KR20240008995A - Anti-reflective film with gas barrier - Google Patents

Abstract

The antireflection film having gas barrier properties according to the present invention includes a substrate, a hard coating layer disposed on at least one side of the substrate, a high refractive index layer disposed as an inorganic silicon nitride layer on the hard coating layer, and a low refractive index layer disposed on the high refractive index layer. As a result, it is possible to provide both anti-reflection performance and barrier performance without adding a separate gas barrier layer, and has excellent interlayer adhesion.

Description

Anti-reflective film with gas barrier properties {ANTI-REFLECTIVE FILM WITH GAS BARRIER}

The present invention relates to an anti-reflection film, and more specifically, to an anti-reflection film with gas barrier properties that provides both a good anti-reflection function and gas barrier properties by imparting gas barrier performance to the anti-reflection film.

Conventionally, various display devices such as LCD, OLED, QLED, and micro LED are widely used in devices such as smartphones and tablet PCs, starting with televisions, which are traditional users. In addition, as smart functions are added to various electronic devices, display devices are being used in various electronic devices that did not previously use display devices.

In this way, various display products such as LCD, OLED, QLED, and micro LED have problems with external light being reflected from the display surface when exposed to external light, and when external light is reflected from the display surface, the visibility of the display is reduced. To improve the problem of reduced visibility of the display, an anti-reflection film is applied to the display.

In addition, in the case of anti-reflection films used in displays, in addition to the anti-reflection performance described above, gas barrier performance that blocks oxygen and moisture from the outside is required to ensure long-term reliability of luminance and color coordinates depending on the driving method of the display. To this end, in the case of existing anti-reflection films, a coating layer with a separate gas barrier property is introduced in addition to the anti-reflection layer to provide gas barrier performance to the anti-reflection film. However, when a separate gas barrier coating is applied, the laminated structure becomes complicated and the number of processing times is increased. Due to the increase, the problem of rising costs arises.

The present invention was created to solve the above-mentioned problems, and the problem to be solved by the present invention is to provide an anti-reflection film that can be applied to displays that require both anti-reflection and gas barrier properties, and has both anti-reflection and barrier properties at the same time. The purpose is to provide an anti-reflection film that can be implemented and has excellent gas barrier properties and excellent interfacial adhesion between the layers constituting the anti-reflection layer.

The above and other objects and advantages of the present invention will become apparent from the following description of preferred embodiments.

The above purpose is to provide an anti-reflection device having gas barrier properties, including a substrate, a hard coating layer disposed on at least one surface of the substrate, a high refractive index layer disposed on the hard coating layer and made of an inorganic silicon nitride layer, and a low refractive index layer disposed on the high refractive index layer. This is achieved by film.

Preferably, the anti-reflective film having gas barrier properties may have a water vapor transmission rate (WVTR) of less than 0.5 g/m ² ·day.

Preferably, the anti-reflection film having gas barrier properties may have a minimum reflection wavelength of more than 450 and less than 650 nm, a minimum reflectance of less than 0.3%, and a total light transmittance of more than 93%.

Preferably, the anti-reflection film having gas barrier properties may have a transmission color coordinate b* of less than 2.0.

Preferably, the anti-reflective film having gas barrier properties may have a cross hatch adhesion of 5B according to ASTM D3359-02.

Preferably, the hard coating layer may include a photocurable material and a silane compound.

Preferably, the hard coating layer may be formed of an ultraviolet curable resin composition containing 3 to 20% by weight of a silane compound.

Preferably, the hard coating layer may further include at least one particle selected from organic particles or inorganic particles.

Preferably, the thickness of the hard coating layer may be 1 to 15㎛.

Preferably, the silicon nitride forming the silicon nitride inorganic layer may be an anti-reflective film having gas barrier properties according to the following formula (1).

(Formula 1)

SixNy

Here, x and y are rational numbers greater than 0, and the ratio of x and y, y/x, is 1.20 to 1.33.

Preferably, the refractive index of the high refractive index layer may be 1.90 to 2.10, and the refractive index of the low refractive layer may be 1.30 to 1.60.

Preferably, the high refractive index layer may have a thickness of 10 to 25 nm, and the low refractive index layer may have a thickness of 90 to 170 nm.

Preferably, the low refractive index layer includes a silane compound and an isocyanate-based compound, and may further include refractive index adjusting particles.

Preferably, the silane compound may contain at least one functional group selected from the group consisting of a vinyl group, an epoxy group, a methacryloxy group, an acryloxy group, an amino group, and an isocyanate group.

Preferably, the isocyanate-based compound may include at least one selected from the group consisting of monomolecular, oligomeric, or polymer compounds having an isocyanate group.

Preferably, the refractive index adjusting particles may be at least one of tin-containing antimony oxide particles, zinc-containing antimony oxide particles, tin-containing indium oxide particles, zinc oxide/aluminum oxide particles, antimony oxide particles, porous silica particles, and hollow silica particles. .

