KR101272862B1 - Optical film - Google Patents

Abstract

The present invention relates to an optical film having a low reflectance and no rainbow phenomenon, including a polyurethane coating layer.

Polyurethane, Isocyanate, Optical Film, Refractive Index, Rainbow

Description

Optical film

The present invention relates to an optical film. More specifically, it relates to an optical film having a low reflectance and no rainbow phenomenon by laminating a polyurethane coating layer on one or the back surface.

Optical films are used in various optical applications, including the production of display members such as LCDs, PDPs, and organic ELs. Such an optical film is required to have excellent transparency and visibility, and in order to satisfy these properties, the reflectance must be low and there should be no rainbow phenomenon.

Such an optical film is used by laminating a surface functional layer such as a hard coating layer and an antireflection layer on a plastic film. A transparent polyester film is generally used as a plastic film, and the coating layer is formed as an intermediate | middle layer in order to improve adhesiveness of the polyester film which is a base material, and a surface functional layer.

In general, the antireflection film is formed by alternately stacking a high refractive index layer and a low refractive index layer as an antireflection layer, and serves to prevent reflection of an external light source by using interference of light.

Acrylic resin or urethane resin is generally used as an intermediate layer for improving adhesion with such functional layers. However, when the coating layer is formed using the above resin, since the refractive index is about 1.5, when the antireflection film is designed, There is a limitation in the anti-reflection performance, there is a problem that interference stains caused by external light reflection, that is, the rainbow phenomenon occurs. This rainbow phenomenon deteriorates visibility and should be improved because it causes eye fatigue when applied to the display member.

The present invention is to provide an optical film having a low reflectance and no rainbow phenomenon. Specifically, the present invention is to provide an optical film having a reflectance of 5 to 10% and no rainbow phenomenon when applied to an antireflection film or a hard coating film.

In order to achieve the above object, the present invention relates to an optical film including a polyurethane coating layer having a refractive index of 1.54 to 1.59.

The present inventors have found that the reflectance is low and the rainbow phenomenon is improved by adjusting the refractive index of the polyurethane coating layer, in particular, of the coating layer of the optical film, thereby completing the present invention.

That is, the present invention includes a polyurethane coating layer as a coating layer applied to the base film and one or both sides thereof, and includes an aromatic isocyanate compound so that the refractive index of the polyurethane coating layer satisfies the range of 1.54 ~ 1.59, wherein the The content of the aromatic isocyanate compound is used in the range of 25 to 90% by weight of the total isocyanate content to find that the refractive index can be satisfied to complete the present invention. If the refractive index is less than 1.54, since the refractive index difference with the upper functional coating layer such as the hard coating layer and the antiglare coating layer is much different, the rainbow property is deteriorated. Adhesion of the deterioration and the appearance unevenness of the coating layer may occur.

Specifically, the present invention is a polyol; Isocyanate compound containing at least one aromatic isocyanate compound of Formula 1; an optical film coated with a polyurethane coating composition for optical film comprising a polyurethane binder having a refractive index of 1.54 ~ 1.59 on one side or both sides of the base film It is about.

[Formula 1]

OCN-Ar-NCO

(In Formula 1, Ar is (C6-C30) arylene substituted or unsubstituted (C1-C5) alkyl.)

Ar in the general formula (1) is preferably naphthylene or phenylene.

In the present invention, the aromatic isocyanate compound preferably contains 25 to 90% by weight of the total isocyanate content, and when used in the above range, the refractive index satisfies the range of 1.54 to 1.59, the objective in the range that satisfies the refractive index range The reflectance and rainbow improvement effect can be achieved. In particular, in the present invention, it is preferable to use naphthalene diisocyanate as the aromatic isocyanate compound of Chemical Formula 1.

The polyol may be a polyester-based polyol or a polyether-based polyol, preferably a polyester-based polyol. More preferably, it is preferable to use a polyester polyol having a weight average molecular weight of 600 to 3000.

