difficult to realize antistatic performance. If the content exceeds 20%, haze due to humidity during coating may easily occur. Scratch degradation may occur.

The proportion of the inorganic particles in the composition of the polymerized organic or inorganic hybrid type ionic liquid copolymer may be 10% to 50%, preferably 15% to 30%, more preferably 20% to 25% have. When the content of the inorganic particles is less than 10%, sufficient film strength can not be obtained when applied to the coating liquid. When the content of the inorganic particles exceeds 50%, the number of particles used increases, so that the molecular weight distribution of the organic copolymer It is difficult to obtain a homogeneous polymer. When dispersed in the coating liquid, it is difficult to form a conductive path, so that the surface resistance can be increased.

The inorganic particles used in the organic hybrid type ionic liquid copolymer may be nanoparticles having an average particle size of 5 to 100 nm, preferably 10 to 50 nm, more preferably 20 to 40 nm , And a reactive functional group such as an acrylic group or a methacrylic group on the surface. The nanoparticles may also be surface treated nanosilica particles. Examples of nanosilica particles that are not specifically limited to the products include TS-100, Aerosil series (Degussa), T-32 (Tokuyama), and E220 (Nippon Silica) ) MEK-Ac (Nissan), Purisol (Gamatake), and xp1184 (nano-resin) are examples of the surface treated with acrylic group.

In the present invention, in addition to the inorganic particle / organic salt hybrid type polymer, a photo-curable resin and a photoinitiator may be further included.

The photocurable resin is at least one selected from the group consisting of a cellulosic polymer, an acrylic polymer, a styrene polymer, an epoxy polymer, a nylon polymer, and a polyolefin polymer. In particular, the photo-curable resin may contain an acrylate-based functional group. For example, the photocurable resin may be a reactive acrylate oligomer group consisting of a urethane acrylate oligomer, an epoxy acrylate oligomer, a polyester acrylate, and a polyether acrylate; And dipentaerythritol hexaacrylate, dipentaerythritol hydroxy pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, dipentaerythritol triacrylate trimethylene, propyl triacrylate, propoxylated glycerol triacrylate Polyfunctional acrylate monomer composed of trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, propoxylated glycerol triacrylate, tripropylene glycol diacrylate, and ethylene glycol diacrylate , And the like. Among these, the photo-curing resin is preferably pentaerythritol triacrylate, dipentaerythritol triacrylate, or ethylene glycol diacrylate in view of the curing rate and shrinkage.

In particular, the photocurable resin may have a weight average molecular weight (Mw) of 100 or more, or 100 to 2,000, preferably 200 or more, more preferably 500 or more. In the present invention, the photocurable resin may have a weight average molecular weight of 1,000 or more in view of the curing rate.

In addition, the coating composition of the present invention may include a photoinitiator for the purpose of curing by ultraviolet irradiation together with the above-mentioned photo-curing resin and a polymer of inorganic particle / organic salt type. Wherein the photoinitiator is selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, hydroxydimethylacetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin butyl ether A single substance or a mixture of two or more substances may be used, but the present invention is not limited to the examples described above.

At this time, the photoinitiator may be added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the photocurable resin. When the photoinitiator is contained in an amount of less than 0.1 part by weight based on 100 parts by weight of the photo-curable resin, sufficient photo-curing may not occur due to ultraviolet irradiation. When the photoinitiator is contained in an amount of more than 10 parts by weight based on 100 parts by weight of the photo- The initiator may remain as an impurity, the crosslinking density may be lowered, the mechanical properties of the film may deteriorate, and the reflectance may be increased. As a result, the film strength of the antistatic film to be finally formed can be lowered.

In particular, the antistatic coating composition of the present invention comprises 30 to 50 parts by weight, preferably 35 to 45 parts by weight, more preferably 35 to 40 parts by weight of an inorganic particle / organic salt type 1 to 20 parts by weight of polymer, preferably 3 to 15, more preferably 5 to 10, and 0.001 to 10 parts by weight, preferably 0.005 to 5, more preferably 0.01 to 1, photoinitiators.

