KR101504906B1 - Paint for transparent film and transparent film coated substrate - Google Patents

Abstract

The present invention relates to an additive base material capable of forming a transparent film having a low refractive index that is excellent in adhesion to a base material, strength, water repellency and whitening resistance, or a transparent film reflecting the shape of a lower layer surface, for example, There is provided a transparent coating film-forming coating material which can form a transparent film having the same unevenness as the unevenness on the surface thereof, and which can be suitably used for forming a transparent film having excellent antireflection performance and anti-glare performance. The present invention also provides a transparent coating film-forming composition comprising a polymerization initiator of a low refractive index fine particle and a matrix forming component and a solvent, wherein (i) when the low refractive index fine particles are treated with a silane coupling agent, the refractive index of the surface treated low refractive index fine particles (Ii) the matrix-forming component is a silicone-based resin and / or an acrylic-based resin and the concentration of the matrix-forming component is from 0.5 to 20 wt% as solid content, and the concentration of the low- refractive-index fine particles is in the range of from 0.1 to 10 wt% % Based on the total weight of the transparent coating film.

Transparent coating, paint, substrate, coating, matrix, silane

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent film-

The present invention relates to a transparent-film-forming paint made from low-refractive-index fine particles, a matrix-forming component, a polymerization initiator and a solvent, a base material, and a transparent film sub-base made of a transparent film formed using the above-mentioned transparent-

More specifically, it is possible to form a transparent film having a low refractive index that is excellent in adhesion to a substrate, strength, water repellency, whitening resistance, and the like, and a transparent film reflecting the added base material or the shape of the lower layer surface, It is possible to form a transparent coating film having the same concavo-convex surface as that of the concavo-convex pattern, and for this purpose, a transparent coating film-forming coating material which can be preferably used for forming a transparent film having excellent antireflection performance, And a transparent film secondary substrate.

Conventionally, it has been known to form an antireflection film on the surface of a substrate such as a glass, a plastic sheet, or a plastic lens in order to prevent reflection of the substrate surface. For example, a fluororesin, magnesium fluoride There is known a method for forming an antireflection film by coating a coating liquid of the same low refractive index material on the surface of a substrate of glass or plastic or applying a coating liquid containing fine particles of low refractive index such as fine silica particles to the surface of a substrate (for example, 7-133105 (Patent Document 1), etc.). [0004] It is also known to form a high refractive index film including fine particles of high refractive index or the like below the antireflection coating in order to improve antireflection performance. In order to impart antiglare property, the surface of the antireflection film is formed with irregularities.

Patent Document 1: JP-A-7-133105

However, in the conventional methods, transparency having a preferable range of antireflection performance and antiglare performance such as excellent in the adhesion, strength, transparency, whitening resistance and the like to the substrate is small and the allowable range of the coating material concentration, viscosity, solvent, coating method, It has been difficult to form the coating with excellent reproducibility.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a coating composition containing a low refractive index fine particle treated with a specific silane coupling agent at a predetermined concentration and containing a specific matrix- , Water repellency and whitening resistance, and a transparent film is formed on the lower layer film having irregularities on the added surface, the surface of the transparent film is planarized to form a transparent film having the same irregularities as the lower irregularities And to develop a transparent coating material and a coating material.

An object of the present invention is to provide a coating film for forming a transparent film having the following constitution.

[1] A transparent film-forming coating composition comprising a low refractive index fine particle, a matrix forming component, a polymerization initiator and a solvent,

(I) the low refractive index fine particles are treated with a silane coupling agent, the refractive index of the surface treated low refractive index particles is in the range of 1.20 to 1.45, the concentration of the low refractive index fine particles is in the range of 0.1 to 10%

(Ii) The coating for forming a transparent film, wherein the matrix-forming component is a silicone resin and / or an acrylic resin and the concentration of the matrix-forming component is in a range of 0.5 to 20% by weight as solids.

[2] The coating material for forming a transparent film according to [2], wherein the matrix-forming component is a resin obtained by polymerizing a silicone-based resin monomer having three or more functional groups and / or an acrylic-

[3] The coating material for forming a transparent film according to any one of [1] to [3], wherein the silicone-based resin is a silicone resin having a (meth) acryloyl group and / or a (meth) acrylate resin having an acrylic resin having a (meth) acryloyl group.

The matrix-forming component includes a resin in which a bifunctional or less resin monomer is polymerized as a water-repellent agent, and the resin is a silicone resin having a (meth) acryloyl group, a fluororesin having a (meth) acryloyl group, A long-chain acrylic resin having a (meth) acryloyl group, and a siloxane-based acrylic resin.

[5] The transparent coating film-forming coating composition according to any one of [1] to [4], wherein the transparent coating film forming coating material comprises (i) a bifunctional and / or trifunctional acrylic resin monomer when the matrix is a silicone resin, Wherein the acrylic resin is a stress-relieving agent.