The anti-reflection film having gas barrier properties according to the present invention is capable of simultaneously implementing anti-reflection and barrier properties, and has the effect of easily securing the luminance and color coordinate reliability of the display.

In addition, the anti-reflection film with gas barrier properties according to the present invention has a high refractive index layer that also functions as a gas barrier layer, so there is no need to form a separate gas barrier coating layer, thereby reducing manufacturing costs by simplifying the processing process. , It also has the effect of excellent interfacial adhesion of the film.

However, the effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description below.

Figure 1 is a cross-sectional view of an anti-reflection film with gas barrier properties according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to embodiments of the present invention and drawings. These examples are merely presented as examples to explain the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples. .

Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. In case of conflict, the present specification, including definitions, will control. Although methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, suitable methods and materials are described herein.

First, the anti-reflection film with gas barrier properties according to one aspect of the present invention will be described in detail with reference to Figure 1, which is a cross-sectional view of the anti-reflection film with gas barrier properties according to an embodiment of the present invention.

Referring to FIG. 1, the anti-reflection film 100 having gas barrier properties according to an embodiment of the present invention includes a substrate 11, a hard coating layer 12, a high refractive index layer 13, and a low refractive index layer 14. It has a sequentially stacked structure. However, Figure 1 shows a structure in which the hard coating layer 12, the high refractive index layer 13, and the low refractive index layer 14 are sequentially stacked only on one side of the substrate 11, but the gas according to an embodiment of the present invention The anti-reflection film 100 having barrier properties includes a structure in which a hard coating layer 12, a high refractive index layer 13, and a low refractive index layer 14 are sequentially stacked on both sides of a substrate 11. Meanwhile, in this specification, when the low refractive index layer and the high refractive index layer are referred to together, they are also referred to as an anti-reflection layer.

Equipment (11)

The substrate 11 is a transparent flexible polymer film, and may be at least one polymer film selected from polyethylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, polyetherimide, polyamideimide, polyimide, and polybenzoxazolo. It is possible, and polyethylene terephthalate is more preferable. However, the substrate 11 is not limited to the above-mentioned polymer materials, and of course, various polymer materials can be used.

Additionally, the substrate 11 may be formed as a single layer, or may be formed as a multilayer structure of two or more layers. When the substrate 11 is formed in a multi-layered structure of two or more layers, the polymer materials constituting each layer may all be the same material, or each layer may be formed of different polymer materials.

In addition, the substrate 11 preferably has a high light transmittance and a low haze value for easy application in the display field. More specifically, the substrate 11 preferably has a total light transmittance of 70% or more in the visible light region (400-700 nm) and a haze value of 3% or less.

In addition, the substrate 11 may contain various additives, such as colorants such as dyes and pigments, ultraviolet absorbers, and antioxidants, to facilitate production and coating within the range that does not impair the effect of the present invention. In this case, various surface treatments can be performed, such as corona discharge treatment or in-line coating treatment. However, when in-line coating is applied to the surface of the substrate 11, it is desirable to consider the refractive index of the substrate 11 and the refractive index of the hard coating layer 12 to prevent problems such as rainbow-like appearance deterioration. .

In addition, the thickness of the substrate 11 can be freely applied depending on the application field, and it is generally desirable to have a thickness of 25 to 500㎛.

Hard coating layer (12)

The hard coating layer 12 includes a photocurable material (ultraviolet curable material) and a silane compound, and preferably further includes at least one particle selected from organic particles or inorganic particles.

Here, the photocurable material included in the hard coating layer 12 is included to ensure surface hardness or prevent surface scratches, and preferably includes an acrylic resin or a thiol-based resin.

At this time, the acrylic resin may include a (meth)acrylate compound as an ultraviolet curable acrylic monomer. The (meth)acrylate compound may be a monofunctional compound with one acrylic functional group in the molecule or a polyfunctional compound with two or more acrylic functional groups, which can be used alone or in combination of two or more.

Among these, monofunctional (meth)acrylate compounds include, for example, methyl (meth)acrylate, n-butyl (meth)acrylate, polyester (meth)acrylate, lauryl (meth)acrylate, and hydroxyethyl. Monofunctional acrylate compounds such as (meth)acrylate and hydroxypropyl (meth)acrylate can be mentioned.

In addition, multifunctional (meth)acrylate compounds can be added for the purpose of improving solvent resistance and hardness, for example, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, Dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate ) Acrylates, etc. can be mentioned.

In addition, thiol-based resins include, for example, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, and 1,3,5-tris (3-mercaptobutyryl). Oxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropanetris(3-mercaptobutyrate), and trimethylolethanetris(3-mer captobutyrate), etc. may be used. However, the thiol-based resin used in the hard coating layer 12 is not limited to the compounds listed above, and UV-curable thiol-based resin can be freely used.