The polyurethane coating composition is a moisture content of 2 to 10% by weight of the total solid content, including 5 to 30% by weight of polyurethane binder, 0.1 to 0.4% by weight of the wetting agent, 0.1 to 0.5% by weight of silica having an average particle diameter of 100 to 200nm It is preferably an acidic or water soluble composition. In addition, the polyurethane binder is preferably an aqueous polyurethane binder having a solid content of 15 to 30% by weight including a reactive emulsifier having an ionic group and water.

The polyurethane coating composition is preferably coated with a dry coating thickness of 15 ~ 80nm.

The base film is preferably a polyethylene terephthalate film.

The optical film according to the present invention also includes an anti-reflection film further comprising a hard coating film or an anti-glare coating layer further comprising a hard coating layer.

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

The base film used in the present invention is preferably a polyester film, more specifically, a film obtained by melt extruding polyethylene terephthalate pellets having an Intrinsic Viscosity of 0.60 to 0.65, because of excellent light transmittance. In this case, preferably, the refractive index is 1.63 to 1.65, more preferably 1.64. Additives or particles may be further added to satisfy the refractive index range. The polyethylene terephthalate film is preferably a stretched film, it is possible to use a uniaxial or biaxially stretched film.

Polyurethane coating layer in the present invention is a polyol; Isocyanate compound comprising at least one aromatic isocyanate compound of Formula 1; reacted to form a polyurethane coating composition for an optical film comprising a polyurethane binder having a refractive index of 1.54 ~ 1.59 to one side or both sides of the base film do.

[Formula 1]

OCN-Ar-NCO

(In Formula 1, Ar is (C6-C30) arylene substituted or unsubstituted (C1-C5) alkyl.)

Ar in the general formula (1) is preferably naphthylene or phenylene. More preferably it is naphthylene, and such a compound is naphthalene diisocyanate.

In the present invention, the aromatic isocyanate compound preferably contains 25 to 90% by weight of the total isocyanate content, and when used in the above range, the refractive index satisfies the range of 1.54 to 1.59, the objective in the range that satisfies the refractive index range The reflectance and rainbow improvement effect can be achieved. Isocyanate compounds that can be used together with the aromatic isocyanate compound can be used as long as it is an isocyanate compound that is commonly used in the art, but preferably hexamethylene diisocyanate is used to control the reaction during prepolymer production. Advantageously, the appearance of the coating layer becomes uniform when the polyurethane composition is made and applied.

When the content of the aromatic isocyanate compound, especially naphthalene diisocyanate is mixed in the range of 25 to 90% by weight can achieve the desired refractive index 1.54 ~ 1.59, the target reflectivity and rainbow improvement effect in this refractive index range Can be achieved.

In the present invention, the polyol may be a polyester-based polyol or a polyether-based polyol, preferably a polyester-based polyol. Polyester-based polyols are polyols prepared from the reaction of carboxylic acids, sebacic acids or acid anhydrides with polyhydric alcohols. The type of the polyol is not limited, and the use of a polyester polyol having a weight average molecular weight of 600 to 3000 is effective for increasing the refractive index of the final reactant, and is advantageous for increasing adhesion and improving physical strength.

The polyurethane coating composition is a moisture content of 2 to 10% by weight of the total solid content, including 5 to 30% by weight of polyurethane binder, 0.1 to 0.4% by weight of the wetting agent, 0.1 to 0.5% by weight of silica having an average particle diameter of 100 to 200nm It is preferably an acidic or water soluble composition.

The polyurethane binder is preferably an aqueous polyurethane binder having a solid content of 15 to 30% by weight including a reactive emulsifier having an ionic group and water. After preparing a water-dispersible or water-soluble polyurethane binder having a solid content of 15 to 30% by weight, it is mixed again with additives such as a wetting agent and silica and water to prepare a water-dispersible or water-soluble coating composition, wherein the total solid content It is easy to adjust the coating thickness to apply the coating so that the content is 2 to 10% by weight.

In the present invention, the reactive emulsifier may have a functional group of an anionic hydrophilic group or a cationic hydrophilic group, and the anionic hydrophilic group and the cationic hydrophilic group may have a polymerizable unsaturated group. The reactive emulsifiers include anionic hydrophilic groups or cationic hydrophilic groups which are ionic hydrophilic groups as functional groups.

