KR101111410B1 - hard coating liquid and film - Google Patents

Abstract

The present invention provides a hard coating solution including a zinc oxide nanorod doped with aluminum in order to include an antistatic function in the hard coating layer without forming an antistatic layer and a hard coating film using the same.

Antistatic, Aluminum Doped Zinc Oxide, Nano Rod, Hard Coating Film

Description

Hard coating liquid and film

The present invention relates to a hard coating liquid and a hard coating film having an antistatic function.

Display products such as LCD, PDP, Touch Panel, OLED, etc. use a hard coating film having a hard coating layer having excellent anti-scratch on a base film as a surface protection material.

However, since the hard coating film does not contain a conventional antistatic agent has a surface resistance of 10 ¹³ Ω / sq or more, there is a disadvantage that a pollution source such as surrounding dust is easily attached to the surface.

In order to impart antistatic property to the hard coating layer, an antistatic agent may be added or an antistatic layer may be formed. However, in the method of applying an antistatic agent such as a surfactant to the resin surface, the antistatic property is remarkably lowered after a long period of time, and thus the practicality may be insufficient as the antistatic agent having a persistence. In addition, antistatic agents such as surfactants are temperature-dependent, and the antistatic effect may be lowered even at low temperatures.

In addition, a method of incorporating carbon black, carbon nanotubes, or the like into a resin and coating may also be proposed. According to this method, however, a transparent coating layer may not be obtained or the selection of the color of the molded article may be limited.

In addition, the method of depositing a metal compound is excellent in antistatic properties and can be used in recent years for a conductive film.

Recently, as conductive polymers such as polyaniline, polypyrrole or polythiophene, which are dissolved in water and an organic solvent, have been developed, they may impart conductivity to an antistatic polyester film or other polymer surface.

Among them, a general method is to prepare doped conductive polymers and coat them on various polymer surfaces including polyester in a suitable solvent. When a coating liquid containing such an electrically conductive polymer is applied to a plastic substrate, it may not satisfy the performance of adhesion, transparency, water resistance, solvent resistance and electrical conductivity to the substrate at the same time. The method of applying an alkali metal Eshs aluminum salt with an antistatic function and an imidazoline-based surfactant may be limited in application of the technology because the surface resistance of the antistatic coating layer varies with humidity.

The present invention can provide a hard coating film having a high permeability and high antistatic property without forming an antistatic layer on the hard coating layer in order to solve the above problems and a hard coating solution for producing the same.

In one aspect, the present invention, it is possible to provide an antistatic hard coating liquid comprising a zinc oxide nanorod doped with aluminum.

In another aspect, the present invention, the base film; And a coating layer formed of an antistatic hard coating solution on one surface of the base film.

In another aspect, the present invention, the base film; A coating layer formed of an antistatic hard coating solution including zinc oxide nanorods doped with aluminum on both sides of the base film; And it can provide an antistatic hard coating film comprising a; protective film attached to both sides of the base film.

The present invention has the effect of having high permeability and high antistatic property without separately forming an antistatic layer on the hard coating layer.

Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings. In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected or connected to that other component, but between components It will be understood that may be "connected", "coupled" or "connected".

Various methods are possible to implement a hard coating solution and a hard coating film having an antistatic function according to embodiments of the present invention.

The antistatic hard coating solution according to the present invention may include zinc oxide nanorods doped with aluminum. Specifically, the antistatic hard coating solution according to the present invention may include a heat or ultraviolet curable resin, a curing initiator, and a solvent together with the zinc oxide nanorods doped with aluminum. Specifically, the antistatic hard coating solution according to the present invention is doped with (A) 100 parts by weight of heat or ultraviolet curable resin, (B) 0.1-20 parts by weight of a curing initiator, (C) 20-100 parts by weight of a solvent and (D) aluminum. 0.1 to 50 parts by weight of the zinc oxide nanorods may be included.

On the other hand, the hard coating film according to the present invention may include a base film and a coating layer formed of an antistatic hard coating solution on one side of the base film. Depending on the application, the hard coating layer of the base film may form a protective film and the other side may form an adhesive layer. This adhesive layer may be formed by laminating a release film.

Hereinafter, the components of the antistatic hard coating solution according to the present invention will be described in detail.