In addition, the silane compound included in the hard coating layer 12 may include a siloxane-based silane compound, and serves to induce interfacial adhesion with the high refractive index layer 13 formed on the hard coating layer 12. Therefore, when the hard coating layer 12 does not contain a silane compound, interfacial peeling occurs due to poor interfacial adhesion with the high refractive index layer 13, which is an inorganic silicon nitride layer.

Here, the silane compound included in the hard coating layer 12 may include at least one functional group selected from the group consisting of a vinyl group, an epoxy group, a methacryloxy group, an acryloxy group, an amino group, and an isocyanate group.

More specifically, the silane compound is a silane containing a functional group consisting of a vinyl group, an epoxy group, a methacryloxy group, an acryloxy group, an amino group, and an isocyanate group, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 3 -Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-clicidoxypropyltrimethoxysilane, 3-clicidoxypropyltriethoxysilane, 3-methacryloxypropylmethyl Dimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, n-2 -(Aminoethyl)-3-aminopropylmethyldimethoxysilane, n-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , 3-isocyanate propyltriethoxysilane, etc., may be in the form of monomers (single molecules), and may be in the form of oligomers or polymers combining at least one of these silanes. In addition, the hard coating layer 12 may include each of these silane compounds alone or two or more types.

Preferably, it may be an acryloxy group-containing silane compound and/or an amino group-containing silane compound, and more preferably, it may be a monomer of 3-methacryloxypropyltrimethoxysilane or 3-aminopropyltrimethoxysilane and an oligomer thereof. There may be at least one selected.

In addition, the hard coating layer 12 is preferably formed of an ultraviolet curable resin composition containing 3 to 20% by weight of a silane compound. At this time, if the silane compound is less than 3% by weight, poor interfacial adhesion with the high refractive index layer (13) occurs, and if it is more than 20% by weight, it causes a decrease in hardness of the hard coating layer (12), resulting in insufficient surface hardening and high refractive index. Problems such as poor interfacial adhesion with the layer 13 or decreased scratch resistance may occur.

Additionally, the hard coating layer 12 may further include at least one particle selected from organic particles or inorganic particles. At this time, the organic particles or inorganic particles play a role in improving the hardness of the hard coating layer 12, providing anti-glare properties, and controlling the refractive index.

Here, the organic particles are beads made of homopolymer or copolymer material obtained by using one or more monomers selected from the group consisting of acrylic, styrene, melamine formaldehyde, propylene, ethylene, urethane, methyl (meth) acrylate, and polycarbonate. Particles can be used. Additionally, the inorganic particles include silica, titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), zinc oxide (ZnO), lead carbonate (PbCO ₃ ), barium sulfate (BaSO ₄ ), calcium carbonate (CaCO ₃ ), and aluminum oxide. One or more particles selected from the group consisting of (Al ₂ O ₃ ) may be used.

Additionally, the thickness of the hard coating layer 12 is preferably 1 to 15 ㎛. At this time, if the thickness of the hard coating layer 12 is less than 1㎛, the adhesion with the high refractive index layer 13 is not sufficient, so interlayer peeling may occur, and defects such as cracks or pinholes of the high refractive index layer 13 cannot be sufficiently compensated, causing gas Barrier properties may deteriorate, and if the thickness of the hard coating layer 12 is more than 15㎛, curl may occur in the film due to the difference in thermal expansion coefficient between the high refractive index layer 13 or the substrate 11, Excessive thickness may reduce the flexibility of the film.

In addition, the hard coating layer 12 is formed using a UV-curable resin composition containing a silane compound using a gravure coat method, a blade coat method, a wire bar coat method, a reverse roll coat method, a reverse roll coat method, an extrusion coat method, and a slide coat method. , it is preferably formed through a wet process such as dip coat method, knife coat method, comma coat method, lip coat method, die coat method, spray coat method, and air knife coat method.

High refractive index layer (13)

The high refractive index layer 13 is disposed as a thin inorganic layer on the hard coating layer 12. More specifically, the high refractive index layer 13 is disposed as a silicon nitride inorganic layer. In the present invention, the high refractive index layer 13 is applied in the form of a thin inorganic film to ensure high refractive index and gas barrier properties at the same time. In addition, processing time can be reduced by forming the high refractive index layer 13, which is an inorganic layer, as a thin film on the hard coating layer 12 and directly forming this thin film.

The silicon nitride constituting the high refractive index layer 13 preferably satisfies the following formula (1).

(Formula 1)

SixNy

Here, x and y are rational numbers greater than 0, and the ratio of x and y, y/x, is 1.20 to 1.33.

At this time, if y/x in Formula 1 is less than 1.20, the problem of appearance characteristics deteriorating due to an increase in the color coordinate b* value occurs, and if it exceeds 1.33, it is difficult to implement due to the component structure of Formula 1.