Examples of the anionic hydrophilic group include -SO ₂ M, -SO ₃ M, -COOM, -PO ₃ M ₂ or -PO ₃ MH functional group (M is an alkaline earth metal atom or ammonium salt such as hydrogen atom, lithium, sodium, potassium, etc.). ), And the like. Examples of the cationic hydrophilic group include those having an alkylamine, an ethoxylate amine derivative, an alkylimidazoline derivative or a quaternary ammonium halide functional group, and may be optionally used.

The anionic reactive emulsifier is an anionic having a polymerizable unsaturated bond, and has a double bond, an alkyl group, an aromatic compound, and an anionic group, as well as an ether group, an ester group, a sulfone group, a sulfoxide group, a sulfide group, and a hydroxyl group. It may be. The anionic group may be composed of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a sulfuric acid group, or a salt thereof. Cationic reactive emulsifiers are cationic with polymerizable unsaturated bonds, and may include alkyl and aromatic compounds in addition to double bonds and cationic groups, ether groups, ester groups, sulfone groups, sulfoxide groups, sulfide groups It may have a functional group, such as a hydroxyl group, simultaneously.

The polyurethane coating composition is preferably coated with a dry coating thickness of 15 to 80 nm because the desired refractive index can be achieved. The coating method may be coated with an in-line coating applied to the surface during the stretching process of the polyester film, or may be carried out offline coating after film production. It is also possible to combine both. Preferably, in-line coating is applied at the same time as the film forming, and thus manufacturing cost is reduced, and the thickness of the coating layer may be changed by extension magnification.

The optical film according to the present invention has a transmittance and reflectance suitable for use as a hard coat film or an antireflection film and has a rainbow improving effect.

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

The method of measuring the physical properties shown in the following Examples and Comparative Examples is as follows.

1) Total light transmittance measurement: After coating the polyurethane coating composition on a polyethylene terephthalate film as a base film, the total light transmittance of the entire film was measured using a total light transmittance meter (Nippon Denshoku 300A).

2) Reflectance measurement: After measuring the visible light region of 200 ~ 800nm using a UV-Visible (Varian, Cary5000) coated with a polyurethane coating composition, the reflectance was measured based on 550nm.

3) Refractive index measurement: The aqueous urethane binder was applied to a polycarbonate film, dried, and measured at room temperature using an ABBE refractometer (DRGO, ATAGO).

4) Rainbow phenomenon measurement: After manufacturing the optical film according to the Examples and Comparative Examples, the hard coating treatment (refractive index of 1.65) on one side of the other side was blackened to determine whether the rainbow occurs with the naked eye. Visual evaluation was performed under a three-wavelength lamp in the dark room.

The evaluation criteria are as follows.

Top: Rainbow is not seen and uniform color

Medium: Rainbow phenomenon is soft and uniform color.

Bottom: Strong rainbow, strong color

5) Measurement of dry coating thickness: SEM (Hitachi S-4300) the cross section of the film by designating the full width of the base film coated with the polyurethane coating composition at 1 m intervals in the vertical direction (TD) of the machine direction at 1 m intervals. The average value was calculated.

Example 1

Preparation of Polyurethane Coating Composition (1)

9% by weight of a polyester-based polyol (polyethylene adipate diol having a weight average molecular weight of 1000), 10% by weight of an isocyanate mixture of 25: 75% by weight of hexamethylene diisocyanate and 2,6-naphthalene diisocyanate, an ionic group 20% by weight of an aqueous polyurethane binder having a solid content of 1% by weight of reactive emulsifier (Asahi Denka, Adecaria Shop SETM, a sulfonic acid ester of polyoxyethylene allyl glycidyl nonyl phenylether) and 80% by weight of water Prepared. The refractive index of the prepared aqueous polyurethane binder was measured to be 1.57.

