KR100789403B1 - Anti-reflection and antistatic film and manufacturing method thereof - Google Patents

Abstract

An anti-static and an anti-reflection film, and a manufacturing method thereof are provided to improve anti-static and anti-reflection effects simultaneously by coating an anti-static layer under a high refraction layer and a low refraction layer. A hard coating layer is coated on a material. A middle-high refraction rate layer containing a conductive polymer is located on the hard coating layer, and have refraction rates 1.6 to 1.75. A high refraction rate layer is located on the middle-high refraction rate layer, and has a refraction rate 1.6 to 1.23. A low refraction rate layer is located on the high refraction rate layer, and has a refraction rate 1.35 to 1.5.

Description

An anti-static and anti-reflection film and a method of preparing the same

1 is a schematic diagram showing a cross section of an antireflective and antistatic film sheet manufactured according to an embodiment of the present invention.

2 is a spectrum obtained by measuring the reflectance of the specimen prepared according to the embodiment of the present invention.

3 is a spectrum obtained by measuring the reflectance of a specimen prepared according to another embodiment of the present invention.

The present invention relates to the production of anti-reflection and anti-static film having excellent wear resistance, and includes a medium and high refractive index layer made of a conductive polymer, a high refractive layer of an inorganic material, and a low refractive coating liquid of a silicon series after treating the wear resistant coating having excellent hardness. It is.

Various displays, liquid crystal displays, plasma display panels, PDAs, etc. have problems of deterioration of image quality due to reflections on the screen, malfunction of devices due to static electricity, and contaminants. There are other problems.

In order to solve this problem of reflection and charging, conventionally, the anti-reflective and antistatic coatings were coated on the plastic substrate, but the defect rate was increased and the restrictions on the products used occurred. come.

Among the antireflective coating films, Japanese Patent Application Laid-Open Nos. Hei 6-230201 and 9-203801 disclose a single wet coating method in which a low refractive index layer having a small refractive index is coated on a substrate. There was a problem that was not very good.

In addition, as for the transparent antistatic coating, a conventional method of wet coating using a sol obtained by dispersing inorganic tin oxide (ATO), antimony zinc oxide (AZO), and indium tin oxide (ITO) in nano sizes is used. Although the inorganic material is a form in which nano particles are dispersed, a binder is required to fix it, and various defects of the coating film occur due to the compatibility problem between the binder and the inorganic material, resulting in haze and permeability. And not only the conductivity is lowered but also the coating conditions are difficult, there is a problem that the defect caused by the influence of humidity.

Recently, a method using a conductive polymer such as polyacetylene, polyaniline, polypyrrole, polythiophene, etc. is mainly used. Polythiophene, an electrically conductive polymer, has high light transmittance and stability against oxygen or heat. Therefore, many studies have been conducted, but there is still a great difficulty in making a desired solution after polymerization because of low solubility in both water and organic solvents. On the other hand, a method of obtaining a conductive polymer film having a uniform surface by using electrolytic polymerization has also been introduced, but this method has a problem that mass production is practically impossible and not suitable for industrial use.

Meanwhile, in order to simultaneously express antireflection and antistatic properties, a method of increasing the minimum reflectivity by wet coating a high refractive inorganic material, ATO, AZO, and ITO mentioned above and then wet coating a low refractive material has been used. There is a problem that the antireflective effect is improved only in the region, but the antireflective effect is not excellent in the entire visible light region, and there is a problem that the defective rate can be significantly reduced when performing the coating operation.

In addition, the Korean Patent Application Publication No. 2006-0045700 discloses a method of containing a conductive material in the low refractive layer, but this method is somewhat improved antistatic performance, but the refractive index of the low refractive layer is increased, the antireflection effect is increased It had a serious problem that was significantly reduced.

In order to solve such a conventional problem, in the present invention, by applying an antistatic layer under the high refractive index layer and the low refractive index layer, not only the antireflection but also the antistatic effect was simultaneously improved, and the refractive index layer was coated with a plurality of layers. The antireflection performance was excellent throughout all visible light.

One embodiment of the present invention (A) described; (B) a hard coating layer applied on the substrate; (C) a medium and high refractive index layer positioned on the hard coating layer and having a refractive index of 1.6 to 1.75 and containing a conductive polymer; (D) a high refractive index layer having a refractive index of 1.6 to 2.35 and positioned on the medium and high refractive index layers; And (E) an antireflection and antistatic film located on the high refractive index layer and including a low refractive index layer having a refractive index of 1.35 to 1.5.

In the present invention, (A) the substrate is polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetate cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinyl A film made of a resin selected from alcohol, polystyrene, polyethylene acetic acid, polyvinylidene chloride, polycarbonate, polyacryl, polymethylpentene, polysulfone, polyamide, and in particular, the substrate (A) has a visible light transmittance of 75 to 92%. And it is preferable to have a thickness of 10-1000 micrometers.