Additionally, the refractive index of the high refractive index layer 13 is preferably 1.90 to 2.10. At this time, if the refractive index of the high refractive layer 13 is less than 1.90, it is difficult to implement due to the component structure of Chemical Formula 1, and if it is more than 2.10, the problem of deterioration of appearance characteristics occurs due to an increase in the color coordinate b* value.

Additionally, the thickness of the high refractive index layer 13 is preferably 10 to 25 nm. At this time, if the thickness of the high refractive index layer 13 is less than 10 nm, the thickness is too thin and the gas blocking performance is reduced, resulting in poor gas barrier properties, and if it is more than 25 nm, the surgical characteristics are deteriorated due to an increase in the color coordinate b* value. do.

In addition, the high refractive index layer 13 is preferably formed through a method such as sputtering, electron beam evaporation, chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition, or plating. It is more preferable to use

Low refractive layer (14)

The low refractive index layer 14 includes a silane compound and an isocyanate-based compound, and may further include refractive index adjusting particles. In the present invention, by introducing an organic low refractive index layer through the low refractive index layer 14, it is easier to secure low refractive index properties compared to inorganic low refractive index materials, and the low refractive layer properties are flexible to prevent cracks caused by bending the film when handling the film. This improves handling.

Here, the silane compound included in the low refractive index layer 14 is a silane compound containing at least one functional group selected from the group consisting of a vinyl group, an epoxy group, a methacryloxy group, an acryloxy group, an amino group, and an isocyanate group. For example, , vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, 3-clicidoxypropyl trimethoxysilane, 3-clicidoxypropyl Doxypropyl triethoxysilane, 3-methacryloxypropyl methyldimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, `3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxy Silane, 3-acryloxypropyl trimethoxysilane, n-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, n-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3- It may be in the form of a single molecule such as aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, or 3-isocyanatepropyltriethoxysilane, and may also be in the form of an oligomer or polymer combining at least one of these silane compounds. In addition, the low refractive index layer 14 may include each of these silane compounds alone or two or more types.

Additionally, the low refractive index layer 14 may further include an acid as a catalyst to promote the hydrolysis reaction of the silane compound. Examples of acids include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, formic acid, and acetic acid.

In addition, the isocyanate-based compound included in the low refractive index layer 14 may be a single molecule, oligomer, or polymer compound having an isocyanate group, and may contain one or two or more of these compounds.

In addition, the low refractive index layer 14 may, if necessary, contain chemical functional groups such as vinyl group, hydroxy group, carboxyl group, acrylic group, isocyanate group, amine group, amide group, urea group, epoxy group, thiol group, etc. A single molecule, oligomer, or polymer compound having a can be further added.

Additionally, the low refractive index layer 14 may further include refractive index control particles in addition to the above-described components. The refractive index of the low refractive index layer 14 can be adjusted by adding refractive index control particles to a binder made of a silane compound and an isocyanate-based compound constituting the low refractive index layer 14.

At this time, the refractive index control particles for increasing the refractive index of the low refractive layer 14 include tin-containing antimony oxide particles, zinc-containing antimony oxide particles, tin-containing indium oxide particles, zinc oxide/aluminum oxide particles, antimony oxide particles, and titanium oxide particles. , it may include particles having one or more high refractive index characteristics selected from zirconium oxide particles, indium oxide particles, zinc oxide particles, tin oxide particles, niobium oxide, cerium oxide, and tantalum oxide.

In addition, refractive index control particles for lowering the refractive index of the low refractive layer 14 include silicon oxide particles, magnesium fluoride particles, silica particles synthesized by reacting silicon alkoxide under a basic catalyst such as ammonia by the sol-gel method, sodium silicate, etc. It is preferable to include colloidal silica as a raw material or fumed silica particles synthesized in the gas phase, and more preferably, it may include particles having a low refractive index selected from porous silica particles or hollow silica particles.

Additionally, the composition for the low refractive index layer forming the low refractive index layer 14 may include one or more organic solvents. Organic solvents may include, for example, alcohol, ketone, toluene, hexane, benzene, etc., but are not limited thereto. Preferably, the composition for a low refractive index layer forming the low refractive index layer 14 may include water and alcohol as a solvent.

Additionally, the refractive index of the low refractive layer 14 is preferably 1.30 to 1.60. At this time, if the refractive index of the low refractive layer 14 is less than 1.30, the content of the refractive index control particles increases, making scratch resistance weak, and if it exceeds 1.60, the anti-reflection characteristics (lowest reflectance or lowest reflection wavelength characteristics) become poor.

Additionally, the thickness of the low refractive layer 14 is preferably 90 to 170 nm. At this time, if the thickness of the low refractive index layer 14 is less than 90 nm or exceeds 170 nm, the anti-reflection characteristics (lowest reflectance or lowest reflection wavelength characteristics) become poor.