10 wt% of the aqueous polyurethane binder, 0.2 wt% of silicone-based wetting agent (Dow Corning, polyester siloxane copolymer), and 0.15 wt% of colloidal silica particles having an average particle diameter of 140 nm were added to water, followed by stirring for 3 hours to obtain a total solid content. The polyurethane coating composition (1) having a content of 2% by weight was prepared.

Preparation of One Side Coating Polyester Film

The polyethylene terephthalate chip from which moisture was removed was placed in an extruder, melt-extruded, and then quenched and solidified with a casting drum having a surface temperature of 20 ° C. to prepare a polyethylene terephthalate sheet having a thickness of 2000 μm. The prepared polyethylene terephthalate sheet was stretched 3.5 times in the machine direction (MD) at 80 ° C. and then cooled to room temperature. Then, after coating the polyurethane coating composition (1) on one surface by a bar coating method (bar coating), the temperature is increased by 1 ℃ per second to 110 ~ 150 ℃ by preheating, drying and stretching 3.5 times in the transverse direction (TD) It was. Thereafter, heat treatment was performed at 235 ° C. in a 5-stage tenter, and thermally fixed at 10 ° C. in the longitudinal and transverse directions at 200 ° C. to prepare a 188 μm biaxially oriented film coated on one surface. The dry coating thickness of the polyurethane coating layer was 40 nm.

The physical properties of the optical film thus obtained are shown in Table 1 below.

[Example 2]

Preparation of Double-coated Polyester Film

The polyethylene terephthalate chip from which moisture was removed was placed in an extruder, melt-extruded, and then quenched and solidified with a casting drum having a surface temperature of 20 ° C. to prepare a polyethylene terephthalate sheet having a thickness of 2000 μm. The prepared polyethylene terephthalate sheet was stretched 3.5 times in the machine direction (MD) at 80 ° C. and then cooled to room temperature. Thereafter, the polyurethane coating composition (1) prepared in Example 1 was coated on both sides by a bar coating method, and then heated up by 1 ° C. per second to 110 to 150 ° C., followed by preheating and drying, followed by a transverse direction (TD). E) to 3.5 times. Thereafter, heat treatment was performed at 235 ° C. in a 5-stage tenter, followed by heat setting at 10 ° C. in the longitudinal and transverse directions at 200 ° C. to prepare a 188 μm biaxially oriented film coated on both sides. The dry coating thickness of the polyurethane coating layer was 40 nm, respectively. The physical properties of the optical film thus obtained are shown in Table 1 below.

[Example 3]

Preparation of Polyurethane Coating Composition (2)

9% by weight of a polyester-based polyol (polyethylene adipate diol having a weight average molecular weight of 1000), 10% by weight of an isocyanate mixture containing 10: 90% by weight of hexamethylene diisocyanate and 2,6-naphthalene diisocyanate, an ionic group An aqueous polyurethane binder having a solid content of 20% by weight of a reactive emulsifier (Asahi Denka, Adecaria Shop SETM, a sulfonic acid ester of polyoxyethylene allyl glycidyl nonyl phenylether) and 80% by weight of water was reacted. Prepared. The refractive index of the prepared aqueous polyurethane binder was measured to be 1.59.

10 wt% of the aqueous polyurethane binder, 0.2 wt% of silicone-based wetting agent (Dow Corning, polyester siloxane copolymer), and 0.15 wt% of colloidal silica particles having an average particle diameter of 140 nm were added to water, followed by stirring for 3 hours to obtain a total solid content. A polyurethane coating composition (2) having a content of 2% by weight was prepared.

Preparation of Double-coated Polyester Film

The polyethylene terephthalate chip from which moisture was removed was placed in an extruder, melt-extruded, and then quenched and solidified with a casting drum having a surface temperature of 20 ° C. to prepare a polyethylene terephthalate sheet having a thickness of 2000 μm. The prepared polyethylene terephthalate sheet was stretched 3.5 times in the machine direction (MD) at 80 ° C. and then cooled to room temperature. Thereafter, the polyurethane coating composition 2 was coated on both sides by a bar coating method, and then heated to 1 ° C. per second to 110 to 150 ° C. and stretched 3.5 times in a transverse direction (TD) through preheating and drying. It was. Thereafter, heat treatment was performed at 235 ° C. in a 5-stage tenter, followed by heat setting at 10 ° C. in the longitudinal and transverse directions at 200 ° C. to prepare a 188 μm biaxially oriented film coated on both sides. The dry coating thickness of the polyurethane coating layer was 40 nm, respectively.