(B) the hard coating layer includes 20 to 50 parts by weight of an ultraviolet curable acrylate oligomer, 1 to 30 parts by weight of a monofunctional or polyfunctional acrylate monomer, 0.1 to 10 parts by weight of a photopolymerization initiator, and 20 to 80 parts by weight of a solvent. It is a layer coated with a composition for preparing a hard coating layer, and particularly preferably has scratch resistance of 4H or more and a thickness of 3 to 10 μm, and if less than 3 μm and more than 10 μm, the scratch resistance and the adhesion decrease, respectively. Problems may arise.

The content unit 'parts by weight' used as a unit of content in the present invention indicates a relative content as in the above-described embodiment, and a separate reference content for the relative parts by weight is not explicitly stated. However, those skilled in the art will not have any difficulty in determining the relative content of each component of the present invention.

Herein, the ultraviolet curable acrylate oligomer is preferably a polyfunctional urethane acrylate having a number average molecular weight of 500 to 5,000,

The reactive diluent may be methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, octyl ( Meta) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate , Stearyl (meth) acrylate, isostearyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-dodecylthioethyl (meth) acrylate, 2- Methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, urethane (meth) acrylate, polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di ( Meta) Arc Elate, bisphenol A-ethylene glycol di (meth) acrylate, 1, 4- butanediol di (meth) acrylate, pentacrylthiotol tetra (meth) acrylate, trimethylol propane tri (meth) acrylate, dipenta Lithitol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylic It is preferable that it is at least one mono- or polyfunctional acrylate monomer selected from the rate and N-vinylpyrrolidone,

The photoinitiator is α-hydroxycyclohexylphenylmethanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, hydroxydimethylacetophenone, 2-methyl -1 [4-methylthiophenyl] -2-morpholinopropane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,2-dimethoxy-1,2-di It is preferably at least one compound selected from phenylethan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and benzophenone.

The (C) medium and high refractive index layer is preferably a coating layer consisting of a urethane acrylate in which ITO, ATO or TiO ₂ is dispersed and a conductive polymer of the following formula.

In Formula 1, X is O, Se, S or NH, R1 and R2 are H, C3 ~ C15 alkyl group, C3 ~ C15 alkyl ether, halogen atom, or heterocycle containing one or more S or O .

Here, the particle size of ITO, ATO or TiO ₂ contained in the (C) medium-high refractive index layer is 10-20 nm, and in particular, the conductive polymer is preferably polythiophene.

In addition, the (D) high refractive index layer is preferably a coating layer made of a heat-drying resin selected from acrylic resin, epoxy resin, melamine resin mixed with ITO, ATO or TiO ₂ , more preferably an oil-based acrylic resin desirable.

In addition, the (E) low refractive index layer is at least one silane coupling agent selected from tetraalkoxysilane, trialkoxysilane and dialkoxysilane; It is preferable that it is a coating layer consisting of at least one fluorine silane selected from tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, and heptadecafluorodecyltriisopropoxysilane, and more preferably, (E) The low refractive index layer may further contain MgF ₂ .

Another aspect of the present invention (a) 20 to 50 parts by weight of an ultraviolet curable acrylate oligomer, 1 to 30 parts by weight of a reactive diluent, 0.1 to 10 parts by weight of a photopolymerization initiator and 20 to 80 parts by weight of a solvent for producing a hard coating layer Preparing a composition; (b) applying a hard coating layer on the substrate by wire coating or depositing the composition for preparing the hard coating layer on the substrate; (c) wet coating on the hard coating layer to apply a medium and high refractive index layer having a refractive index of 1.6 to 1.75 and a conductive polymer; (d) wet coating on the medium and high refractive index layers to apply a high refractive index layer having a refractive index of 1.6 to 2.35; (e) at least one silane coupling agent selected from tetraalkoxysilanes, trialkoxysilanes and dialkoxysilanes; And a sol-gel polymerization method for a composition liquid containing at least one fluorine silane selected from tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, and heptadecafluorodecyltriisopropoxysilane. Polymerizing to obtain a polysiloxane oligomer having a refractive index of 1.40 to 1.47 and a number average molecular weight of 1,000 to 3,000; And (f) wet coating the polysiloxane oligomer on the high refractive index layer to apply a low refractive index layer having a refractive index of 1.35 to 1.5.

Wherein step (a) comprises 20 to 50 parts by weight of an ultraviolet curable acrylate oligomer, 1 to 30 parts by weight of a monofunctional or polyfunctional acrylate monomer, 0.1 to 10 parts by weight of a photopolymerization initiator, and 20 to 80 parts by weight of a solvent. It is preferable to be carried out using a composition for preparing a hard coating layer,

However, the ultraviolet curable acrylate oligomer is a polyfunctional urethane acrylate having a number average molecular weight of 500 ~ 5,000,

The reactive diluent may be methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, octyl ( Meta) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate , Stearyl (meth) acrylate, isostearyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-dodecylthioethyl (meth) acrylate, 2- Methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, urethane (meth) acrylate, polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol D (meta) arc Relate, bisphenol A- ethylene glycol di (meth) acrylate, 1, 4- butanediol di (meth) acrylate, pentacrylthiotol tetra (meth) acrylate, trimethylol propane tri (meth) acrylate, and pent Acritritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylic At least one monofunctional or polyfunctional acrylate monomer selected from Rate and N-vinylpyrrolidone,

The photoinitiator is α-hydroxycyclohexylphenylmethanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, hydroxydimethylacetophenone, 2-methyl -1 [4-methylthiophenyl] -2-morpholinopropane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,2-dimethoxy-1,2-di It is preferable to select and use at least one compound selected from phenylethan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and benzophenone.