In addition, the low refractive layer 14 is formed using the composition for the low refractive index layer described above, using the gravure coat method, blade coat method, wire bar coat method, reverse roll coat method, reverse roll coat method, extrusion coat method, slide coat method, and dip coat method. It is preferably formed through a wet process such as a coat method, knife coat method, comma coat method, lip coat method, die coat method, spray coat method, and air knife coat method.

The anti-reflective film 100 having gas barrier properties according to an embodiment of the present invention preferably has a water vapor transmission rate (WVTR) of less than 0.5 g/m ² ·day. At this time, if the moisture permeability is more than 0.5 g/m ² ·day, the barrier performance required by the display device cannot be achieved and the long-term reliability of luminance and color coordinates cannot be secured.

The anti-reflection film 100 having gas barrier properties according to an embodiment of the present invention preferably has a minimum reflection wavelength of more than 450 and less than 650 nm, a minimum reflectance of less than 0.3%, and a total light transmittance of more than 93%. If the value is outside the above range, the anti-reflection properties are poor and it cannot be used as an anti-reflection film.

The anti-reflection film 100 having gas barrier properties according to an embodiment of the present invention preferably has a transmission color coordinate b* of less than 2.0. At this time, if the transmission color coordinate is 2.0 or more, the yellowish color becomes stronger, resulting in poor appearance.

In addition, the anti-reflective film 100 having gas barrier properties according to an embodiment of the present invention preferably has a cross hatch adhesion of 5B or more according to ASTM D3359-02. At this time, if the cross hatch adhesion is less than 5B, interfacial peeling occurs due to poor interfacial adhesion.

The anti-reflection film with gas barrier properties according to an embodiment of the present invention has both gas barrier properties and anti-reflection performance by achieving the above-described laminated structure, the refractive index and thickness of the high refractive index layer, and the refractive index and thickness of the low refractive index layer. , Outside this range, it is difficult to secure anti-reflection characteristics because the reflectance characteristics are poor.

Hereinafter, the present invention will be described in more detail through examples. This example is intended to explain the present description in more detail, and the scope of the present invention is not limited to the example.

[Example]

[Example 1]

1. Formation of hard coating layer

Prepare a UV-curable resin composition containing a silane compound (solid content 20 wt%, DCT product, PC series). Afterwards, the prepared ultraviolet curable resin composition was applied to one side of a 100㎛ thick polyester base film (Toray Co., Ltd. product, Lumiror) using a bar coater, dried at 80°C for 1 minute, and the accumulated light amount of the high-pressure mercury ultraviolet lamp was 300mJ. It was irradiated and cured under conditions of /cm2 to form a hard coating layer with a thickness of 5㎛.

2. Formation of high refractive index layer

Introduce the film with the hard coating layer into the sputter deposition device, apply a Si target, and adjust the ratio of argon gas and nitrogen gas to form a high refractive index layer with a thickness of 20 nm using SixNy (refractive index 1.99) with y/x of 1.32. did.

3. Formation of low refractive index layer

After mixing 124g of alkoxy silane oligomer (Shin-Etsu, KR-513) as a silane compound and 7.4g of formic acid as an acid catalyst in a solvent mixed with 372g of isopropyl alcohol (IPA) and 124g of DI water (Daejeong Chemical), Stir for 3 hours. Afterwards, 313.7 g of isopropyl alcohol was added and stirred for 30 minutes to prepare a first mixed solution. Afterwards, 93.6 g of the primary mixture and 7.2 g of 3-aminopropyltrimethoxysilane (Shin-Etsu, KBM-903) were mixed with 180 g of isopropyl alcohol, stirred for 10 minutes, then mixed with 36 g of Di water and stirred for another 10 minutes. It was stirred. Here, 162 g of an isocyanate compound (Samwon, CAT-45) diluted in an isopropyl alcohol solvent at a weight ratio of 1:5 was added, mixed with hollow silica particle dispersion (catalyst, THRULYA 4320), and stirred to form a coating film. A composition for a low refractive index layer with a refractive index of 1.35 was prepared. The prepared composition for the low refractive index layer was bar-coated on the upper surface of the high refractive index layer and then thermally cured at 130°C for 1 minute to form a low refractive index layer with a thickness of 130 nm to prepare an anti-reflection film.

[Example 2]

In Example 1, when forming a high refractive index layer, SixNy (refractive index 2.08) with y/x of 1.25 was used as the silicon nitride of the high refractive index layer, and when forming a high refractive index layer with a thickness of 23 nm, a hollow silica particle dispersion (catalyzable) was used to form a low refractive index layer. , THRULYA 4320), a dispersion of titanium oxide (TiO ₂ ) particles (Seokkyung AT, SG-TO50) was mixed and then stirred to prepare a composition for a low refractive index layer with a film refractive index of 1.57, thereby forming a low refractive index layer with a thickness of 100 nm. An anti-reflective film was manufactured in the same manner as in Example 1, except for forming.