Meanwhile, the coating composition according to the above embodiments may further include an organic solvent. When such an organic solvent is added, the composition is not limited. However, considering the proper viscosity of the coating composition and the film strength of the finally formed film, the amount of the organic solvent is preferably 50 to 100 parts by weight based on 100 parts by weight of the photo- 500 parts by weight, more preferably 100 to 400 parts by weight, and most preferably 150 to 350 parts by weight.

At this time, the type of the organic solvent that can be used is not limited in its constitution, but may be selected from the group consisting of lower alcohols having 1 to 6 carbon atoms, acetates, ketones, cellosolve, dimethylformamide, tetrahydrofuran, propylene glycol monomethyl ether, And xylene may be used alone or in combination of two or more.

The lower alcohol may be methanol, ethanol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, or diacetone alcohol. However, the present invention is not limited to the above examples. The above-mentioned acetates may be methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, or cellosolve acetate. The ketones may be methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, or acetone. However, the present invention is not limited to the above-described examples.

In addition, the antistatic coating composition according to the above embodiments may further include at least one additive selected from the group consisting of a leveling agent, a wetting agent, a defoaming agent, and silica having a volume average particle diameter of 1 to 50 nm. The additive may be added in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the photocurable resin.

The leveling agent serves to uniformize the surface of the coated film using an antistatic coating composition. In addition, since the wetting agent serves to lower the surface energy of the antistatic coating composition, it helps to uniformly coat the antistatic coating composition on the transparent substrate layer.

At this time, the defoaming agent may be added to remove bubbles in the antistatic coating composition. The silica is added as inorganic particles to improve scratch resistance and film strength in the coating film. When silica having a volume average particle diameter of 1 to 50 nm is used, a transparent coating film can be secured, And thus it is preferable.

In addition, the coating composition of the present invention may further include fluorine-based silane, and specifically, it is preferable to use tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriisopropoxysilane , And one kind or two or more kinds of these fluorosilanes may be used, but the present invention is not limited to the above examples.

In another embodiment of the present invention, the present invention provides a low reflection film having antistatic function, which is produced using the antistatic coating composition as described above. In particular, the antistatic film of the present invention includes a transparent substrate layer and an antistatic hard coat layer formed on the transparent substrate layer and formed of the antistatic coating composition as described above.

The method for forming the antistatic hard coat layer using the antistatic coating composition on the transparent substrate layer is not limited in its constitution, but may be applied by a roll coating method, a bar coating method, a spray coating method, a dip coating method, The same wet coating method can be used. The composition of the thus formed antistatic hard coat layer is replaced with the description of the antistatic coating composition described above.

The material of the transparent base material of the transparent base layer is not particularly limited in its constitution, and any material conventionally used in the technical field of the production of the antistatic film may be used. Specifically, it may be at least one member selected from the group consisting of triacetylcellulose (TAC) polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC) and norbornene polymers. However, . Preferably, when an antistatic film is applied to a polarizing plate for a high resolution display, triacetyl cellulose (TAC) can be used. The transparent base layer preferably has a transmittance of at least 85%. Further, the haze value may be 1% or less and the thickness may be 30 to 120 탆, but the present invention is not limited to the above-mentioned haze value and thickness.

Such an antistatic film contains an inorganic particle / organic salt type polymer as described above in an antistatic hard coat layer and is applied to an antistatic film such as a transmittance, a haze, a surface resistance, a scratch, a pencil hardness, It was found that the required physical properties were excellent.

Specifically, the antistatic film according to the above-described embodiment has a transmittance of 90% or more and a haze of 5 or less, a surface resistance of 10 ⁸ to 10 ¹² Ω / m ² , an average reflectance measured according to JIS-K- Is 1.5% or less, the physical properties required for an antistatic film for a display device are excellent.

The antistatic hard coating layer of the present invention may have a thickness of 40 to 200 nm and a refractive index of 1.2 to 1.45.

The antistatic film according to the above embodiment may further include an antiglare layer further stacked on the antistatic hard coat layer and / or the back surface of the transparent base layer. At this time, the thickness of the anti-glare layer may be 50 to 200 nm.