In addition, the step (c) is preferably carried out using a resin in which a urethane acrylate in which ITO, ATO or TiO ₂ is dispersed and a conductive polymer of the following formula is mixed.

[Formula 1]

In Formula 1, X is O, Se, S or NH, R1 and R2 are H, C3 ~ C15 alkyl group, C3 ~ C15 alkyl ether, halogen atom, or heterocycle containing one or more S or O

In addition, the wet coating of step (c) is coated by a conventional coating method, in particular bar coating method and heat-dried for 30 seconds to 2 minutes at 60 ~ 100 ° C, preferably 65 ~ 80 ° C After curing with UV.

In addition, the wet coating of the step (d) and (f) is performed only the coating and drying step of the step (c), there is no need to perform a separate UV curing.

In particular, it is preferable to excellently improve the final physical properties of the product by post-curing the final product for 1 to 3 hours after the step (f).

In addition, the polysiloxane oligomer obtained in step (e) may be diluted to be used so that the concentration of silicon oxide (SiO ₂₎ is calculated by the solid content in step (f) to 0.5 to 15% by weight.

Hereinafter will be described in more detail with respect to specific embodiments of the present invention.

First, the base material of the present invention is, for example, polyester film such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetate cellulose film, acetyl cellulose Transparent polymer such as butylate film, polyvinyl chloride film, polyvinyl alcohol film, polystyrene film, polyethylene acetate film, polyvinylidene chloride film, polycarbonate film, polyacryl film, polymethylpentene film, polysulfone film, polyamide film Films can be used.

The higher the transparency, the better the transparent polymer film is, and the visible light transmittance is preferably about 75 to 92%. That is, the transparent polymer film used for manufacturing the low reflection film should generally have a visible light transmittance of 75 to 92%. In addition, the thickness of the transparent polymer film is preferably 10 to 1000 µm, more preferably 20 to 200 µm.

In addition, in the present invention, the hard coating layer preferably has a thickness of 3 ~ 10㎛. In this case, the oligomer included in the hard coating composition may preferably have a number average molecular weight of 500 to 5000, and may be used after dilution with each monomer according to viscosity and physical properties.

The ends of the oligomers consist of acrylates or methacrylates and are divided into urethane acrylates, epoxy acrylates, polyester acrylates, acrylic acrylates, silicone acrylates or amino acrylates, etc., depending on the structure of the main chain. The structure of the oligomers determines the main properties of the final product.

Looking specifically at the properties of each, urethane acrylate includes a urethane bond as a repeating unit and usually has a flexible physical properties. In addition, there are various types, and depending on the type of isocyanate, it is divided into aliphatic urethane acrylate and aromatic urethane acrylate. Among these, the aliphatic urethane acrylate is yellowing type and has 2 to 6 functional groups. Aromatic urethane acrylates are yellowing type and have fast reactivity.

On the other hand, epoxy acrylate contains an epoxy bond in the main chain and causes yellowing, but has excellent hardness, solvent resistance, and curability. In addition, polyester acrylate is low in viscosity and excellent in weather resistance. Acrylic acrylate has good weather resistance and water resistance, especially adhesion to all materials. In addition, amino acrylate is used as a curing accelerator to improve the surface hardening and has the disadvantage of causing yellowing. Silicone acrylates are used as wetting agents, slip agents or release agents.

In the present invention, it is preferable to use a polyfunctional urethane acrylate capable of maximizing the surface hardness by improving the crosslinking density within the range of no yellowing of the oligomer and does not adversely affect the flexibility.

The content is preferably 20 to 50 parts by weight. If the content is less than 20 parts by weight, the surface hardness is not sufficient, and if it exceeds 50 parts by weight it is not preferable because the viscosity problem and coating adhesion decrease phenomenon occurs.

In the present invention, the ultraviolet reactive diluent is a monomer having a molecular weight of 500 or less and is mainly used for the purpose of lowering the viscosity of the ultraviolet curable composition. These monomers can be used alone or in combination, and show the difference in characteristics as follows depending on the number of functional groups.

First, monofunctional (monofunctional) monomers have the disadvantages of excellent adhesion and flexibility to the substrate, but low reactivity and stickiness when used in excess. Bifunctional monomers are most commonly used because of their suitable viscosity, reactivity and flexibility. Trifunctional monomers have the advantages of high hardness and reactivity. 4 to 6 functional monomers are excellent in reactivity and have high crosslinking density and excellent hardness, but have low flexibility.