[Comparative example]

[Comparative Example 1]

In Example 1, when forming the hard coating layer, a UV-curable resin composition containing a silane compound (solid content 20 wt%, DCT product, PC series) was used instead of a UV-curable resin composition containing no silane compound (solid content 50 wt%, ARAKAWA, Beamset). -381) was used, and an antireflection film was manufactured in the same manner as in Example 1, except that a high refractive index layer with a thickness of 15 nm was formed when forming a high refractive index layer and a low refractive index layer with a thickness of 140 nm was formed when forming a low refractive index layer.

[Comparative Example 2]

In Example 1, an anti-reflection film was manufactured in the same manner as in Example 1, except that SixNy (refractive index 2.24) with y/x of 1.05 (refractive index 2.24) was used when forming the high refractive index layer and a high refractive index layer with a thickness of 15 nm was formed.

[Comparative Example 3]

In Example 1, the same method as Example 1 except that a low refractive index layer with a thickness of 130 nm was formed using a composition for a low refractive index layer with a coating film refractive index of 1.31 when forming a high refractive index layer with a thickness of 5 nm and a low refractive index layer with a thickness of 5 nm. An anti-reflection film was manufactured using this method.

[Comparative Example 4]

In Example 1, the same method as Example 1 except that a low refractive index layer with a thickness of 130 nm was formed using a composition for a low refractive index layer with a coating film refractive index of 1.38 when forming a high refractive index layer with a thickness of 30 nm and a low refractive index layer with a thickness of 30 nm. An anti-reflection film was manufactured using this method.

[Comparative Example 5]

In Example 1, instead of forming a high refractive index layer of SixNy by introducing it into a sputter deposition device when forming a high refractive index layer, a UV curable resin composition (solid content 40 wt%, Toyo ink, TYZ 65-) containing zirconia particles and having a refractive index of 1.65 was used. 05) was diluted with a 1:1 mixed solvent of MEK and PGME, then stirred to prepare a resin composition for a high refractive index layer with a solid content of 3 wt%, applied on the hard coating layer using a bar coater, and dried at 80°C for 1 minute. , forming a high refractive index layer with a thickness of 120 nm by irradiating and curing under the conditions of an integrated light amount of 300 mJ/㎠ from a high-pressure mercury ultraviolet lamp, and forming a low refractive index layer with a thickness of 100 nm through a composition for a low refractive index layer with a film refractive index of 1.35 when forming a low refractive layer. An anti-reflection film was manufactured in the same manner as Example 1, except for forming a layer.

[Comparative Example 6]

In Example 1, when forming a low-refractive layer, a UV-curable resin composition (solid content 50 wt%, ARAKAWA, Beamset-381) was diluted with a solvent containing a 1:1 mixture of MEK and PGME, and a hollow silica particle dispersion (catalyst, THRULYA 4320) was diluted with a 1:1 mixed solvent. ) is mixed and then stirred to apply a composition for a low refractive index layer with a film refractive index of 1.37 using a bar coater on the upper surface of the high refractive index layer. After drying at 80°C for 1 minute, the accumulated light amount of a high-pressure mercury ultraviolet ray lamp is 300mJ/㎠. An antireflection film was manufactured in the same manner as in Example 1, except that it was irradiated and cured to form a low refractive index layer with a thickness of 130 nm.

[Comparative Example 7]

In Example 1, an antireflection film was manufactured in the same manner as in Example 1, except that a low refractive index layer with a thickness of 140 nm was formed using a composition for a low refractive index layer with a coating film refractive index of 1.28.

[Comparative Example 8]

In Example 1, when forming a high refractive index layer, SixNy (refractive index 2.08) with y/x of 1.25 was used, and when forming a high refractive index layer with a thickness of 23 nm, a hollow silica particle dispersion (catalytically active) was used to form a low refractive layer. , THRULYA 4320), a low refractive index layer composition with a film refractive index of 1.62 was used by mixing titanium oxide (TiO ₂ ) particle dispersion (Seokkyung AT, SG-TO50) and stirring to form a low refractive index layer with a thickness of 110 nm. An anti-reflective film was manufactured in the same manner as in Example 1, except for forming.

[Comparative Example 9]

In Example 1, an antireflection film was manufactured in the same manner as in Example 1, except that a low refractive index layer with a thickness of 80 nm was formed using a composition for a low refractive index layer with a coating film refractive index of 1.32.

[Comparative Example 10]

In Example 1, an anti-reflection film was manufactured in the same manner as in Example 1, except that when forming the low refractive index layer, a low refractive index layer with a thickness of 180 nm was formed using a composition for a low refractive index layer with a coating film refractive index of 1.35.

For the films prepared in Examples 1 and 2 and Comparative Examples 1 to 10, the physical properties were evaluated through the following experimental examples, and the results are shown in Tables 1 and 2.