The physical properties of the optical film thus obtained are shown in Table 1 below.

Example 4

Preparation of Polyurethane Coating Composition (3)

9% by weight of a polyester-based polyol (polyethylene adipate diol having a weight average molecular weight of 1000), 10% by weight of an isocyanate mixture containing 75: 25% by weight of hexamethylene diisocyanate and 2,6-naphthalene diisocyanate, an ionic group 20% by weight of an aqueous polyurethane binder having a solid content of 1% by weight of reactive emulsifier (Asahi Denka, Adecaria Shop SETM, a sulfonic acid ester of polyoxyethylene allyl glycidyl nonyl phenylether) and 80% by weight of water Prepared. The refractive index of the prepared aqueous polyurethane binder was measured to be 1.54.

10 wt% of the aqueous polyurethane binder, 0.2 wt% of silicone-based wetting agent (Dow Corning, polyester siloxane copolymer), and 0.15 wt% of colloidal silica particles having an average particle diameter of 140 nm were added to water, followed by stirring for 3 hours to obtain a total solid content. A polyurethane coating composition (3) having a content of 2% by weight was prepared.

Preparation of Double-coated Polyester Film

The polyethylene terephthalate chip from which moisture was removed was placed in an extruder, melt-extruded, and then quenched and solidified with a casting drum having a surface temperature of 20 ° C. to prepare a polyethylene terephthalate sheet having a thickness of 2000 μm. The prepared polyethylene terephthalate sheet was stretched 3.5 times in the machine direction (MD) at 80 ° C. and then cooled to room temperature. Thereafter, the polyurethane coating composition 3 is coated on both sides by a bar coating method, and then heated to 1 ° C. per second to 110 to 150 ° C. and stretched 3.5 times in a transverse direction (TD) by preheating and drying. It was. Thereafter, heat treatment was performed at 235 ° C. in a 5-stage tenter, followed by heat setting at 10 ° C. in the longitudinal and transverse directions at 200 ° C. to prepare a 188 μm biaxially oriented film coated on both sides. The dry coating thickness of the polyurethane coating layer was 40 nm, respectively.

[Example 5]

Preparation of Double-coated Polyester Film

The polyethylene terephthalate chip from which moisture was removed was placed in an extruder, melt-extruded, and then quenched and solidified with a casting drum having a surface temperature of 20 ° C. to prepare a polyethylene terephthalate sheet having a thickness of 2000 μm. The prepared polyethylene terephthalate sheet was stretched 3.5 times in the machine direction (MD) at 80 ° C. and then cooled to room temperature. Thereafter, the polyurethane coating composition (2) prepared in Example 3 was coated on one surface by a bar coating method, and the polyurethane coating composition (3) prepared in Example 4 was used as a bar coating method. After coating on the opposite side, the temperature was increased by 1 ° C. per second to 110 to 150 ° C., followed by preheating and drying, followed by stretching 3.5 times in the transverse direction (TD). Thereafter, heat treatment was performed at 235 ° C. in a 5-stage tenter, followed by heat setting at 10 ° C. in the longitudinal and transverse directions at 200 ° C. to prepare a 188 μm biaxially oriented film coated on both sides. The dry coating thickness of the polyurethane coating layer was 40 nm, respectively.

Comparative Example 1

The polyethylene terephthalate chip from which moisture was removed was placed in an extruder, melt-extruded, and then quenched and solidified with a casting drum having a surface temperature of 20 ° C. to prepare a polyethylene terephthalate sheet having a thickness of 2000 μm. The prepared polyethylene terephthalate sheet was stretched 3.5 times in the machine direction (MD) at 80 ° C. and then cooled to room temperature. Thereafter, the temperature was increased by 1 ° C. per second to 110 to 150 ° C., followed by preheating and drying to draw 3.5 times in the transverse direction (TD). Thereafter, heat treatment was performed at 235 ° C. in a 5-stage tenter, followed by heat setting at 10 ° C. in the longitudinal and transverse directions at 200 ° C. to prepare an uncoated 188 μm biaxially oriented film.

