KR100892920B1 - Composition for antistatic antiglare hard coat, and a film prepared therefrom - Google Patents

Abstract

The present invention relates to an antistatic anti-glare hard coating composition and a film prepared therefrom, and more particularly, comprising silica hollow microspheres having an average particle diameter of 10 to 1000 nm, an antistatic agent, an ultraviolet curable resin, a photoinitiator and a solvent. It relates to an antistatic anti-glare hard coating composition and a film prepared therefrom.

Anti-glare, Anti-Static, Hard Coating, Silica Hollow Microspheres, UV Curing Resin, Diffuse Reflective, Scratch Resistance

Description

Antistatic anti-glare hard coating composition and film produced therefrom {COMPOSITION FOR ANTISTATIC ANTIGLARE HARD COAT, AND A FILM PREPARED THEREFROM}

Figure 1 shows a transmission electron micrograph after sintering silica hollow microspheres of the present invention.

Figure 2 shows a schematic diagram of the antistatic anti-glare hard coating film of the present invention.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic / anti-glare hard coating composition for preventing dust contamination and glare of a plasma display (PDP), a liquid crystal display (LCD), and a film prepared therefrom, in particular using silica hollow microspheres. In addition to excellent anti-glare function and scratch resistance, relates to a low-cost, high-efficiency anti-static anti-glare hard coating agent that also provides an antistatic function to one coating agent.

Recently, various displays have undergone antiglare treatment to prevent glare from reflected light through scattering of external light and antistatic treatment to prevent contamination by external environment in order to secure the clarity of image quality.

Such antistatic / anti-glare treatment methods include a method of separately preparing an antistatic layer and an antiglare layer, and a method of forming irregularities on the surface of a base film in a step before forming an antistatic layer.

However, the method of forming each layer is not only expensive in the manufacturing process, but must also consider the adhesiveness, shrinkage and refractive index of the resin of each layer. In addition, when a special roll is used to form the unevenness, relatively expensive equipment is required, and there is a problem of aggregation of the antistatic material on the uneven portion.

Korean Patent Laid-Open Publication Nos. 2006-0051879 and 2006-0135787 describe display coatings that provide antistatic, scratch, and anti-glare functions by forming a coating film in the order of substrate / antistatic layer / hard coating layer / low refractive layer. have.

However, this technology is composed of multiple layers, so that the antistatic layer located at the lower layer requires an excessive amount of antistatic material to obtain an antistatic effect by a relatively thick hard coating layer, and thus the light transmittance and surface strength are reduced, and antistatic Metal oxides, which are used as materials, generally have a higher refractive index than binder resins, and an antistatic layer using metal oxides has a refractive index higher than that of a base film or a hard coating layer. have.

Therefore, the present invention includes a silica hollow microspheres and an antistatic agent at the same time in a specific content, which can simultaneously impart an antistatic effect that can achieve excellent scratch resistance and anti-glare and prevent the adsorption of dust as a source of external environmental pollution. An object of the present invention to provide an antistatic anti-glare hard coating composition.

Another object of the present invention is to provide an antistatic anti-glare hard coating film prepared from the coating composition.

The present invention to achieve the above technical problem,

Silica hollow microspheres with an average particle diameter of 10 to 1000 nm;

Antistatic agent;

Ultraviolet curable resins;

Photoinitiators; And

menstruum

It provides a composition for antistatic anti-glare hard coating comprising a.

The present invention also provides a hard coat film comprising an antistatic anti-glare hard coating layer prepared from the coating composition.

Hereinafter, the present invention will be described in detail.

In the present invention, an antistatic anti-glare hard coating agent can be formed by using silica hollow microspheres to form a single layer film having high light transmittance, low haze, and excellent scratch resistance and having an antistatic function.

The antistatic anti-glare hard coating composition of the present invention includes silica hollow microspheres, an antistatic agent, an ultraviolet curable resin, a photoinitiator, and a solvent.

The silica hollow microspheres contribute to the function of scattering external light and to improve scratch resistance against external stimuli. In particular, the content and size of the hollow microspheres are important in the antistatic anti-glare hard coating composition of the present invention. In addition, the shape of the hollow silica microspheres is not particularly limited, but a spherical shape is more preferable.