[Experimental example]

(1) Measurement of lowest reflectance and lowest reflected wavelength

The lowest reflectance and lowest reflection wavelength of the anti-reflection films according to Examples and Comparative Examples were measured using a spectrophotometer UV3600 (Shimadzu). More specifically, the back side of the anti-reflection film (sample film) according to the examples and comparative examples was uniformly scratched with 320-150 waterproof sandpaper and black paint was applied to completely eliminate reflection from the back side. , Measured at an incident light angle of 5° with respect to the antireflection layer surface, that is, the low refractive index layer surface. Here, the lowest reflectance is the minimum value in the wavelength range of 380 nm to 780 nm, and the wavelength value at that time is the minimum reflection wavelength.

(2) Transmittance measurement

Transmittance was measured using NDH-5000 (D65/10°, Nippon Denshoku) on the anti-reflective films according to Examples and Comparative Examples.

(3) Color coordinate b* measurement

The color coordinate b* value of the anti-reflective film according to the examples and comparative examples was measured in transmission mode using SA-4000 (D65/10°, Nippon Denshoku).

(4) Water vapor transmission rate (WVTR) measurement

For the anti-reflective films according to Examples and Comparative Examples, the water vapor transmission rate (g/m) was measured in the thickness direction of the film under conditions of 38°C and 100% relative humidity using a water vapor permeability meter (PERMATRAN W3/31) manufactured by Mocon Inc., USA. ² ·day) was measured.

(5) Adhesion measurement

For the anti-reflective films according to examples and comparative examples, the low refractive index layer and the high refractive index layer, which are anti-reflective layers, are The adhesion of the interlayer interface was evaluated. At this time, the evaluation criteria are as follows.

5B: 0%

4B: Less than 5%

3B: less than 15%

2B: less than 35%

1B: Less than 65%

0B: 65% or more

(6) Scratch resistance

The number of wounds was observed when a load of 250 gf/cm ² was applied to the anti-reflective film according to Examples and Comparative Examples using steel wool (steel wool #0000) and reciprocated 10 times. At this time, the evaluation criteria are as follows.

Level 5: When there are no wounds

Level 4: When there are 1 to 5 wounds

Level 3: When there are 6 to 10 wounds.

Level 2: When there are 11 or more wounds

Level 1: When there is a wound on the entire surface

item Example 1 Example 2 Comparative Example 1 Comparative example 2 Comparative example 3 Comparative example 4 Minimum reflectance (%) 0.05 0.28 0.17 0.13 0.33 0.17 Minimum reflected wavelength (nm) 567 474 606 558 611 591 Transmittance (%) 95.33 93.24 95.32 90.00 96.06 89.02 b* 1.59 -1.11 1.83 2.85 0.75 3.29 WVTR (g/m ² ·day) 0.16 0.12 0.21 0.31 1.15 0.09 Adhesion 5B 5B 0B 5B 5B 5B Scratch resistance Level 4 Level 4 Level 4 Level 4 Level 4 Level 4

item Comparative Example 5 Comparative Example 6 Comparative example 7 Comparative example 8 Comparative Example 9 Comparative Example 10 Minimum reflectance (%) 0.11 0.06 0.23 0.74 0.90 0.15 Minimum reflected wavelength (nm) 599 568 606 517 374 782 Transmittance (%) 96.11 95.23 95.07 92.85 92.81 92.40 b* 0.76 1.59 2.06 0.9 -1.13 3.49 WVTR (g/m ² ·day) 6.10 0.17 0.15 0.11 0.15 0.17 Adhesion 5B 0B 5B 5B 5B 5B Scratch resistance Level 4 Level 4 Level 2 Level 4 Level 4 Level 4

Looking at Table 1 and Table 2 above, the anti-reflection films according to Examples 1 and 2 that satisfy all the configurations of the present invention have excellent anti-reflection characteristics in terms of lowest reflectance, lowest reflection wavelength, and transmittance, and have low WVTR and high It can be seen that it has barrier properties or excellent adhesion. In addition, it can be seen that the anti-reflective films according to Examples 1 and 2, which satisfy all the configurations of the present invention, have strong scratch resistance and good appearance.

On the other hand, it can be seen that Comparative Example 1, in which no silane compound was used in the hard coating layer, lacks adhesion because it is impossible to induce interfacial adhesion between the hard coating layer and the high refractive index layer (silicon nitride inorganic layer). In this way, if the interfacial adhesion is insufficient, interfacial peeling occurs and gas barrier properties are reduced due to decreased durability during use.

In addition, in Comparative Example 2, where the Si and N ratio y/x value in Formula 1 is less than 1.20, the problem of deterioration of appearance characteristics due to yellowness occurs due to an increase in b* value, and the transmittance is also poor.