According to another embodiment, the antistatic film may further include an anticorrosion layer laminated on the antistatic hard coat layer and / or on the transparent base layer side of the antistatic film. The thickness of the contaminated layer may be 100 nm or less, or may be 100 nm or less, and the contaminated layer may be formed using a monofunctional and polyfunctional acrylate containing a fluorine group, but the present invention is limited thereto It is not.

On the other hand, the present invention provides a display device comprising the above-mentioned antistatic film according to still another embodiment. Such a display device may be a high-resolution flat panel display, specifically, an LCD, a PDP, an OLED, or a rear-projection TV.

In the present invention, matters other than those described above can be added or subtracted as required, and therefore, the present invention is not particularly limited thereto.

INDUSTRIAL APPLICABILITY As described above, according to the present invention, it is possible to produce a film having a low reflectance and an excellent antistatic property, exhibiting excellent light transmittance and haze characteristics, exhibiting high scratch resistance and low reflectance, And the like.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[Synthesis Examples and Synthesis Comparative Examples]

Synthesis Example 1

An organic liquid hybrid type ionic liquid copolymer containing a functional group to which silica particles are bonded is prepared as shown in Reaction Scheme 1 below.

[Reaction Scheme 1]

Copolymer synthesis of organic salts

A monomer containing quaternary ammonium cations and (meth) acrylate, a dimethylaminoethyl methacrylate quaternary nitrogen compound (Dimethylaminoethyl), and a quaternary ammonium compound are added to a 4-neck reactor equipped with a temperature controller, a condenser and a gas- 40 g of methacrylate quaternary nitrogen compound, DQ-100, manufactured by kyoeisha), 15 g of epoxy acrylate (Glycidyl acrylate) and 20 g of methyl (meth) acrylate were dissolved in a solvent. Methyl ethyl ketone (MEK) and ethanol were used as a solvent, and dissolved at a temperature of 70 ° C and a stirring speed of 100 to 300 rpm under nitrogen purging. After the monomer was dissolved, 0.5 g of an initiator selected from azobisisobutylnitrile (AIBN) and benzoyl peroxide (BPO), 0.3 g of n-dodecylmercaptan as a chain transfer agent was slowly dropped and the mixture was stirred for 16 hours Followed by stirring to prepare a terpolymer having a quaternary ammonium-based functional group.

After 10 g of (meth) acrylic acid was added to the terpolymer thus obtained, 0.1 g of dimethyl benzyl amine was further added, and the mixture was stirred at a temperature of 100 ° C. For 8 hours to synthesize an ionic liquid copolymer (weight average molecular weight: 150,000) containing a first functional group bonded with an organic salt.

Preparation of inorganic particle / organic salt type polymer

20 g of silica particles having no surface treatment (TS-100, average particle size of 20 nm) and 12 g of acrylic isocyanate were dissolved in methyl ethyl ketone (MEK) and ethanol, and then the catalyst dibutyltin 0.2 g of dibutyltin dilaurate (DBTDL) was added, and the mixture was stirred under a nitrogen purging temperature of 100 ° C for 16 hours to prepare silica-substituted silica particles.

Thereafter, 20 g of the acrylic-substituted silica particles thus obtained and 10 g of the copolymer of the organic base salt synthesized as described above were dissolved in propylene glycol monomethyl ether, , And 0.5 g of an initiator selected from azobisisobutylnitrile (AIBN) and benzoyl peroxide (BPO) were mixed and stirred for 16 hours to obtain an organic hybrid type ionic liquid copolymer containing a functional group having silica particles bonded thereto .

Synthesis Example 2

Except that the terpolymer was synthesized by dissolving monomers by using propylene glycol monomethyl ether as a solvent, to obtain an organic / inorganic hybrid (1) having a functional group to which silica particles were bonded in the same manner as in Synthesis Example 1 Type ionic liquid copolymer.

