KR100548826B1 - Anti-static Hard Coating Solution and Hard Coating Film - Google Patents

Abstract

The antistatic hard coating solution according to the present invention comprises (A) 100 parts by weight of heat and radiation curable resin, (B) 0.1 to 20 parts by weight of a curing initiator, (C) 20 to 100 parts by weight of a solvent, and (D) C ₆₀ , It is characterized by consisting of 0.001 to 0.1 parts by weight of fullerene (fullerene) selected from the group consisting of C ₇₀ , C ₇₆ , C ₈₂ , and C ₈₄ . In addition, the hard coat film according to the present invention is a base film, a coating layer formed of an antistatic hard coating liquid on one side of the base film, an adhesive layer formed on the other side of the base film, and the other of the adhesive layer It is characterized by consisting of a release film attached to the side.

Antistatic, hard coating, coating film, optical article

Description

Anti-Static Hard Coating Solution and Hard Coating Film {Anti-static Hard Coating Solution and Hard Coating Film}             

1 is a cross-sectional view schematically showing the structure of an antistatic hard coat film according to the present invention.

Brief description of the main symbols in the drawings

1: base film 2: hard coating layer

3: adhesion layer 4: release film

Field of invention

The present invention relates to a hard coating liquid and a hard coating film having an antistatic function. More specifically, the present invention relates to a hard coating film having high permeability and low haze without making an antistatic layer separately, and a hard coating solution for producing the same.

Background of the Invention

Generally, in displays such as CRT (Cathod Ray Tube), LCD (Liquid Crystal Display), and PDP (Plasma Display Panel), the hard coating film with the hard coating layer having excellent anti-scratch on the base film as a surface protection material. I'm using. However, such a hard coating film has a disadvantage that surface dust is easily attached to the surface because the surface resistance is 10 ¹³ dl / sq or more. Therefore, an antistatic agent may be added to the hard coating layer or an antistatic layer may be introduced separately.

Known techniques for imparting antistatic properties include a method of adding a cationic, anionic or nonionic surfactant. However, this method is sensitive to the environment, and when a large amount of surfactant of a polymer is added, there is a problem in decreasing the film strength and adhesion.

Japanese Patent Laid-Open No. 2002-114066 discloses a method of adding antistatic metal particles to impart antistatic properties. However, when a large amount of inorganic particles of the metal oxide is used, there is a problem in that haze increases and hardness of the hard coating layer decreases.

Japanese Patent Laid-Open No. 5-339306 discloses a technique using a combination of an alkali metal or aluminum salt with an antistatic function and an imidazoline-based surfactant. Since the antistatic layer introduced in this way does not progress smoothly if the antistatic layer is not at the top, and thus the antistatic function may be significantly reduced, a functional layer such as antireflection or UV blocking or near infrared blocking may be formed on the layer. There is a problem that coating is difficult. Furthermore, since the surface resistance changes with humidity due to moisture in the air serving as a medium for ion conduction, there is a problem in that reliability of product quality is lowered.

In order to solve the above problems, the present inventors have come to develop a hard coating solution and a hard coating film manufactured using the same to include an antistatic function in a hard coating layer without forming an antistatic layer separately.

An object of the present invention is to provide an antistatic hard coating film excellent in transparency without increasing the haze and a hard coating liquid for producing the same.

Another object of the present invention is to provide an antistatic hard coating film having excellent film strength without increasing haze and a hard coating solution for producing the same.

Still another object of the present invention is to provide a hard coating film having an antistatic function and a hard coating solution for producing the same without forming a separate antistatic layer.                         

Still another object of the present invention is to provide a hard coating film having excellent adhesion and no peeling off from a surface thereof, and a hard coating solution for producing the same.

The above and other objects of the present invention can be achieved by the present invention described below.

Summary of the Invention

The antistatic hard coating solution according to the present invention is composed of a fullerene selected from the group consisting of heat and radiation curable resins, curing initiators, solvents and C ₆₀ , C ₇₀ , C ₇₆ , C ₈₂ , and C ₈₄ , ( A) 100 parts by weight of heat and radiation curable resin, (B) 0.1 to 20 parts by weight of curing initiator, (C) 20 to 100 parts by weight of solvent, and (D) C ₆₀ , C ₇₀ , C ₇₆ , C ₈₂ , and C _{It is characterized} by consisting of 0.001 to 0.1 parts by weight of fullerene (fullerene) selected from the group consisting of ₈₄ .

On the other hand, the hard coat film according to the present invention is a base film, a coating layer formed of an antistatic hard coating liquid on one side of the base film, an adhesive layer formed on the other side of the base film, and the other of the adhesive layer It is characterized by consisting of a release film attached to the surface.

Hereinafter, the content of the present invention will be described in detail.

Detailed Description of the Invention

Antistatic Hard Coating Liquid

Description of each component of the antistatic hard coating solution according to the present invention is as follows.