In addition, it can be seen that Comparative Example 3, in which the high refractive index layer was too thin, had poor gas barrier properties and lacked gas barrier properties.

In addition, in Comparative Example 4, where the high refractive layer thickness was excessive, the b* value increased, causing a problem of deterioration in appearance characteristics due to yellowness and poor transmittance.

In addition, it can be seen that Comparative Example 5, in which the high refractive index layer was disposed of an organic material rather than an inorganic silicon nitride layer, failed to secure gas barrier properties due to the absence of an inorganic layer, and thus had anti-reflection performance but did not have gas barrier performance.

In addition, it can be seen that in Comparative Example 6, where an ultraviolet curable resin composition was used in the low refractive index layer, poor adhesion occurred between the low refractive index layer and the high refractive index layer. In this way, when poor interfacial adhesion occurs, interfacial peeling occurs and gas barrier properties deteriorate due to decreased durability during use.

In addition, it can be seen that Comparative Example 7, in which the refractive index of the low refractive layer was excessively low, had poor scratch resistance due to the excessive content of refractive index control particles.

In addition, it can be seen that Comparative Example 8, in which the refractive index of the low refractive layer was too high, had poor anti-reflection properties because the lowest reflectance was too high.

In addition, it can be seen that Comparative Example 9, in which the low refractive index layer was too thin, had poor anti-reflection properties due to poor lowest reflectance and lowest reflection wavelength characteristics.

In addition, it can be seen that Comparative Example 10, in which the low refractive index layer was too thick, had poor anti-reflection properties due to poor lowest reflection wavelength properties.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concept of the present invention defined in the following claims are also possible. falls within the scope of rights.

100: Anti-reflection film
11: Description
12: Hard coating layer
13: High refractive index layer
14: low refractive index layer

Claims (17)

write;
A hard coating layer disposed on at least one side of the substrate;
A high refractive index layer disposed on the hard coating layer and made of an inorganic silicon nitride layer; and
a low refractive index layer disposed on the high refractive index layer;
An anti-reflective film having gas barrier properties, including. According to paragraph 1,
The anti-reflection film having gas barrier properties has a water vapor transmission rate (WVTR) of less than 0.5 g/m ² ·day. According to paragraph 1,
The anti-reflection film having gas barrier properties has a minimum reflection wavelength of more than 450 and less than 650 nm, a minimum reflectance of less than 0.3%, and a total light transmittance of more than 93%. According to paragraph 1,
The anti-reflection film with gas barrier properties is an anti-reflection film with gas barrier properties wherein the transmission color coordinate b* is less than 2.0. According to paragraph 1,
The anti-reflection film with gas barrier properties is an anti-reflection film with gas barrier properties that has a cross hatch adhesion of 5B according to ASTMD3359-02. In paragraph 1
The hard coating layer is an anti-reflective film having gas barrier properties including a photocurable material and a silane compound. According to clause 6,
The hard coating layer is an anti-reflective film having gas barrier properties formed of an ultraviolet curable resin composition containing 3 to 20% by weight of a silane compound. According to clause 6,
The hard coating layer is an anti-reflection film having gas barrier properties, further comprising at least one particle selected from organic particles or inorganic particles. According to paragraph 1,
An anti-reflection film with gas barrier properties wherein the hard coating layer has a thickness of 1 to 15 ㎛. According to paragraph 1,
The silicon nitride forming the silicon nitride inorganic layer is an anti-reflective film having gas barrier properties according to the following formula (1):
(Formula 1)
SixNy
Here, x and y are rational numbers greater than 0, and the ratio of x and y, y/x, is 1.20 to 1.33. According to paragraph 1,
The high refractive index layer has a refractive index of 1.90 to 2.10, and the low refractive index layer has a refractive index of 1.30 to 1.60. According to paragraph 1,
An anti-reflection film with gas barrier properties, wherein the high refractive index layer has a thickness of 10 to 25 nm, and the low refractive index layer has a thickness of 90 to 170 nm. According to paragraph 1,
The low refractive index layer is an anti-reflection film having gas barrier properties including a silane compound and an isocyanate-based compound. According to clause 13,
The low refractive index layer is an anti-reflective film having gas barrier properties, further comprising refractive index control particles. According to clause 13,
The silane compound is an anti-reflective film having gas barrier properties, including at least one functional group selected from the group consisting of a vinyl group, an epoxy group, a methacryloxy group, an acryloxy group, an amino group, and an isocyanate group. According to clause 13,
The isocyanate-based compound includes at least one selected from the group consisting of monomolecular, oligomeric, or polymer compounds having an isocyanate group. According to clause 14,
The refractive index adjusting particles are at least one of tin-containing antimony oxide particles, zinc-containing antimony oxide particles, tin-containing indium oxide particles, zinc oxide/aluminum oxide particles, antimony oxide particles, porous silica particles, and hollow silica particles, and have gas barrier properties. An anti-reflective film.