1 is a transmission electron micrograph (TEM) after silica hollow microsphere firing. As shown in Figure 1, the hollow silica microspheres used in the antistatic anti-glare hard coating composition of the present invention are hollow spherical particles, the average particle diameter is 10 to 1000 nm. In view of dispersibility and anti-glare properties, particles having a uniform distribution are preferable, more preferably, the average particle diameter is 50 to 700 nm, and more preferably the average particle diameter is 100 to 500 nm. When the average hollow particle diameter of the silica hollow microspheres of the present invention is less than 10 nm, light scattering scattering does not occur well, and when it exceeds 1000 nm, transparency and haze may occur due to whitening.

The silica hollow microspheres used in the antistatic anti-glare hard coating composition of the present invention have an outer wall thickness of the hollow spheres of 3 to 200 nm, preferably 10 to 180 nm, more preferably 30 to 150 nm, and more preferably. Preferably 50 to 100 nm. If the outer wall thickness of the hollow spheres of the silica hollow microspheres is less than 3 nm, the strength of the silica hollow microspheres is weak and the particles are broken, and if the thickness exceeds 200 nm, the dispersibility of the particles decreases.

The silica hollow microspheres are preferably included in 0.1 to 15% by weight of the solid content of the antistatic anti-glare hard coating composition of the present invention, more preferably contained in 3 to 10% by weight. The solid content means the remaining components except for the solvent among the components included in the antiglare coating agent of the present invention. When the content of the hollow silica microspheres is less than 0.1% by weight of the solid content, the effect of light scattering and scattering by the added silica hollow microspheres particles is insignificant, and the gloss may be high, which may affect the anti-glare property, and exceeds 15 wt%. In this case, the haze is severe and the sharpness of the screen may be degraded.

The silica hollow microspheres may be used commercially available, preferably those synthesized by using a sacrificial core or emulsion method.

In addition, the antistatic agent included in the antistatic anti-glare hard coating composition of the present invention, indium tin oxide (ITO), antimony doped tin oxide (ATO), antimony doped zinc oxide (AZO), gold, silver, nickel, etc. It may be selected from the group consisting of a metal powder and a metal oxide of, and may be used to disperse or dissolve in an organic solvent such as alcohol or ester. The antistatic agent may be included in an amount of 1 to 30% by weight, preferably 1 to 15% by weight of the solid content of the antistatic anti-glare hard coating composition of the present invention.

If the antistatic agent content is less than 1% by weight of solids in the total composition, the surface resistance value is increased to exhibit an antistatic effect. If the antistatic agent content is more than 30% by weight, haze and light transmittance are significantly lowered, thereby increasing the sharpness of the screen. This can be degraded.

The ultraviolet curable resin included in the antistatic anti-glare hard coating composition of the present invention is preferably 55 to 98% by weight of the solids, and more preferably 76 to 91% by weight of the total coating composition.

It is preferable that the light transmittance of the said ultraviolet curable resin is 80% or more, and it is more preferable that it is 90% or more. The compound which has 2 or more acrylic functional groups in a molecule | numerator from a viewpoint of the scratch resistance of a film by the said ultraviolet curable resin is preferable. As an example of the said ultraviolet curable resin, the ultraviolet curable resin which has two or more functional groups is trimethylol propane triacrylate, aliphatic polyurethane diacrylate, hexadiol diacrylate, tetraethylene glycol diacrylate, dipentaerythritol Hexaacrylate, pentaerythritol triacrylate, pentaerythritol tetrakis (3-mechemtopropionate) and the like. More preferably, there are three or more acrylate functional groups. The compound which has 2 or more acrylic functional groups in a molecule | numerator can be used individually, or 2 or more types can be mixed and used for it.

In addition, the photoinitiator included in the antistatic anti-glare hard coating composition of the present invention is preferably included in 0.1 to 5% by weight based on the total weight. When the content of the photoinitiator is less than 0.1% by weight, since the photoinitiator cannot form radicals, hardening of the antistatic anti-glare hard coating agent is unlikely to occur, and when it exceeds 5% by weight, the radical reaction of the photoinitiator is promoted to store the coating agent. There is a fear that the stability is lowered.