(A) Heat and UV curable resin

The heat and ultraviolet curable resin (A) used in the antistatic hard coating liquid consists of a compound having two or more functional groups. Available functional groups include those having an unsaturated double bond such as (meth) acrylate and reactive substituents such as epoxy or silanol groups.

Among them, a functional group having an unsaturated double bond may be preferable in which curing may easily occur by irradiation of an activation energy ray.

Specific examples of such functional groups include ethylene glycol diacrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, trimethylol propane tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylates, polyol poly (meth) acrylates, di (meth) acrylates of bisphenol A-diglycidyl ether, polyhydric compounds obtained by esterifying polyhydric alcohols and polyhydric carboxylic acids and their anhydrides and acrylic acids Ester (meth) acrylate, polysiloxane polyacrylate, urethane (meth) acrylate, pentaerythritol tetra methacrylate, glycerin tri methacrylate and the like. Or a fluorine-containing epoxy acrylate containing fluorine, a fluorine-containing alkoxysilane, or the like. For example 2- (fefluorodecyl) ethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 3- (perfluoro-9-methyldecyl) -1, 2-epoxy propane , (Meth) acrylic acid-2,2,2-trifluoroethyl, (meth) acrylic acid-2-trifluoromethyl 3,3,3-trifluoropropyl, and the like.

The compounds specifically listed above may be used alone or in combination of two or more thereof. In the present invention, the composition ratio of other components may be determined based on 100 parts by weight of the heat and ultraviolet curable resin (A), but the present invention is not limited thereto.

(B) curing initiator

The curing initiator (B) used in the antistatic hard coating liquid helps to cure the coating liquid.

Specific examples thereof include benzoin compounds such as benzoin, benzoin methyl ether and benzoin isopropyl ether, carbonyl compounds such as benzyl, benzophenone and acetophenone, azo compounds such as azobisisobutylnitrile and azodibenzoyl, Photopolymerization initiators such as a mixture of diketones and tertiary amines may be used, but the present invention is not limited thereto.

The amount of the curing initiator may be in the range of 0.1 to 20 parts by weight based on 100 parts by weight of the heat and ultraviolet curable resin (A), but the present invention is not limited thereto.

(C) solvent

Specific examples of the solvent (C) used in the antistatic hard coating solution include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, propanol and isopropanol, ketones such as methyl isobutyl ketone and MEK, methyl acetate and ethyl acetate Ester, such as, aromatic compounds, such as toluene, xylene, benzene, ether, such as diethyl ether, etc. are mentioned, but this invention is not limited to this.

(D) Zinc Oxide Nanorods Doped with Aluminum

Aluminum-doped zinc oxide nanorods (D) used in the antistatic hard coating solution are used to impart an antistatic function to the hard coating layer. In this case, an aluminum-doped zinc oxide nanorod having excellent conductivity selected from aluminum 0.1-10 at.% Doped zinc oxide nanorods is used (see FIG. 1).

Since the hard coating solution is provided with the aluminum oxide-doped zinc oxide nanorods (D) to impart antistatic properties, the production of a coating film having antistatic properties without stacking an antistatic layer separately when manufacturing a hard coating film is difficult. It is possible.

The content of the zinc oxide nanorods (D) doped with aluminum used in the hard coating solution may range from 0.1 to 50 parts by weight, but the present invention is not limited thereto.

Hereinafter, the hard coat film in which the hard coat layer is formed on the base film with the hard coat solution described above will be described in detail.

2 is a cross-sectional view of an antistatic hard coating film according to an embodiment.

Referring to FIG. 2, the hard coating film 100 according to the present invention may include a base film 110 and a coating layer 120 formed of an antistatic hard coating solution on one side of the base film 110.

Since the hard coating film 100 according to the present invention is used as a protective film and a functional film in a liquid crystal display, a plasma display panel, a touch panel, etc., the other side of the base film 110, that is, the surface on which the hard coating layer 120 is formed The adhesive layer may be formed on the opposite side of the substrate as described with reference to FIG. 2.

3 is a cross-sectional view of an antistatic hard coating film according to another embodiment.

Referring to FIG. 3, the antistatic hard coating film 200 may be formed by curing the prepared hard coating solution on the base film 210 to form a hard coating layer 220 having antistatic property, and the base film 210. The adhesive layer 230 is formed on the other side of the. Thereafter, the adhesive film 230 may be manufactured by attaching the release film 240 to the other side of the adhesive layer 230.