Synthesis Example 3

Except that 10 g of [meth] acrylic acid was added to the terpolymer, except that the terpolymer was synthesized by dissolving monomers by using isopropyl alcohol as a solvent. An organic liquid hybrid type ionic liquid copolymer containing a functional group having silica particles bonded thereto was prepared in the same manner as in Synthesis Example 1. [

Synthesis Example 4

To the terpolymer was added 0.1 g of dimethylaminopyridine instead of 0.1 g of dimethyl benzyl amine to prepare an ionic liquid copolymer (weight average molecular weight: 100,000 ) Was synthesized in the same manner as in Synthesis Example 1, an organic liquid hybrid type ionic liquid copolymer containing a functional group having silica particles bonded thereto was prepared.

Synthesis Example 5

Except that an ionic liquid copolymer (weight average molecular weight: 100,000) comprising acrylic-substituted silica particles and a first functional group bonded with an organic salt was dissolved in methyl ethyl ketone (MEK) and ethanol, An organic liquid hybrid type ionic liquid copolymer containing functional groups having silica particles bonded thereto was prepared in the same manner as in Example 1.

Synthesis Example 6

(Weight average molecular weight: 100,000) containing a first functional group having an organic salt bonded thereto using 20 g of silica sol (MEK-AC, XP1184, Purisol) instead of acrylic-substituted silica particles , An organic liquid hybrid type ionic liquid copolymer containing a functional group to which silica particles were bonded was prepared in the same manner as in Synthesis Example 1. [

Synthesis Example 7

(Weight average molecular weight: 100,000) containing 20 g of silica sol (MEK-AC, XP1184, Purisol) instead of acrylic-substituted silica particles and containing a first functional group to which an organic salt is bonded Was prepared in the same manner as in Synthesis Example 1, except that the reaction was carried out in the same manner as in Synthesis Example 1 except that the content was changed to 12 g, to prepare an organic hybrid type ionic liquid copolymer containing functional groups having silica particles bonded thereto.

Synthesis Comparative Example 1

50 g of a halogen-added silane compound and 15 g of N-methyl-imidazole were reacted at 85 ° C to form an ammonium-based organic hybrid type An ionic liquid compound was prepared.

[Reaction Scheme 2]

[Examples and Comparative Examples]

Example 1: HD 1

An antistatic hard coating liquid composition was prepared using the ionic liquid copolymer of the organic / inorganic hybrid type prepared in Synthesis Example 1, with the composition shown in Table 1 below.

At this time, pentaerythritol triacrylate and dipentaerythritol triacrylate, which are polyfunctional acrylate monomers, were used as photo-curable compounds, and one or more of Irgacure 184, Irgacure 903 and Darocure 1173 as photoinitiators were used. In addition, the interfacial additives are those commonly used in the industry, and the products of DIC are used.

Examples 2 to 7

An antistatic hard coating liquid composition was prepared in the same manner as in Example 1, except that the organic liquid hybrid type ionic liquid copolymer prepared in Synthesis Examples 2 to 7 was used.

Comparative Example 1: HD 2

An antistatic hard coating liquid composition was prepared in the following manner, after preparing an organic-salt-based ionic liquid copolymer free of functional groups to which silica particles were bonded in the following manner.

First, 40 g of a monomer (DQ-100, kyoeisha) containing quaternary ammonium cations and (meth) acrylate was added to a 4-neck reactor equipped with a thermostat, a condenser and a gas introducing device, 15 g of epoxy acrylate (Glycidyl acrylate) and 20 g of methyl (meth) acrylate were dissolved in a solvent. Propylene glycol monomethyl ether was used as a solvent and dissolved at a temperature of 70 ° C and a stirring speed of 100 to 300 rpm under nitrogen purge. After the monomer was dissolved, 0.5 g of an initiator selected from azobisisobutylnitrile (AIBN) and benzoyl peroxide (BPO), 0.3 g of n-dodecylmercaptan as a chain transfer agent was slowly dropped, , To thereby prepare a terpolymer having a quaternary ammonium-based functional group bonded thereto.

After 10 g of (meth) acrylic acid was added to the terpolymer thus obtained, 0.1 g of 4-dimethylaminopyridine was further added, and the mixture was stirred at a temperature of 100 ° C For 8 hours to synthesize an ionic liquid copolymer containing a functional group to which an organic salt is bonded.

As described above, an antistatic hard coating liquid composition was prepared using an organic salt-based ionic liquid copolymer containing no functional group bonded with silica particles.