As the photoinitiator, 2-hydroxyl-2-methyl-1-phenyl propanone, n-butylamine, triethylamine, 2-hydroxyl-1- (4- (2-hydroxyethoxy) phenyl) -2 -Methylpropanone, 1-hydroxycyclohexyl phenyl methol, 2,2'-dimethoxy-1,2-diphenylethanone, diphenylphosphoryl mesityl methanone, phenylphosphorylbis (methylmethanone) ), (s) -2-benzyl-2- (dimethylamino) -1- (4-merpolynophenyl) butanone, 2-methyl-2- (4- (methylthio) phenyl) -2-merpoly There is one or more selected from the group consisting of nopropanone, but is not limited thereto, and known photoinitiators may be used in addition to the above examples.

The solvent included in the antistatic anti-glare hard coating composition of the present invention is preferably at least one selected from the group consisting of alcohols, ketones, esters, ethers and amides, wherein the alcohols are isopropanol and methanol. It is more preferably at least one selected from the group consisting of ethanol, propanol, butanol and ethylene glycol, the ketones are selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and methylcyclohexanone More preferably, the ester is at least one member selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, benzyl acetate, ethyl formate, propyl formate, butyl formate, and ethyl lactate, and the ether Propylene glycol monomethyl ether, dioxane, tetrahydrofuran, ethylene It is preferably at least one selected from the group consisting of recall dimethyl ether, propylene glycol and dimethyl ether, and the amides are at least one selected from the group consisting of dimethylformamide, diketylacetamide and n-methylpyrrolidone. More preferred.

The solvent may be used alone, may be used by mixing a plurality of solvents, preferably a plurality of solvents of alcohols or ethers may be mixed.

The solvent is added to control the coating property, it may be added in the remaining amount according to the content of the other ingredients.

The antistatic anti-glare hard coating composition of the present invention may further include one or more additives selected from the group consisting of a dispersing agent and a smoothing agent, if necessary, and the content of the additive is the total anti-glare coating weight of each type. It is preferably from 0.1 to 5% by weight relative to.

The dispersant includes Anti-Terra-U (unsaturated polyamine) and Disperbyk-103 of BYK chemie Co., and the leveling agent is Byk-370 (polyester-modified hydroxy functional polydimethylsiloxane solution) of BYK chemie Co. And Byk-371 (polyester-modified acrylic functional polydimethylsiloxane solution) and the like, but is not limited thereto, and other dispersants and levelers may be included in the present invention.

Especially. Preferably, the composition for antistatic antiglare hard coating of the present invention comprises silica hollow microspheres having an average particle diameter of 10 to 1000 nm, an antistatic agent; UV curable resin, 0.1 to 5% by weight photoinitiator, 0.1 to 5% by weight dispersant, 0.1 to 5% by weight leveling agent, and 50 to 95% by weight solvent, wherein the silica hollow microspheres 1 to 15% by weight of the total solids %, Antistatic agent may comprise 1 to 30% by weight of the total solids, and 55 to 98% by weight of the total solids of the ultraviolet curable resin.

The antistatic antiglare hard coat film of the present invention prepared from the composition for hard coating comprises an antistatic antiglare hard coat layer comprising silica hollow microspheres, an antistatic agent, and an ultraviolet curable resin having an average particle diameter of 10 to 1000 nm. The hard coating layer is characterized in that it is coated on one side or both sides of the transparent substrate.

FIG. 2 is a cross-sectional schematic diagram of an antistatic antiglare hard coating film having an antistatic antiglare hard coating film including silica hollow microspheres, antistatic agent particles, and an ultraviolet curable resin on one surface of a transparent substrate.

The antistatic anti-glare hard coating film may have a light transmittance of 90 to 99%, a haze of 2 to 50, a pencil hardness of 3H or more, and a surface resistance of 10 ⁸ to 10 ¹¹ Ω / cm ² , Preferably, the light transmittance may be 92 to 99%, haze of 5 to 30%, pencil hardness of 4H or more, and surface resistance of 10 ⁶ to 10 ¹⁰ μs / cm ² .