According to the embodiment presented in the present invention, in order to improve the crosslinking density and curing rate within a range that does not impair flexibility, it is preferable to use a mixture of two or more acrylate monomers among the various monomers. For example, the trifunctional pentaerythritol triacrylate and the tetrafunctional pentaerythritol tetraacrylate may be mixed to improve the crosslinking density or the trifunctional trimethylol propane triacrylate may be added to the mixture to provide crosslinking density and The curing speed can be improved.

The content of the mono / polyfunctional acrylate monomer is preferably 1 to 30 parts by weight. If the content is less than 1 part by weight, there is almost no dilution effect, causing a problem of high viscosity. If the content is more than 30 parts by weight, flexibility is reduced, shrinkage of the cured layer occurs, and adhesion to the substrate is reduced.

It is preferable to use hydroxy ethyl acrylate excellent in sclerosis | hardenability among a monofunctional monomer as a monomer. This improves the adhesion to the base film without any primer treatment. At this time, the content is preferably 1 to 30% by weight, if it exceeds 30 parts by weight, since the volatilization is relatively high, the toxicity of the ultraviolet curable composition is increased.

In the present invention, the photopolymerization initiator only initiates the reaction by absorbing ultraviolet rays to generate free radicals, most of which do not participate in the reaction. Initiators vary the wavelength range absorbed according to the type, there are yellowing type and low yellowing type. In general, it absorbs a wavelength of 300 ~ 360nm, when used in combination of two or more to absorb a variety of wavelengths to promote reactivity. In addition, when the coating thickness is thin, the higher the content of the initiator, the better the reactivity, and when the coating thickness is thick, the total curing rate increases as the content decreases.

Examples of the photoinitiator in the present invention include α-hydroxycyclohexylphenylmethanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, hydroxydimethylacetophenone, 2-methyl-1 [4-methylthiophenyl] -2-morpholinopropane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,2-dimethoxy-1, Preference is given to using those containing 2-diphenylethan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide or benzophenone.

Any low yellow type initiator may be used without limitation, but it is preferable to use an α-hydroxyalkylphenone-based material, more preferably 1-hydroxycyclohexylphenyl ketone or α, α-dimethoxy-α-hydroxy Acetophenone is used individually or in mixture with each other.

The content of the photopolymerization initiator is preferably 0.1 to 10 parts by weight. When the content is less than 0.1 parts by weight, the reactivity is slow. When the content is more than 10 parts by weight, the reactivity is increased but the surface hardness is lowered.

Although the conventional method may be used, it is preferable to use the wire bar coating method. Specifically, the ultraviolet curable composition of the present invention was applied to a film, and then irradiated with ultraviolet air after heating and drying by irradiating hot air. The type of ultraviolet lamp used for ultraviolet irradiation is also not particularly limited as long as it is commonly used. The cured coating film is formed by irradiating ultraviolet light with a light quantity of 600 to 1000 mJ / cm ² while moving a lamp having an output of 60 to 240 W / cm by a belt conveyor.

In addition, looking at the optical design method and the coating method for the medium and high refractive index layer and the high refractive index layer, it is generally preferred to maintain the medium and high refractive index between 1.6 and 1.75 in the optical design. In order to obtain accurate refractive index in the optical design, a medium refractive index layer was prepared by dispersing a medium refractive urethane acrylate and a high refractive index TiO ₂ in a urethane acrylate. Depending on the refractive index, the ratio of the medium refractive index to the high refractive index varies.

And in order to express conductivity, it is especially preferable to mix polythiophene among conductive polymers.

In the present invention, the polymer used to form the conductive layer is a conjugated system having a heterocycle structure, and specifically, a heterocycle conjugated system including oxygen (O), selenium (Se), nitrogen (N) or sulfur (S) atoms. It is a polymer. More preferably, as the conjugated polymer of the heterocycle-based structure used in the present invention, pyrrole, thiophene, furan, serenophene and derivatives thereof may be used as represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1, X is O, Se, S or NH, and R1 and R2 are H, C3 ~ C15 alkyl group, C3 ~ C15 alkyl ether, halogen atom or at least one atom such as S, O together with a hydrocarbon It is a substituent of a structure that includes more than one and forms a cycle structure, and in some cases may include a functional group including its own doping function.

The high refractive layer includes inorganic materials such as TiO ₂ , ITO, ATO, and is preferably designed using the Macleod program, an optical design program. It is preferable that the particle size is 10-20 nm, and it is used by dispersing it in an organic solvent together with a trace amount of acrylic resin, and the amount of acrylic resin is used so that the amount of the acrylic resin provides only a binder function and does not affect maintaining high refractive index. desirable.

As for the wet coating of the outermost low refractive index layer, it is preferable that the low refractive index layer has a refractive index of 1.35 to 1.5, and if the refractive index is less than 1.35, the types of materials that can be used are extremely limited, whereas if the refractive index exceeds 1.5, There is a problem that the antireflection effect may be lowered when the refractive layer is combined with the high refractive layer.