Although the base film 210 used for this invention is not specifically limited, it may be a film or sheet form, and the well-known transparent base material applied to a display can also be used.

Specific examples thereof include polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), triacetyl cellulose (TAC), polyolefin (PO), polyvinyl alcohol (PVA), polyamide (PA) Polyvinyl chloride (PVC) and the like, but is not limited thereto.

In addition, the base film 210 may add an infrared absorber or an ultraviolet absorber to the transparent support. The addition amount in the case of adding this infrared absorber can use 0.01-10 weight% with respect to the total weight of a transparent support body.

The hard coating layer 220 provided with the antistatic property of the hard coating film may be prepared by curing the hard coating solution of the present invention prepared above. The method of laminating the hard coat layer 220 to the base film 210 is obtained by mixing the curable resin (A), the curing initiator (B), the solvent (C), and the zinc oxide nanorods (D) doped with aluminum. After mixing it well and applying it using a method such as roll coating, dip coating, knife coating, bar coating, spin coating, and the like, it can be cured using a halogen lamp, a high pressure mercury lamp, and a metal halide lamp. It is not limited in method.

The hard coating layer 220 of the hard coat film has a surface resistivity in the range of 10 ² to 10 ¹² Ω / sq, but may be more preferably in the range of 10 ⁸ to 10 ¹² Ω / sq. If the 10 ¹² Ω / sq or more surface resistivity in the case of the less failure to have sufficient surface antistatic function and not suitable for preventing the attachment, such as contamination of dust, 10 ² Ω / sq is because a large amount of the antistatic agent is to be added to the adhesive strength Becomes weak, and the problem that haze increases arises.

The coating film after laminating the hard coat layer 2 is formed to a thickness in the range of 0.1 to 30 μm, and especially in consideration of the fact that it does not affect the transparency and the haze of the film, a thickness in the range of 0.5 to 15 μm may be preferable. have. When the thickness of the coating film exceeds 15 μm, there is a disadvantage in that the permeability decreases and the haze becomes high. In the case of 0.5 μm or less, problems in scratch resistance and durability occur.

Since the hard coating film 200 according to the present invention is used as a protective film and a functional film in a liquid crystal display, a plasma display panel, a touch panel, etc., the other side of the base film 210, that is, the surface on which the hard coating layer 220 is formed The adhesive layer 230 is formed on the opposite side of the. The material used for an adhesion layer is not specifically limited, The well-known adhesive used in the field of this invention can be used.

Specific examples thereof include an acrylic pressure sensitive adhesive, an ultraviolet curable pressure sensitive adhesive, a thermosetting pressure sensitive adhesive, and the like. A sunscreen may be contained in this adhesion layer for UV protection, and a black pigment and carbon black may be included for color contrast improvement.

The release film 240 used for the hard coating film 200 is laminated in order to protect the adhesive layer 230. The base material used is not particularly limited, but a film or sheet may be preferable. Specific examples thereof include polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), triacetyl cellulose (TAC), polyolefin (PO), polyvinyl alcohol (PVA), polyamide (PA) Polyvinyl chloride (PVC), and the like, but is not limited thereto.

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.

Example 1

In Example 1, Igacure 184 (trade name) of Ciba-geigy Co., Ltd. as a photoinitiator (B) in a hard coating solution curable resin (A) of 100 parts by weight of 75% by weight of the urethane acrylate oligomer and 25% by weight of the acrylate monomer. Parts by weight, 1 part by weight of aluminum oxide-doped zinc oxide nanorods (D) and 100 parts by weight of toluene (C) were added to less than 1 part by weight of a smoothing agent and a UV absorber, and then mixed to prepare an antistatic hard coating solution. It was.

The hard coating solution was formed on a PET film (trade name A4100 from Toyobo) using a bar coater to form a hard coating film, and then dried at 100 ° C. for 30 seconds, followed by UV curing for 30 seconds using a mercury lamp of 80 W / cm. (See FIG. 4).

Example 2

In Example 2, Igacure 184 (trade name) manufactured by Ciba-geigy as a photoinitiator (B) in 100 parts by weight of a solid coating of a urethane acrylate 75% by weight of a hard coating liquid (A) and a solid content of 75% by weight of an acrylate monomer and 25% by weight of an acrylate monomer. Parts by weight, 3 parts by weight of zinc-doped zinc oxide nanorods (D) and 100 parts by weight of toluene (C) were added to less than 1 part by weight of a smoothing agent and a ultraviolet absorber, and then mixed to prepare an antistatic hard coating solution. It was.