In addition, the antistatic anti-glare hard coating film of the present invention may be used as a transparent substrate, a transparent film or glass to which the composition for hard coating of the present invention can be applied, polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polyethylene naphthalate (PEN), triacetyl cellulose (TAC), polycarbonate (PC), polyimide (PI), polyethylene (PE), polypropylene (PP), polyethersulfone (PES), polyvinyl It is preferable that it is a film containing at least 1 sort (s) of resin chosen from the group which consists of alcohol (PVA), polyvinyl chloride (PVC), cellophane, and aromatic polyamide, or glass base materials, such as quartz glass or soda glass, It is more preferable that it is a film containing at least one resin selected from the group consisting of terephthalate (PET) and polymethyl methacrylate (PMMA) resin.

In particular, the cured film of the hard coating film of the present invention, that is, the hard coating layer is composed of a single layer can be given simultaneously antistatic and anti-glare effect. Moreover, it is preferable that the cured film thickness of the said film is 0.5-5 micrometers.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Example  One

(Silica Hollow Microsphere Dispersion Preparation)

33.3 wt% of solid content in dispersion medium of dipentaerythritol hexaacrylate, an ultraviolet curing resin monomer, 66.7 wt% of solid content of trimethylpropane triacrylate in dispersion medium, 3 wt% of BYK-Dispersant (by BYK Gardner GMBH) as a dispersant, A dispersion medium was prepared by adding 11% by weight of a solvent alcohol and 11% by weight of ether.

Silica hollow microsphere dispersions were prepared by adding silica hollow microspheres with an average particle diameter of 500 nm as solids content of 12.9 wt% relative to the dispersion.

(Anti-glare Hard Coating Agent)

Dipentaerythritol hexaacrylate, an ultraviolet curing resin monomer, has a solid content of 72 wt% in the anti-glare heart coating agent, a trimethylpropane triacrylate in the anti-glare heart content 23 wt% in the heart coating agent, and anti-glare silica hollow microspheres. 5% by weight of solid content in the hard coating agent, and 1% by weight of a leveling agent, 44% by weight of alcohol as a solvent, and 43% by weight of ether were placed in a light-permeable container and stirred, followed by 2,2-dimethoxy as a photoinitiator. Anti-glare hard coat was prepared by adding 1% by weight of -1,2-diphenyl ethanone (2,2-dimethoxy-1,2-diphenylethanone).

(Prevention of anti-glare hard coating agent)

ITO powder is added to the anti-glare hard coating agent in an amount of 4% by weight of solids as compared to the anti-static anti-glare hard coating agent to prepare a coating solution by stirring the two solutions to be uniformly mixed.

(UV cured film production)

The antistatic anti-glare hard coating agent was coated on a transparent acrylic plate by bar coating, dried at 50 ° C., and cured by irradiating ultraviolet light in air using a high pressure mercury lamp (500 mJ / cm ² ).

Example  2

Antistatic anti-glare hard coating agent was prepared in the same manner as in Example 1, except that the coating solution was prepared by adding ITO powder in an amount of 8% by weight compared to the anti-static anti-glare hard coating agent and mixing the two solutions uniformly. And a UV cured film.

Example  3

The antistatic antiglare hard coating agent was prepared in the same manner as in Example 1, except that ITO powder was added in an amount of 11% by weight compared to the antistatic antiglare hard coating agent, and the coating solution was prepared by stirring the mixture so that the two solutions were uniformly mixed. And UV cured coatings were prepared.

Example  4

The antistatic antiglare hard coating agent was prepared in the same manner as in Example 1, except that ITO powder was added in an amount of 20% by weight to the antistatic antiglare hard coating agent, and the coating solution was prepared by stirring the mixture so that the two solutions were uniformly mixed. And UV cured coatings were prepared.

Example  5

An antistatic anti-glare hard coating agent and a UV cured film were prepared in the same manner as in Example 1, except that the antistatic material was ATO.

Example  6

An antistatic anti-glare hard coating agent and a UV cured film were prepared in the same manner as in Example 2, except that the antistatic material was ATO.

Example  7

An antistatic anti-glare hard coating agent and a UV cured coating film were prepared in the same manner as in Example 3 except that the antistatic material was ATO.