In addition, in order to improve the antireflection effect, the difference in refractive index between the low refractive index layer and the high refractive index layer is preferably 0.1 or more. When the difference in refractive index is less than 0.1, the synergistic effect of the layers is not obtained in the antireflection effect, and in some cases, the antireflection The effect may be rather deteriorated. Therefore, the difference in refractive index between the low refractive index layer and the high refractive index layer is preferably 0.1 or more, and more preferably, the use of the low refractive index layer and the high refractive index layer having a refractive index difference of 0.2 or more is effective for antireflection. to be.

In order to prepare a low refractive index layer having such a refractive index, fluorine-based silane was introduced, tridecafluorooctyltriethoxysilane (trade name: DYNASYLAN F8261, Degussa-Huls), heptadecafluorodecyltrimethoxysilane (trade name: TSL8233) , Toshiba silicon, KBM-7803, Shinetsu), heptadecafluorodecyltriisopropoxysilane (trade name: XC95-A9715, Toshiba Silicone) and the like can be used.

When the fluorine-based silane alone is used, problems such as deterioration in hardness, wettability or poor adhesion may occur. In order to solve this problem, it is preferable to use a silane coupling agent in combination.

As a representative example of this, as the alkoxysilane, tetraalkoxysilane, such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane and ethyltrimethoxysilane , Ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, hep Yltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxy Silane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminoprop Triethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, etc. Trialkoxysilanes include, but are not limited to, dialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane.

In particular, at least one silane coupling agent selected from tetraalkoxysilane, trialkoxysilane and dialkoxysilane among the above-mentioned compounds; And at least one fluorine silane selected from tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, and heptadecafluorodecyltriisopropoxysilane by a sol-gel polymerization method. It is preferable to obtain a polysiloxane oligomer having a refractive index of 1.40 to 1.47 and a number average molecular weight of 1,000 to 3,000 by polymerization.

The polysiloxane oligomer can be concentrated or diluted if necessary, with the concentration of silicon oxide (SiO ₂ ) being calculated as the solids content in the polysiloxane solution, preferably from 0.5 to 15% by weight. If the concentration of silicon oxide is less than 0.5% by weight, it is difficult to obtain a desired thickness by a single coating process, and when it exceeds 15% by weight, it is difficult to secure the stability and storage of the solution.

The low refractive binder synthesized by the above may cause the surface tension to be lowered by fluorine-based silane, so that the wettability may not be completely improved, and a surface leveling agent may be introduced to solve this problem. It is preferable to use, in particular BYK-301, 306 can be used.

If the content thereof is preferably used in the range of 0.05 to 0.2% by weight, if it exceeds 0.2%, it may cause a decrease in reflectance and a decrease in adhesion. If the content is less than 0.05%, the leveling property may not be improved.

The mixing ratio of the silane coupling agent and the fluorine-based silane is extremely limited due to the above-mentioned reasons. To solve this problem, another low refractive filler MgF ₂ may be used. Specifically, the existing MgF ₂ can be applied by depositing using a pellet form.

According to one embodiment, MgF ₂ may be dispersed and milled at a size of 20 nm to prepare a 4% dispersion in IPA, which may be further lowered when mixed with the above-mentioned low refractive binder. In addition, the problem of the fluorine-based silane can be solved by increasing the amount used, but MgF ₂ is a filler form, so the hardness may be reduced when used in excess. The curing conditions may be carried out by post-curing in an oven by roll coating to 120 ℃ in the case of polyethylene terephthalate (PET) according to one embodiment.

Example

The following examples are only intended to illustrate the present invention in detail, the scope of the present invention is never limited to the embodiments can be interpreted.

Example 1 Application of Hard Coating Layer

7.25 parts by weight of 6-functional urethane acrylate oligomer (EB1290, SK-UCB Co. Ltd.), 6.33 parts by weight of 6-functional aromatic urethane acrylate oligomer (SC2100T, Miwon Co., Ltd.), 1.64 parts by weight of unsaturated polyfunctional acrylic Rate Monomer (PETIA, SK-UCB Co. Ltd), 0.89 parts by weight of unsaturated polyfunctional acrylate monomer (TMPTA, SK-UCB Co. Ltd), 0.94 part by weight of 5-functional acrylate monomer (DPHA, SK-UCB Co. Ltd.). Ltd), 1.96 parts by weight of acrylate monomer (HDDA, SK-UCB Co. Ltd), 0.35 parts by weight of acrylate monomer (TPGDA, SK-UCB Co. Ltd), and then 39.38 parts by weight of methyl ethyl ketone, 39.38 parts by weight Diluted in toluene and then dissolved. 1.27 parts by weight of a photopolymerization initiator (Irgacure 184, Ciba-Geigy), 0.42 parts by weight of a photopolymerization initiator (Irgacure 907, Ciba-Geigy) and 0.22 parts by weight of a photopolymerization initiator (TPO, Ciba-Geigy) were added and stirred. After preparing the mixed solution, the wire directly coated on PET film and then dried at 70 ° C., and then irradiated with ultraviolet (600mJ / ㎠) to perform a crosslinking reaction to form a hard coating layer having a coating thickness of 5㎛. The physical properties were evaluated according to the following items and the results are shown in Table 1 below.