(A) Heat and radiation curable resin

The heat and radiation curable resin (A) used in the antistatic hard coating solution according to the present invention consists of a compound having two or more functional groups. Examples of the functional group that can be used include an unsaturated double bond such as (meth) acrylate and a reactive substituent such as an epoxy group or a silanol group. Among these, the functional group which has an unsaturated double bond which harden | curates easily by irradiation of an activation energy ray is preferable.

Specific examples of such functional groups include ethylene glycol diacrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) Polyesters obtained by esterifying acrylates, polyol poly (meth) acrylates, di (meth) acrylates of bisphenol A-diglycidyl ether, polyhydric alcohols and polyhydric carboxylic acids, and their anhydrides and acrylic acids ( Meta) acrylate, polysiloxane polyacrylate, urethane (meth) acrylate, pentaerythritol tetramethacrylate, glycerin trimethacrylate 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-epoxypropane , (Meth) acrylic acid-2,2,2-trifluoroethyl, (meth) acrylic acid-2-trifluoromethyl 3,3,3-trifluoropropyl, and the like. These compounds can be used 1 type or in mixture of 2 or more types. In the present invention, the composition ratio of the other components is determined based on 100 parts by weight of the heat and radiation curable resin (A).

(B) curing initiator

The curing initiator (B) used in the antistatic hard coating solution according to the present invention helps to cure the coating solution. Specific examples thereof include benzoin compounds such as benzoin, benzoin methyl ether, and benzoin isopropyl ether, benzyl, and benzo. Photopolymerization initiators, such as carbonyl compounds, such as phenone and acetophenone, azo compounds, such as azobisisobutylnitrile and azodibenzoyl, and a mixture of a ketone and a tertiary amine, can be used. As for the usage-amount of the initiator in this invention, the range of 0.1-20 weight part is suitable with respect to 100 weight part of said heat and radioactive curable resin (A).

(C) solvent

Specific examples of the solvent (C) used in the antistatic hard coating solution according to the present invention include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, propanol, isopropanol, ketones such as methyl isobutyl ketone, MEK, and acetic acid. Esters such as methyl and ethyl acetate, aromatic compounds such as toluene, xylene and benzene, ethers such as diethyl ether, and the like, but are not particularly limited thereto.

The content of a suitable solvent (C) for use in the present invention is 20 to 100 parts by weight based on 100 parts by weight of the curable resin (A). More preferably, it is 50-100 weight part. If it is less than 10 parts by weight, it is difficult to apply uniformly due to the high viscosity, and if more than 100 parts by weight, pinholes may be generated after application and drying.

(D) fullerene

Fullerene (D) used in the antistatic hard coating liquid according to the present invention is used to give an antistatic function to the hard coating layer, from the group consisting of C ₆₀ , C ₇₀ , C ₇₆ , C ₈₂ , and C ₈₄ Use the fullerene selected.

The fullerene (D) used in the present invention is preferably used together with a binder. Specific examples of binders that can be used include gelatin, starch, polyvinyl alcohol, butadiene copolymers, synthetic polymers such as polyvinyl chloride, polyacrylamide, polyurethane, polystyrene, polycarbonate, polypropylene, and the like.

Since the hard coating solution according to the present invention imparts antistatic properties by adding the fullerene (D), it is possible to manufacture a coating film having antistatic properties without separately stacking an antistatic layer when preparing a hard coating film.

The content of fullerene (D) used in the hard coating solution according to the present invention is suitably in the range of 0.001 to 0.1.

Antistatic hard coating film

In the antistatic hard coating film according to the present invention, the hard coating solution prepared above is cured on the base film 1 to form a hard coating layer 2 having antistatic property, and on the other side of the base film 1 After the formed pressure-sensitive adhesive layer 3 is formed, the release film 4 is attached to the other side of the pressure-sensitive adhesive layer is prepared.

Although the base film 1 used for this invention is not specifically limited, A film or sheet form is preferable, A well-known transparent base material applied to a display can 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 are preferable. Moreover, you may add an infrared absorber or an ultraviolet absorber to a transparent support body. The addition amount in the case of adding an infrared absorber uses 0.01-10 weight% with respect to the total weight of a transparent support body.

The hard coat layer 2 provided with the antistatic property of the hard coat film according to the present invention is prepared by curing the hard coat solution of the present invention prepared above. The method of laminating the hard coating layer is to mix the curable resin (A), the curing initiator (B), the solvent (C), and the antistatic agent (D), and then mix the roll coating, dip coating, knife coating, bar coating, and spin. After coating using a coating method, it is cured using a halogen lamp, a high pressure mercury lamp, and a metal halide lamp.

The hard coat layer 2 of the hard coat film according to the present invention generally has a surface resistivity in the range of 10 ² to 10 ¹² Pa / sq, but more preferably in the range of 10 ⁸ to 10 ¹² Pa / sq. If the surface resistivity is more than 10 ¹² Ω / sq, the surface antistatic function is not sufficient to prevent the adhesion of dust, etc. If the surface resistivity is less than 10 ² Ω / sq, a large amount of antistatic agent should be added so that the adhesive strength is It becomes weak and there is a problem that haze increases.