Example  8

An antistatic anti-glare hard coating agent and a UV cured coating film were prepared in the same manner as in Example 1, except that the silica hollow microspheres were mixed in a solid content of 0.5 wt% in the anti-glare hard coating agent.

Example  9

An antistatic anti-glare hard coating agent and a UV cured coating film were prepared in the same manner as in Example 1 except that the silica hollow microspheres were mixed in a solid content of 10 wt% in the anti-glare hard coating agent.

Comparative example  One

It was prepared in the same manner as in Example 1 except that no antistatic agent was added.

Comparative example  2

It was prepared in the same manner as in Example 1 except for replacing the silica hollow microspheres with ordinary silica particles.

Comparative example  3

A silica hollow microspheres were prepared in the same manner as in Example 1 except that the hollow microspheres were not added.

Comparative example  4

An antistatic anti-glare hard coating agent and a UV cured coating film were prepared in the same manner as in Example 1 except that the coating material was prepared by mixing 20 wt% of the solid content in the anti-glare hard coating agent.

Comparative example  5

An antistatic anti-glare hard coating agent and a UV cured coating film were prepared in the same manner as in Comparative Example 4 except that ITO powder was prepared by mixing 20% by weight of solid content with respect to the antistatic anti-glare hard coating agent.

Comparative example  6

An antistatic antiglare hard coating agent and a UV cured coating film were prepared in the same manner as in Example 8 except that the solid content of ITO powder was added in an amount of 1% by weight compared to the antistatic antiglare hard coating agent.

Physical properties of the antistatic anti-glare hard coating film prepared according to Examples 1 to 9 and Comparative Examples 1 to 6 were evaluated according to the following method, and the results are summarized in Table 1 below.

(1) light transmittance and haze

Total light transmittance and total haze were measured using a spectrophotometer (NIPPON DENSHOKU, NDH300A, Japan).

(2) glossiness

Glossiness was measured at 60 ° / 60 ° using a gloss meter (BYK Gardner, Germany).

(3) surface resistance

It measured using the parallel electrode connected to the multimeter (surface resistor ST-3).

(4) pencil hardness

Pencil hardness was measured under a 500g load using a pencil hardness tester (Yoshimitsu, Japan), which is an ASTM D3502 measuring method.

division Silica Content / Solid Content (wt%) Antistatic Agent Content / Solid Content (wt%) Light transmittance (%) Haze (%) Glossiness Pencil Hardness (H) Surface Resistance (Ω / cm ² ) Example 1 5 ITO 4 96.7 6.8 112 4 10 ¹⁰ Example 2 5 ITO 8 97.1 11.3 89 4 10 ⁹ Example 3 5 ITO 11 96.8 13.2 78 4 10 ⁸ Example 4 5 ITO 20 93.2 21.1 45 4 10 ⁸ Example 5 5 ATO 4 97.4 8.7 102 4 10 ¹¹ Example 6 5 ATO 8 96.9 15.7 72 4 10 ¹⁰ Example 7 5 ATO 11 97.2 19.3 61 4 10 ⁹ Example 8 0.5 ITO 4 98.9 4.5 125 4 10 ¹⁰ Example 9 10 ITO 4 95.3 24.5 83 4 10 ¹⁰ Comparative Example 1 5 - 97.3 6.1 118 4 10 ¹² Comparative Example 2 5 ITO 4 95.4 1.4 130 4 10 ¹² Comparative Example 3 - ITO 4 97.1 1.8 140 3 10 ¹² Comparative Example 4 20 ITO 4 87.9 48.6 42 5 10 ¹² Comparative Example 5 20 ITO 20 88.8 61.3 16 5 10 ¹¹ Comparative Example 6 0.5 ITO 1 98.2 1.2 163 3 10 ¹²

As shown in Table 1, the antiglare film of Examples 1 to 9 had excellent light transmittance of 96.7 to 99.4%, haze 4.5 to 24.5, pencil hardness of 4H, and surface resistance of 10 ⁸ to 10 ¹¹ Pa / cm ^2. It can be seen that the anti-glare function and scratch resistance is excellent and at the same time provides excellent antistatic performance.