Scratch resistance

It was visually discriminated after 10 round trips using steel wool of # 0000 under a load of 1 kg.

A +: No scratches, very good

A: 1-3 thick lines, good

B: 3 or more string scratches

Pencil hardness

Under the conditions of Japanese Industrial Standards (JIS-K5400), evaluation was made using a pencil hardness meter (manufactured by Shee) and a pencil of various standards (manufactured by Mitsu-Bishi). The load in the measurement is 1 kg and the size of the pencil used is 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, 9H.

Adhesion

After cross-cutting the size of 10 mm X 10 mm on the surface of the coating film at intervals of 1 mm, test the adhesion force using Nichiban tape (Nichiban, Japan) and determine the number remaining without peeling. Evaluated.

Item evaluation Wear resistance A Pencil hardness 3H Adhesion 100/100

Example 2: Application of Medium and High Index Layers

In order to apply the medium and high refractive layers to the wear-resistant film prepared in Example 1, a medium and high refractive index layer was prepared by dispersing a medium refractive urethane acrylate and a high refractive index TiO ₂ in a urethane acrylate.

2.5 parts by weight of DPHA (SK-Cytech) having a refractive index of 1.4897, 0.15 parts by weight of a photopolymerization initiator (Irgacure 184, Ciba-Geigy), and 4.7 parts by weight of TiO ₂ powder having a refractive index of 1.89 (20-30 nm), followed by dispersion. 58 parts by weight of propyl alcohol, 20 parts by weight of acetone, and 14.8 parts by weight of ethyl cellosolve were diluted.

8 parts by weight of polythiophene (Bayer, Baytron PH), a conductive polymer, is mixed with 100.15 parts by weight of the prepared medium and high refractive solution, followed by stirring. This was coated with a wire bar (# 7) and heat-dried at 70˚C, followed by UV irradiation.

Example 3: Application of High Refractive Index Layer

8.5 parts by weight of TiO ₂ powder having a refractive index of 1.89 (particle size: 20-30 nm) was mixed and dispersed in 50 parts by weight of ethyl acetate, 30 parts by weight of N-propyl alcohol, and 11.5 parts by weight of ethyl cell solution. 100 parts by weight of the high refractive index solution, 1.0 part by weight of the heat-drying acrylic resin AA-952V (Aekyung Industrial Co., Ltd.) was mixed and stirred.

The high refractive index coating liquid was coated on the film coated with the medium and high refractive index layers prepared in Example 2 with a wire bar (# 5), followed by heat drying at 70 ° C., followed by UV irradiation.

Example 4 Coating of Low Refractive Index Layer (1)

65 parts by weight of tetraethoxysilane, 15 parts by weight of tridecafluorooctyltriethoxysilane (trade name: DYNASYLAN F8261, Degussa-Huls), 0.04 part by weight of nitric acid, 75 parts by weight of water, 90 parts by weight of ethanol at 60 ° C The polymerization was carried out for 2 hours on a conditional vitreous reactor to obtain a polysiloxane oligomer. To 30 parts by weight of the low refractive index preparation liquid, 0.02 parts by weight of BYK-306 and 10 parts by weight of MgF 2 dispersion (IPA 4%) were mixed, followed by mixing 120 parts by weight of IPA. The low refractive solution was coated with a wire bar (# 3) on the film coated with the high refractive index prepared in Example 3 and then cured to 120 ° C. and then after curing in an oven.

Example 5 Application of Low Refractive Index Layer (2)

120 parts by weight of tetraethoxysilane, 0.04 parts by weight of nitric acid, 110 parts by weight of water, and 90 parts by weight of ethanol were subjected to polymerization for 2 hours on a 50 ° C. conditioner to obtain a polysiloxane oligomer. 10 parts by weight of the MgF ₂ dispersion (IPA 4%) was mixed with 30 parts by weight of the low refractive index coating solution, and then 130 parts by weight of IPA were mixed. The low refractive solution was coated with a wire bar (# 3) on the film coated with the high refractive index prepared in Example 3, and then cured at 120 ° C. and then cured in an oven.

Comparative Example 1

In order to compare the reflectance for the conventional film, antistatic was implemented in a conventional manner. Specifically, proceed in the same manner as in Examples 1 to 3, 5, but does not use the conductive polymer in Example 2, instead MgF ₂ dispersion (30g) in a low refractive index coating solution containing a polysiloxane oligomer prepared in Example 5 IPA 4%) 10g was mixed and then 130g of IPA was mixed, and 6g of polythiophene, which is a conductive polymer, was further mixed. The low refractive solution was coated with a wire bar (# 3) on the film coated with the high refractive index prepared in Example 3 and then cured to 120 ° C. and then after curing in an oven.

reflectivity

The spectral reflectance at 400-700 nm was measured using the spectrometer UV3300 (made by Hitachi Corporation).