The physical properties of the optical film thus obtained are shown in Table 1 below.

Comparative Example 2

Preparation of Polyurethane Coating Composition (4)

9% by weight of a polyester-based polyol (polyethylene adipate diol having a weight average molecular weight of 1000), 10% by weight of hexamethylene diisocyanate, a reactive emulsifier having an ionic group (Asahi Denka, polyoxy ethylene allyl glycidyl nonyl phenyl ether An aqueous polyurethane binder having a solid content of 20% by weight was prepared by reacting 1% by weight of adecaria shop SETM), which is a sulfonic acid ester, and 80% by weight of water. The refractive index of the prepared aqueous polyurethane binder was measured to be 1.53.

10 wt% of the aqueous polyurethane binder, 0.2 wt% of silicone-based wetting agent (Dow Corning, polyester siloxane copolymer), and 0.15 wt% of colloidal silica particles having an average particle diameter of 140 nm were added to water, followed by stirring for 3 hours to obtain a total solid content. A polyurethane coating composition (4) having a content of 2% by weight was prepared.

Preparation of Double-coated Polyester Film

The polyethylene terephthalate chip from which moisture was removed was placed in an extruder, melt-extruded, and then quenched and solidified with a casting drum having a surface temperature of 20 ° C. to prepare a polyethylene terephthalate sheet having a thickness of 2000 μm. The prepared polyethylene terephthalate sheet was stretched 3.5 times in the machine direction (MD) at 80 ° C. and then cooled to room temperature. Thereafter, the polyurethane coating composition 4 was coated on one surface by a bar coating method, and then heated to 1 ° C. per second to 110 to 150 ° C., followed by preheating and drying, and stretched 3.5 times in the transverse direction (TD). . Thereafter, heat treatment was performed at 235 ° C. in a 5-stage tenter, followed by heat setting at 10 ° C. in the longitudinal and transverse directions at 200 ° C. to prepare a 188 μm biaxially oriented film coated on both sides. The dry coating thickness of the polyurethane coating layer was 40 nm, respectively.

[Table 1]

As shown in the table, the total light transmittance of the present invention is 90% or more, the reflectance is less than 10% while the rainbow phenomenon hardly occurred.

Claims (11)

Polyols; Isocyanate compound containing at least one aromatic isocyanate compound of Formula 1; 5 to 30% by weight of polyurethane binder having a refractive index of 1.54 to 1.59, 0.1 to 0.4% by weight of a wetting agent, silica having an average particle diameter of 100 to 200nm An optical film coated with one or both sides of a base film of a polyurethane coating composition having a total solids content of 2 to 10% by weight, including 0.1 to 0.5% by weight. [Formula 1] OCN-Ar-NCO (In Formula 1, Ar is (C6-C30) arylene substituted or unsubstituted (C1-C5) alkyl.) The method of claim 1, In Formula 1 Ar is naphthylene or phenylene optical film. 3. The method of claim 2, The aromatic isocyanate compound of Chemical Formula 1 is naphthalene diisocyanate. The method of claim 1, The aromatic isocyanate compound comprises 25 to 90% by weight of the total isocyanate content. The method of claim 1, The polyol is a polyester-based polyol having a weight average molecular weight of 600 ~ 3000. delete The method of claim 1, The polyurethane binder is an optical film which is an aqueous polyurethane binder having a solid content of 15 to 30% by weight including a reactive emulsifier having an ionic group and water. The method of claim 1, The polyurethane coating composition is an optical film coated with a dry coating thickness of 15 ~ 80nm. The method according to any one of claims 1 to 5, 7 and 8, The base film is an optical film of polyethylene terephthalate film. 10. The method of claim 9, The optical film is an optical film which is a hard coating film. 10. The method of claim 9, The optical film is an optical film that is an antireflection film.