In addition, in the antiglare films prepared according to Comparative Examples 1 to 6, the transmittance and glossiness were observed to be low, and the haze was higher than that of Examples 1 to 9 of the present invention containing silica microhollow spheres having an equivalent particle size in equivalent amounts. In addition, it can be seen that the surface resistance is large and the pencil hardness is low.

As described above, the antistatic anti-glare hard coating composition of the present invention and the film prepared therefrom have excellent surface of 10 ⁸ to 10 ¹¹ Ω / cm ² by utilizing silica hollow microspheres and antistatic agent having excellent light scattering effect. It has a resistance and provides excellent physical properties as a display coating agent having excellent light transmittance, glossiness, and pencil hardness.

In particular, the antistatic anti-glare hard coating composition of the present invention can maximize the scattering effect of light because the hollow microspheres particles can be highly dispersed during drying after coating, including silica hollow microspheres, according to the present invention The film produced from the hard coating agent has the advantage of shortening the manufacturing process and cost reduction effect by simultaneously giving excellent antistatic, anti-glare function, scratch resistance and the like.

The antistatic anti-glare hard coating composition of the present invention can be widely used in LCD, PDP and OLED.

Claims (10)

Silica hollow microspheres with an average particle diameter of 10 to 1000 nm; Antistatic agent; Ultraviolet curable resins; Photoinitiators; And menstruum Including; The silica hollow microspheres are antistatic anti-glare hard coating composition comprising 0.1 to 15% by weight relative to the total amount of solids consisting of the remaining components except for the solvent in the total composition. delete The method of claim 1, The antistatic agent is included in 1 to 30% by weight based on the total amount of solids consisting of the remaining components except for the solvent in the total composition, The UV curable resin is included in the total composition of 55 to 98% by weight based on the total amount of solids consisting of the remaining components except for the solvent, The photoinitiator is an antistatic anti-glare hard coating composition comprising 0.1 to 5% by weight based on the total amount of the solvent in the total composition. The antistatic agent according to claim 1, wherein the antistatic agent is composed of a metal powder or a metal oxide of indium tin oxide (ITO), antimony doped tin oxide (ATO), antimony doped zinc oxide (AZO), and gold, silver, or nickel. Antistatic anti-glare hard coating composition is selected from one or more from the group. The composition for antistatic antiglare hard coating according to claim 1, further comprising at least one additive selected from the group consisting of a dispersing agent and a leveling agent. The method of claim 5, wherein Silica hollow microspheres with an average particle diameter of 10 to 1000 nm; Antistatic agent; Ultraviolet curable resins; Photoinitiators; Dispersants; Leveling agent; And menstruum Including; The silica hollow microspheres is 0.1 to 15% by weight relative to the total amount of solids consisting of the remaining components excluding the solvent in the total composition, the antistatic agent is 1 to 30% by weight relative to the total amount of solids consisting of the remaining components except the solvent in the composition, and UV-curable Resin is included in the composition of 55 to 98% by weight based on the total amount of solids consisting of the remaining components excluding the solvent, The photoinitiator is 0.1 to 5% by weight relative to the total amount of the solvent in the total composition, the dispersing agent is 0.1 to 5% by weight relative to the total amount of the solvent in the total composition, the leveling agent is 0.1 to 5% relative to the total amount of the solvent in the total composition Wt%, and the solvent is 50 to 95% by weight relative to the total amount including the solvent in the total composition. An antistatic antiglare hard coating layer prepared from the composition for antistatic antiglare hard coating according to claim 1, wherein the light transmittance is 90 to 99%, and the haze is 4.5. To 50, a pencil hardness of 3H or more, and an antistatic anti-glare hard coating film having a surface resistance of 10 ⁸ to 10 ¹¹ dl / cm ² . The antistatic anti-glare hard coating film according to claim 7, wherein the cured film of the film is a single layer. The antistatic anti-glare hard coating film of claim 7, wherein the cured film thickness of the film is 0.5 to 5 µm. According to claim 1, wherein the outer wall thickness of the silica hollow microspheres of 3 to 200 nm antistatic anti-glare hard coating composition.

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