The coating film after laminating the hard coat layer 2 of the present invention is formed to a thickness in the range of 0.1 to 30 μm. In particular, the thickness in the range of 0.5 to 15 μm is considered in consideration of not affecting the transparency and the haze of the film. desirable. If the thickness of the coating film exceeds 15 μm, there is a disadvantage in that the permeability decreases and the haze becomes high, and in the case of 0.5 μm or less, problems in scratch resistance and durability occur.

Since the hard coat film 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, or the like, the other side of the base film 1 (the opposite side to the surface on which the hard coating layer 2 is formed) The pressure-sensitive adhesive layer 3 is formed. 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 4 used for the hard coat film according to the present invention is laminated in order to protect the adhesive layer. The base material used is not particularly limited, but a film or sheet form is preferable. Specific examples thereof include polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), triacetyl cellulose (TAC), polyolefin (PO), polyvinyl alcohol (PVA), polyamide (PA) And polyvinyl chloride (PVC).

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

Example 1

In Example 1 of the present invention, Igacure 184 (Ciba-geigy Co., Ltd.) as a photoinitiator (B) in a hard coating solution curable resin (A) of 100 parts by weight of the urethane acrylate 75% by weight oligomer and 25% by weight of the acrylate monomer. 10 parts by weight, and 33 parts by weight of a solvent (C) in which 0.025 mg of C ₆₀ (D) is dissolved per 1 g of toluene are added at an amount of less than 1 part by weight of a smoothing agent and a ultraviolet absorber, and then mixed with the antistatic hard coating solution. Was prepared. 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.

Example 2

In Example 2 of the present invention, a hard coat film was prepared under the same conditions as in Example 1 except that 100 parts by weight of a solvent (C) in which C ₆₀ dissolved 0.025 mg per 1 g of toluene was used.

Example 3

In Example 3 of the present invention, a hard coat film was prepared under the same conditions as in Example 1 except that 33 parts by weight of C ₆₀ dissolved in 0.1 mg of C ₆₀ per g of toluene was used.

Example 4

In Example 4 of the present invention, a hard coat film was prepared under the same conditions as in Example 1 except that 100 parts by weight of the solvent (C) dissolved in 0.1 mg of C ₆₀ per 1 g of toluene was used.

Comparative Example 1

In Comparative Example 1 of the present invention, Igacure of Ciba-geigy Co., Ltd. as a photoinitiator (B) in 100 parts by weight of a curable resin (A) of the hard coating solution as a urethane acrylate 75% by weight of oligomer and 25% by weight of acrylate monomer 10 parts by weight of 184 (trade name) 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. 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.

The following physical properties 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.

(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 × 1 mm on the surface of the film, adhered with cellophane tape, and then peeled off. The result was shown as the number (*) of the cell which has just stuck to the film.

(4) Surface resistivity: Electric resistance was measured using Hiresta's MCP-HT450.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Disc film Haze 1.0 1.0 0.6 1.3 0.5 1.00 Permeability (%) 90 90 90 89 91 90 Membrane strength (H) 3 3 3 3 3 2 Adhesiveness (* / 100) 100 100 100 100 100 - Surface resistivity (Ω / sq) 8 × 10 ¹¹ 8 × 10 ¹¹ 9 × 10 ¹¹ 9 × 10 ¹¹ 10 ¹³ or more (Not measurable) 10 ¹³ or more (Not measurable)

As can be seen in Table 1, the hard coating film prepared using the hard coating liquid according to the present invention is excellent in transmittance without increasing the haze, and is suitable for application to an optical article because it maintains a film strength of 3 H or more. It can be seen that.

The present invention provides an antistatic hard coating film having excellent transparency and film strength without increasing the haze and having an antistatic function and excellent adhesiveness without peeling off the surface without forming a separate antistatic layer, and for producing the same. It has the effect of providing the hard coating solution.

Simple modifications and variations of the present invention can be readily used by those skilled in the art, and all such variations or modifications can be considered to be included within the scope of the present invention.

Claims (4)

An antistatic hard coating liquid comprising a heat and radiation curable resin, a curing initiator, a solvent, and a fullerene selected from the group consisting of C ₆₀ , C ₇₀ , C ₇₆ , C ₈₂ , and C ₈₄ . According to claim 1, 100 parts by weight of the heat and radiation curable resin (A), 0.1 to 20 parts by weight of the curing initiator (B), 20 to 100 parts by weight of the solvent (C), and C ₆₀ , C ₇₀ , C ₇₆ , C ₈₂ , and C ₈₄ An antistatic hard coating liquid, characterized in that consisting of 0.001 to 0.1 parts by weight of the fullerene (fullerene) selected from the group consisting of. A base film, a coating layer formed of the antistatic hard coating solution of claim 1 or 2 on one side of the base film, an adhesive layer formed on the other side of the base film, and the other side of the adhesive layer An antistatic hard coat film comprising a release film. The antistatic hard coating film according to claim 3, wherein the film strength is at least 3 H, the transmittance is at least 85%, and the surface resistivity is 10 ⁸ to 10 ¹² Pa / sq.

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