The hard coating solution was formed on a PET film (trade name A4100 from Toyobo) using a bar coater to form a hard coating film, and then dried at 100 ° C. for 30 seconds, followed by UV curing for 30 seconds using a mercury lamp of 80 W / cm. (See FIG. 5).

Example 3

In Example 3, Igacure 184 (trade name) of Ciba-geigy Co., Ltd. Parts by weight, 5 parts by weight of aluminum oxide-doped zinc oxide nanorods (D) and 100 parts by weight of toluene (C) were added to less than 1 part by weight of a smoothing agent and a UV absorber, and then mixed to prepare an antistatic hard coating solution. It was.

The hard coating solution was formed on a PET film (trade name A4100 from Toyobo) using a bar coater to form a hard coating film, and then dried at 100 ° C. for 30 seconds, followed by UV curing for 30 seconds using a mercury lamp of 80 W / cm. (See FIG. 6).

Example 4

In Example 4, Igacure 184 (trade name) of Ciba-geigy Co., Ltd. Part by weight, 7 parts by weight of zinc-doped zinc oxide nanorods (D) and 100 parts by weight of toluene (C) were added to less than 1 part by weight of a smoothing agent and a UV absorber, and then mixed to prepare an antistatic hard coating solution. It was.

The hard coating solution was formed on a PET film (trade name A4100 from Toyobo) using a bar coater to form a hard coating film, and then dried at 100 ° C. for 30 seconds, followed by UV curing for 30 seconds using a mercury lamp of 80 W / cm. (See FIG. 7).

Comparative Example 1

In Comparative Example 1, Igacure 184 (trade name) of Ciba-geigy Co., Ltd. as a photoinitiator (B) in a hard coat solution of curable resin (A) with a urethane acrylate 75% by weight of oligomer and 100 parts by weight of 25% by weight of acrylate monomer. 10 parts by weight and 100 parts by weight of the toluene solvent (C) were added after the leveling agent and the ultraviolet absorber were added to less than 1 part by weight to prepare a hard coating solution. In Comparative Example 1, unlike the examples described above, aluminum oxide-doped zinc oxide nanorods (D) were not added.

The hard coating solution was formed on a PET film (trade name A4100 by Toyobo) using a bar coater to form a hard coating film, and then dried at 100 ° C. for 30 seconds, followed by UV curing for 30 seconds using a 80 W / cm mercury lamp. I was.

Physical properties as described below were measured by the hard coat film and the original film prepared in Examples 1 to 4 and Comparative Example 1, and the results are shown in Table 1 below. Table 1 is a table showing the results of measuring the haze, permeability, film strength, adhesion and surface resistivity of Examples and Comparative Example 1.

Table 1

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Disc film Haze 1.2 1.3 1.7 1.7 0.6 1.00 Permeability (%) 90 89 88 88 91 90 Membrane strength (H) 3 3 3 3 3 2 Adhesiveness (* / 100) 100 100 100 100 100 - Surface resistance (Ω / sq) 5 × 10 ¹¹ 1 × 10 ¹⁰ 1.1 × 10 ⁹ 5 × 10 ⁸ 10 of ¹³ or more 10 of ¹³ or more

(1) Haze and permeability measurement: Haze and permeability were measured using the haze and permeability measuring instrument of Nippon Denshoku Kogyu Co., Ltd., Japan.

(2) Measurement of membrane strength: The membrane strength was measured using a pencil hardness tester having a load of 1 kg / cm 2 and a slope of 45 ^° .

(3) Adhesion test: The film was made with a cross hatch cutter to have 100 cells of 1 mm x 1 mm, and then attached with cellophane tape, followed by peel test. The results are shown as the number of cells that are still attached to the film.

(4) Surface resistance: Surface resistance was measured using a Megaresta Model HO709 manufactured by Shishido electrostatic.

As can be seen in Table 1, the hard coating film prepared by using the hard coating solution according to the present invention is excellent, it is suitable for applying to an optical article because it maintains a film strength of more than 3 H and excellent antistatic properties I could see that.

Although the present invention has been described above with reference to the drawings, the present invention is not limited thereto.