Comparative Example 2: HD 3

As shown in the following Table 1, an antistatic hard coating liquid composition was prepared in the same manner as in Example 1, except that an n-silica dispersion in which acrylate was surface-treated was used in place of the organic hybrid type ionic liquid copolymer .

Comparative Example 3: HD 4

As shown in the following Table 1, an antistatic hard coating solution was prepared in the same manner as in Example 1, except that a nanosilica dispersion in which methacrylate was surface-treated was used in place of the organic hybrid type ionic liquid copolymer A composition was prepared.

Comparative Example 4: HD 5

As shown in the following Table 1, except that a nanosilica dispersion (nanoparticle size 40 to 50 nm) having a surface treated with methacrylate was used in place of the ionic liquid copolymer of the organic / inorganic hybrid type, An antistatic hard coating liquid composition was prepared.

Comparative Example 5: HD 6

As shown in the following Table 1, in place of the ionic liquid copolymer of the organic / inorganic hybrid type, the nanosilica inorganic particle surface treated with acrylate and the organic salt ionic liquid copolymer synthesized as in Comparative Example 1 were blended antistatic hard coating liquid composition was prepared in the same manner as in Example 1,

Comparative Example 6: HD 7

As shown in the following Table 1, instead of the ionic liquid copolymer of the organic / inorganic hybrid type, the nanosilica inorganic particle surface treated with methacrylate and the organic salt ionic liquid copolymer synthesized as in Comparative Example 1 were blended an antistatic hard coating liquid composition was prepared in the same manner as in Example 1, except that the antistatic hard coating liquid composition was blended.

Comparative Example 7: HD 8

As shown in the following Table 1, in place of the ionic liquid copolymer of the organic hybrid type, methacrylate-treated nanosilica inorganic particles (nanoparticle size 40 to 50 nm) and organic An antistatic hard coating liquid composition was prepared in the same manner as in Example 1, except that the ionic liquid copolymer was blended.

Comparative Example 8: HD 9

As shown in the following Table 1, except that the ionic liquid compound of the organic / inorganic hybrid type of Synthesis Comparative Example 1 was used in place of the ionic liquid copolymer of the organic / inorganic hybrid type, To prepare a hard hard coating liquid composition.

When an ionic liquid compound other than the organic / inorganic hybrid type ionic liquid copolymer is used, the organic / inorganic hybrid copolymer is dissolved in the organic solvent. On the other hand, in order to use the water-dispersed silica sol, It is necessary to further include a step of preparing methacrylate so as to allow water dispersion, so that the process efficiency is remarkably lowered.

The compositions of the antistatic hard coating solution compositions of Examples 1 to 7 and Comparative Examples 1 to 8 as described above are shown in Table 1 below (unit: wt%).

Photocurable compound Photoinitiator surface
Treated nano
Silica dispersion Nano
Silica weapon
particle Organic salt copolymer Abs
Hybrid copolymer Abs
Hybrid compound Interface
Activator Example 1 (HD1) 85 7 - - - 8 - 0.1 Example 2 85 7 - - - 8 - 0.1 Example 3 85 7 - - - 8 - 0.1 Example 4 85 7 - - - 8 - 0.1 Example 5 85 7 - - - 8 - 0.1 Example 6 85 7 - - - 8 - 0.1 Example 7 85 7 - - - 8 - 0.1 Comparative Example 1
(HD2) 85 7 - - 8 - - 0.1 Comparative Example 2
(HD3) 85 7 8 - - - - 0.1 Comparative Example 3
(HD4) 85 7 8 - - - - 0.1 Comparative Example 4
(HD5) 85 7 8 - - - - 0.1 Comparative Example 5
(HD6) 85 7 - 4 4 - - 0.1 Comparative Example 6
(HD7) 85 7 - 4 4 - - 0.1 Comparative Example 7
(HD8) 85 7 - 4 4 - - 0.1 Comparative Example 8
(HD9) 85 7 - - - - 8 0.1

[Production Example and Comparative Production Example]

Antistatic coating films of Production Example 1 and Comparative Production Examples 1 to 7 were prepared using the hard coating solutions of Example 1 and Comparative Examples 1 to 7, respectively, in the following manner.