Water resistance

An impregnation experiment was conducted for 150 hours while maintaining an aqueous solution having a concentration of 10% sodium chloride at a temperature of 35 ° C. Swelling, peeling and discoloration of the appearance were visually observed and evaluated.

Haze

It measured by Hazemeter HM-150 (Murakami Corporation) based on JISK7105 standard.

Solvent resistance

After immersion for 2 hours in toluene, methyl ethyl ketone at room temperature, it was evaluated as poor or good depending on the physical properties of the coating film.

Exterior

The film material after coating was visually evaluated to determine whether there were any unsatisfactory elements such as foreign matter or dust, and judged as the presence or absence thereof. Table 2 shows the test results of the specimens prepared in Examples 4 and 5 and Comparative Example 1.

Item Example 4 Example 5 Comparative Example 1 reflectivity 0.9% (single side) 1.1% (single side) 2.2% (single side) conductivity 1 * 10 ¹⁰ (Ω / □) 1 * 10 ¹⁰ (Ω / □) 1 * 10 ¹⁰ (Ω / □) Water resistance Good Good Good Haze 0.5% 0.3% 0.3% Pencil hardness 2H 2H 2H Adhesion 100/100 100/100 100/100 Scratch resistance A A A Solvent resistance Good Good Good Exterior Good Good Good

The anti-reflective and antistatic transparent film produced according to the present invention could overcome the defect rate caused by the direct coating on the substrate and the limitation of the coating conditions by the type of the substrate, as well as increase the productivity due to the film coating, as well as in various displays. It showed an effect that can easily meet the required shape and size.

Claims (11)

(A) description; (B) A composition for producing a hard coat layer, which is placed on the substrate and comprises 20 to 50 parts by weight of an ultraviolet curable acrylate oligomer, 1 to 30 parts by weight of a reactive diluent, 0.1 to 10 parts by weight of a photopolymerization initiator, and 20 to 80 parts by weight of a solvent. Hard coating layer is applied to; (C) a layer having a medium refractive index and a high refractive index positioned on the hard coating layer and composed of a urethane acrylate in which ITO, ATO or TiO ₂ is dispersed and a conductive polymer of the following formula, and having a refractive index of 1.6 to 1.75; (D) a high refractive index layer which is located on the layer of the medium refractive index and high refractive index and the refractive index is 1.6 ~ 2.35; And (E) an antireflection and antistatic film comprising a low refractive index layer on the high refractive index layer and having a refractive index of 1.35 to 1.5, The ultraviolet curable acrylate oligomer is a polyfunctional urethane acrylate having a number average molecular weight of 500 to 5,000, The reactive diluent may be methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, octyl ( Meta) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate , Stearyl (meth) acrylate, isostearyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-dodecylthioethyl (meth) acrylate, 2- Methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, urethane (meth) acrylate, polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di ( Meta) Arc Elate, bisphenol A-ethylene glycol di (meth) acrylate, 1, 4- butanediol di (meth) acrylate, pentacrylthiotol tetra (meth) acrylate, trimethylol propane tri (meth) acrylate, dipenta Litritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate And one or more monofunctional or polyfunctional acrylate monomers selected from N-vinylpyrrolidone, The photoinitiator is α-hydroxycyclohexylphenylmethanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, hydroxydimethylacetophenone, 2-methyl -1 [4-methylthiophenyl] -2-morpholinopropane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,2-dimethoxy-1,2-di Anti-reflective and antistatic film, characterized in that at least one compound selected from phenylethan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and benzophenone. [Formula 1]