For example, the antistatic hard coating solution may include zinc oxide nanorods doped with aluminum, and may include heat or ultraviolet curable resins, curing initiators, and solvents together with the zinc oxide nanorods doped with aluminum. . However, thermal or ultraviolet curable resins and curing initiators and solvents may not be included in the antistatic hard coating solution or replaced with other components or components of the same function to the extent necessary to form a hard coding layer on the base film of the hard coding film. Can be. For example, the curing initiator may not be included in the coating liquid when the heat or ultraviolet curing resin has sufficient curing property.

The hard coat film described with reference to FIG. 2 has been described as including a coating layer on one side of the base film and the base film, but may be implemented as a hard coat film described with reference to FIG. It may be.

Although the adhesive layer was formed between the coating layer and the release film in the above embodiment, the adhesive layer may adhere the coating layer and the release film without forming a separate adhesive layer between the coating layer and the release film.

In the above embodiment, the antistatic hard coat film comprises a base film and a coating layer comprising aluminum oxide doped zinc oxide formed on one side of the base film, the adhesive layer formed on the other side of the base film, the adhesion Although described as including a release film attached to the other side of the layer, the present invention is not limited thereto. For example, the hard coat film may include a base film, a coating layer formed of the antistatic hard coating liquid of claim 1 on both sides of the base film, and a protective film attached to both sides of the base film.

1 is a TEM and EDS photograph of an aluminum doped zinc oxide nanorod used in one embodiment.

2 is a cross-sectional view of an antistatic hard coating film according to an embodiment.

3 is a cross-sectional view of an antistatic hard coating film according to another embodiment.

Figure 4 is a SEM photograph of the surface of the antistatic hard coating film of Example 1.

5 is a SEM photograph of the surface of the antistatic hard coating film of Example 2.

6 is a SEM photograph of the surface of the antistatic hard coating film of Example 3.

7 is a SEM photograph of the surface of the antistatic hard coating film of Example 4.

Claims (8)

Zinc oxide nanorods doped with aluminum; And one or more of thermal or ultraviolet curable resins, curing initiators, and solvents; In the aluminum-doped zinc oxide nanorods, aluminum is doped at 0.1-10 at.% Of the aluminum oxide-doped zinc oxide nanorods, 0.1 to 20 parts by weight of the curing initiator (B), 20 to 100 parts by weight of the solvent (C), and 0.1 to 50 parts by weight of zinc-doped zinc oxide nanorods based on 100 parts by weight of the heat or ultraviolet curable resin (A). Disclaimer, the hard coating liquid. delete delete The method of claim 1, Aluminum oxide-doped zinc oxide nanorods are conductive, characterized in that the nanorods are in the form of nanorods having a thickness of 2nm ~ 1μm and a length of 10nm ~ 10μm, hard coating solution. Base film; And A coating layer formed of an antistatic hard coating solution including zinc oxide nanorods doped with aluminum on one side of the base film; Including; In the aluminum-doped zinc oxide nanorods, aluminum is doped at 0.1-10 at.% Of the aluminum oxide-doped zinc oxide nanorods, The antistatic hard coating solution further comprises a heat or ultraviolet curable resin, a curing initiator, and a solvent, 0.1 to 20 parts by weight of the curing initiator (B), 20 to 100 parts by weight of the solvent (C), and 0.1 to 50 parts by weight of zinc-doped zinc oxide nanorods based on 100 parts by weight of the heat or ultraviolet curable resin (A). Disclaimer, hard coating film. The method of claim 5, An adhesive layer formed on the other side of the base film; And A release film attached to the other side of the adhesive layer; Further comprising, a hard coating film. Base film; A coating layer formed of an antistatic hard coating solution including zinc oxide nanorods doped with aluminum on both sides of the base film; And A protective film attached to both sides of the base film; Including; In the aluminum-doped zinc oxide nanorods, aluminum is doped at 0.1-10 at.% Of the aluminum oxide-doped zinc oxide nanorods, The antistatic hard coating solution further comprises a heat or ultraviolet curable resin, a curing initiator, and a solvent, 0.1 to 20 parts by weight of the curing initiator (B), 20 to 100 parts by weight of the solvent (C), and 0.1 to 50 parts by weight of zinc-doped zinc oxide nanorods based on 100 parts by weight of the heat or ultraviolet curable resin (A). Disclaimer, hard coating film. delete

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