First, the hard coating composition was coated on a triacetellated cellulose film with a # 10 mayer bar, dried at 90 ° C for 2 minutes, cured (5 μm) at a UV energy of 150 mJ / cm ^{2 at} a rate of 8 m / min, To prepare a coating film.

Further, 15 g of pentaerythritol triacrylate as a polyfunctional acrylate monomer, 10 g of dipentaerythritol heptaacrylate (DPHA), 5 g of IGACURE 184 as a photopolymerization initiator, and 10 g of methyl isobutyl ketone (MIBK) dispersion of hollow silica particles 200 g of polyvinyl alcohol (200 g) and a leveling agent 5 g of a polyether siloxane copolymer Tego 450 were diluted with a MIBK / 2-BuOH mixed solvent (weight ratio 1/1) to obtain a low reflection coating with a solid content concentration of 2.5 wt% A composition was prepared.

The low reflection coating composition thus prepared was coated on the hard coating film with a # 4 mayer bar, dried at 60 ° C for 1 minute, and cured at a UV energy of 150 mJ / cm ² under a nitrogen purge at a rate of 5 m / min (100 nm).

The coating films of Production Example 1 and Comparative Production Examples 1 to 7 prepared as described above were subjected to physical property evaluation in the following manner, and the measurement results thereof are shown in Table 2 below.

1. Reflectance

The average reflectance was calculated by measuring the visible light region with Solidspec 3700 (SHIMADZU).

2. My Scratchy Castle

# 0000 A load was applied to a steel wool, and the scratch resistance was measured by reciprocating 10 times at a speed of 24 rpm.

○: 1 or less scratches less than 1 cm visible

△: Less than 5 scratches visible

X: Over 5 scratches visible

3. Surface resistance

Hiresta IP MCP-HT260 (MTISUBISH CHEMICAL).

4. Humidity Resistance

A film coated on an oven at a temperature of 60 DEG C and a humidity of 90% was placed for 240 hours, and then the presence or absence of a change in the coating film was measured.

Manufacturing example
One compare
Manufacturing example
One compare
Manufacturing example
2 compare
Manufacturing example
3 compare
Manufacturing example
4 compare
Manufacturing example
5 compare
Manufacturing example
6 compare
Manufacturing example
7 compare
Manufacturing example
8 Hard coating solution HD1 HD2 HD3 HD4 HD5 HD6 HD7 HD8 HD9 Average reflectance (%) 1.2 1.2 > 2 > 2 > 2 > 2 > 2 > 2 > 2 Surface resistance (Ω / m ² ) 10 ¹⁰ 10 ^10-11 over over over 10 ¹² 10 ¹² 10 ¹² over Transmittance (%) 95.7 95.7 94.5 94.6 94.7 94.7 94.8 94.8 94.3 Hayes 0.2 0.3 4.5 4.5 2.5 6.5 8.0 8.0 > 10 Scratch resistance 200g ○ - ○ ○ ○ - - - - 150g ○ - - - - - - - - 100g - △ - - - △ △ △ - Wet heat test
(240H) ○ △ ⁺ (120H) X X X ? (60H) ? (60H) ? (60H) X

As shown in the above Table 2, the antistatic film of Preparation Example 1 using the hard coat layer coating composition comprising the organic / inorganic hybrid type ionic liquid copolymer according to the present invention had excellent antiscratching performance as well as high scratch resistance .

In particular, the antistatic coating film of Preparation Example 1 exhibits excellent scratch resistance of less than 1 scratch under 1 cm, which is visually confirmed even under a load of 150 g and 200 g, and has excellent antistatic performance of 10 ¹⁰ Ω / m < ² >, and has excellent properties that can simultaneously ensure a low reflectance of 1.5% or less, a low haze of 0.3 or less, and a high transmittance of 95% or more. In addition, the antistatic coating film of Production Example 1 shows that the organic hybrid copolymer showing antistatic function does not show whitening phenomenon at all at a temperature of 60 캜 and a humidity of 90% even in an anti-wet heat test.