In Formula 1, X is O, Se, S or NH, R1 and R2 are H, C3 ~ C15 alkyl group, C3 ~ C15 alkyl ether, halogen atom, or heterocycle containing one or more S or O . delete delete The method of claim 1, wherein the (A) substrate is polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetate cellulose, acetyl cellulose butyrate, polyvinyl chloride, A film made of a resin selected from polyvinyl alcohol, polystyrene, polyethylene acetic acid, polyvinylidene chloride, polycarbonate, polyacrylic, polymethylpentene, polysulfone, polyamide; (D) the high refractive index layer is a coating layer made of a heat-drying resin selected from acrylic resin, epoxy resin, melamine resin mixed with ITO, ATO or TiO ₂ ; The low refractive index layer (E) may comprise at least one silane coupling agent selected from tetraalkoxysilane, trialkoxysilane and dialkoxysilane; Anti-reflective and antistatic, characterized in that the coating layer consisting of at least one fluorine-based silane selected from tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriisopropoxysilane film. The method of claim 4, wherein the substrate (A) has a visible light transmittance of 75 to 92% and a thickness of 10 to 1000 mu m; (B) the hard coating layer has a scratch resistance of 4H or more and a thickness of 3 ~ 10㎛; (C) the particle size of ITO, ATO or TiO ₂ included in the layer of medium refractive index and high refractive index is 10-20 nm and the conductive polymer is polythiophene; The (E) low refractive index layer is an antireflection and antistatic film, characterized in that it further comprises MgF ₂ . (a) preparing a composition for preparing a hard coating layer comprising 20 to 50 parts by weight of an ultraviolet curable acrylate oligomer, 1 to 30 parts by weight of a reactive diluent, 0.1 to 10 parts by weight of a photopolymerization initiator, and 20 to 80 parts by weight of a solvent; (b) applying a hard coating layer on the substrate by wire coating or depositing the composition for preparing the hard coating layer on the substrate; (c) wet coating on the hard coating layer to apply a layer having a medium refractive index and a high refractive index having a refractive index of 1.6 to 1.75 and a conductive polymer; (d) applying a high refractive index layer having a refractive index of 1.6 to 2.25 by wet coating on the layer of medium refractive index and high refractive index applied in step (c); (e) at least one silane coupling agent selected from tetraalkoxysilanes, trialkoxysilanes and dialkoxysilanes; And at least one fluorine silane selected from tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, and heptadecafluorodecyltriisopropoxysilane by a sol-gel polymerization method. Polymerizing to obtain a polysiloxane oligomer having a refractive index of 1.40 to 1.47 and a number average molecular weight of 1,000 to 3,000; And (f) wet coating the polysiloxane oligomer on the high refractive index layer applied in step (d) to apply a low refractive index layer having a refractive index of 1.35 to 1.5. The method of claim 6, wherein step (e) is performed by polymerizing at 30 to 50 ° C. for 30 minutes to 4 hours; Calculating the solids content in step (f) and diluting the polysiloxane oligomer so that the concentration of silicon oxide (SiO ₂₎ is 0.5 to 15% by weight; The wet coating of step (c) is carried out by coating with a bar coating method and heat-curing at 65-80 ° C. for 30 seconds to 2 minutes, followed by UV curing; The wet coating of steps (d) and (f) is carried out by coating with a bar coating method and heat drying at 65-80 ° C. for 30 seconds to 2 minutes; After the step (f) (g) further comprising the step of post-curing the final product for 1 to 3 hours, characterized in that it comprises an anti-reflective and antistatic film. According to claim 7, wherein the step (a) is 20 to 50 parts by weight of UV curable acrylate oligomer, 1 to 30 parts by weight of monofunctional or polyfunctional acrylate monomer, 0.1 to 10 parts by weight of photopolymerization initiator and 20 to 80 It is carried out using a composition for producing a hard coating layer containing a weight part of the solvent; The ultraviolet curable acrylate oligomer is a polyfunctional urethane acrylate having a number average molecular weight of 500 to 5,000, The reactive diluent may be methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, octyl ( Meta) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate , Stearyl (meth) acrylate, isostearyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-dodecylthioethyl (meth) acrylate, 2- Methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, urethane (meth) acrylate, polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di ( Meta) Arc Elate, bisphenol A-ethylene glycol di (meth) acrylate, 1, 4- butanediol di (meth) acrylate, pentacrylthiotol tetra (meth) acrylate, trimethylol propane tri (meth) acrylate, dipenta Litritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate And one or more monofunctional or polyfunctional acrylate monomers selected from N-vinylpyrrolidone, The photoinitiator is α-hydroxycyclohexylphenylmethanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, hydroxydimethylacetophenone, 2-methyl -1 [4-methylthiophenyl] -2-morpholinopropane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,2-dimethoxy-1,2-di Method for producing an antireflective and antistatic film, characterized in that at least one compound selected from phenylethan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and benzophenone. The method according to claim 8, wherein the step (c) is performed by applying a resin in which urethane acrylate in which ITO, ATO or TiO ₂ is dispersed and a conductive polymer of the following formula is applied. Manufacturing Method: [Formula 1]

In Formula 1, X is O, Se, S or NH, R1 and R2 are H, C3 ~ C15 alkyl group, C3 ~ C15 alkyl ether, halogen atom, or heterocycle containing one or more S or O . 10. The method of claim 9, wherein as the substrate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetate cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinyl alcohol Using a film made of a resin selected from polystyrene, polyethylene acetate, polyvinylidene chloride, polycarbonate, polyacryl, polymethylpentene, polysulfone, polyamide; The step (c) is a method for producing an anti-reflective and antistatic film, characterized in that is carried out by applying a heat-drying resin selected from acrylic resin, epoxy resin, melamine resin mixed with ITO, ATO or TiO ₂ . The method of claim 10, wherein the substrate has a visible light transmittance of 75 to 92% and a thickness of 10 to 1000 ㎛; The hard coating layer has a scratch resistance of 4H or more and a thickness of 3 to 10 μm; The particle size of ITO, ATO or TiO ₂ contained in the layer of medium refractive index and high refractive index is 10-20 nm and the conductive polymer is polythiophene; The low refractive index layer is a method for producing an antireflection and antistatic film, characterized in that it further comprises MgF ₂ .

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