On the other hand, it can be seen that Comparative Production Examples 1 to 7 can not be used as an antistatic low reflection coating film. Particularly, Comparative Preparation Example 1 in which an organic-based salt copolymer is applied exhibits an antistatic function, but is vulnerable to humidity, resulting in bleeding out of the organic-based salt copolymer. Further, in the case of the surface-treated nanosilica dispersions in Comparative Production Examples 2 to 4, the haze of the silica dispersion was high, and the optical characteristics including the transmittance were remarkably decreased. On the other hand, in the case of Comparative Examples 5 to 7 in which inorganic nanoparticles of silica and organic salt copolymer were blended, crosslinking with the photo-curable compound did not occur, and the reflectance and haze of the optical characteristics were remarkably lowered.

Claims (14)

Wherein the ionic liquid copolymer comprises a first functional group to which an organic salt is bonded and a second functional group to which silica particles are bonded, And the first functional group is prepared from a quaternary ammonium-based conductive monomer. delete The method according to claim 1,
Wherein the ionic liquid copolymer has a weight average molecular weight of 50,000 to 200,000. In the first aspect,
The first functional group may be at least one selected from the group consisting of a pyridinium cation, a pyridinium cation, a pyrrolidinium cation, a pyrroline skeleton, a pyrrole skeleton, an imidazolium cation, a tetrahydropyrimidinium cation, a dihydropyrimidinium cation , A cation selected from the group consisting of a pyrazolium cation, a pyrazolinium cation, a tetraalkylammonium cation, a trialkylsulfonium cation, and a tetraalkylphosphonium cation and a cation selected from the group consisting of Cl ^- , Br ^- , I ^- , AlCl ₄ ^{- _{Al 2 Cl 7 -, BF 4}} -, PF 6 -, ClO 4 -, NO 3 -, CH 3 COO -, CF 3 COO -, CH 3 SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) _{^{2 n -, (CF 3 SO}} 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, (HF) n -, (CN) 2 n -, C 4 F 9 SO 3 - , One or two anions selected from the group consisting of (C ₂ F ₅ SO ₂ ) ₂ N ^- , C ₃ F ₇ COO ^- , (CF ₃ SO ₂ ) (CF ₃ CO) N ^- ≪ / RTI > by weight of the composition. The method according to claim 1,
Wherein the silica particles comprise a (meth) acrylic group on the surface. The method according to claim 1,
Wherein the ionic liquid copolymer is prepared by surface-initiated polymerization. delete The method according to claim 1,
An antistatic coating composition further comprising a photocurable resin and a photoinitiator. 9. The method of claim 8,
Wherein the photo-curing resin comprises a reactive acrylate oligomer group consisting of a urethane acrylate oligomer, an epoxy acrylate oligomer, a polyester acrylate, and a polyether acrylate; And
Acrylate, dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylene propyl triacrylate, propoxylated glycerol triacrylate, trimethylpropane ethoxy triacrylate At least one member selected from the group consisting of polyfunctional acrylate monomers consisting of 1,6-hexanediol diacrylate, propoxylated glycerol triacrylate, tripropylene glycol diacrylate, and ethylene glycol diacrylate, ≪ / RTI > 9. The method of claim 8,
Wherein the photoinitiator is selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, hydroxydimethylacetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin butyl ether Selected antistatic coating composition. 9. The method of claim 8,
With respect to 100 parts by weight of the total composition,
35 to 40 parts by weight of a photocurable resin,
1 to 20 parts by weight of an organic-inorganic hybrid type ionic liquid copolymer containing a functional group to which silica particles are bound, and
0.01 to 1 part by weight of a photoinitiator
≪ / RTI > A transparent base layer; And
An antistatic film laminated on said transparent substrate layer and comprising an antistatic hard coat layer formed from the coating composition according to any one of claims 1, 3 to 6 or 8 to 11. 13. The method of claim 12,
Wherein the antistatic film has a transmittance of 90% or more and a haze of 5 or less, a surface resistance of 10 ⁸ to 10 ¹² Ω / m ² , and an average reflectance of 1.5% or less as measured in accordance with JIS-K-7105. A display device comprising an antistatic film according to claim 12.