[6] The coating film for forming a transparent film, wherein the polymerization initiator comprises a phosphine-based polymerization initiator or a cation-based photopolymerization initiator.

[7] The solvent is a mixed solvent of a solvent (A) having a boiling point of 50 to 100 ° C. and a solvent (B) having a boiling point of 100 to 200 ° C. The content of the solvent (A) %, And the content of the solvent (B) is in the range of 10 to 50 wt%.

[8] The silane coupling agent having the surface treated with the low refractive index fine particles is a silane coupling agent having at least one functional group selected from a (meth) acryloyl group, an epoxy group (glycidyl group), a urethane group, an amino group and a fluorine group By weight based on the total weight of the coating composition.

[9] A transparent film secondary substrate made of a transparent film formed by using the transparent film forming coating material of any one of [1] to [9] above a substrate.

Hereinafter, the transparent coating film-forming coating material according to the present invention will be described in more detail.

Coating for forming a transparent film

The transparent coating film-forming paint according to the present invention is prepared from low refractive index fine particles, a matrix forming component, a polymerization initiator and a solvent.

Low refractive index fine particles

In the present invention, low refractive index fine particles surface-treated with a silane coupling agent or acrylic ester or the like are used.

The average particle size of the low refractive index fine particles used is preferably in the range of 20 to 500 nm, more preferably 40 to 100 nm, and the refractive index is preferably in the range of 1.15 to 1.40.

As long as the low-refractive index fine particles of low refractive index particularly limited _{but, SiO 2, Al 2 O 3} , TiO 2, ZrO 2, SnO 2 and CeO _2, etc. of the inorganic oxide or its composite oxides, for example SiO ₂ -Al ₂ O ₃ , TiO ₂ -Al ₂ O ₃ , TiO ₂ -ZrO ₂ , SiO ₂ -TiO ₂ , SiO ₂ -TiO ₂ -Al ₂ O _3, and the like can be used. -133105, WO 00/37359, JP-A-2001-233611, and JP-A-2003-192994 are silica-based fine particles having a cavity therein and have a low refractive index, are fine particles in a colloidal region, It is preferable to adopt it as being excellent.

Specifically, the fine particles are in the form of hollow spheres having cavities inside the outer ends having pores, and silica-based fine particles containing a solvent and / or a gas in the production of the fine particles are preferable in the cavities. It is preferable that the outer end thickness is usually in the range of 1 nm to 50 nm and is in the range of 1/50 to 1/5 of the average particle size. On the other hand, the outer end layer is preferably composed of only silica. On the other hand, when the transparent oxide (MO _x ) is included as described above, MO _x / SiO ₂ of 0.0001 to 0.2 is preferably high in transparency.

Examples of the silane coupling agent include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane , Vinyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltris (? -Methoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl- , 3,3-trifluoropropyldimethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? -Glycidoxymethyltrimethoxysilane,? -Glycidoxymethyl triethoxy Silane,? -Glycidoxyethyltrimethoxysilane,? -Glycidoxyethyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? - (? -Glycidoxymethoxy) propyltrimethoxysilane, [gamma] - (meth) acrylooxymethyltrimethoxysilane, [gamma] - (Meth) acryloyloxyethyltrimethoxysilane,? - (meth) acryloxyethyltriethoxysilane,? - (meth) acryloxypropyltrimethoxysilane, Silane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, Hexyltriethoxysilane, octyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyl, hexyltriethoxysilane, hexyltriethoxysilane, hexyltriethoxysilane, hexyltriethoxysilane, Perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, triple uro-propyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane , N-beta (aminoethyl) gamma -aminopropyl N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, and methyltrichlorosilane.

In particular, the silane-based coupling agent having at least one functional group selected from a (meth) acrolyl group, an epoxy group (glycidyl group), a urethane group, an amino group and a fluorine group is excellent in reactivity with the low refractive index fine particles, Surface treatment can be carried out, and the obtained surface-treated low refractive index fine particles have excellent dispersibility in a coating material and a transparent coating film. On the other hand, the surface-treated low refractive index fine particles are excellent in reactivity with the following matrix forming component, and thus a transparent coating excellent in transparency, strength, abrasion resistance and the like can be obtained.

On the other hand, the low refractive index fine particles may be treated with a hydrophobic acrylic ester resin having a hydrophilic property.

Examples of the polyfunctional acrylic ester resin having hydrophobicity include pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentane erythritol hexaacrylate, Methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl acrylate, n-stearyl acrylate, , 6-hexanediol dimethacrylate, perfluorooctylethyl methacrylate, trifluoroethyl methacrylate, and urethane acrylate.

As a surface treatment method of the low refractive index fine particles, for example, a method of adding a silane coupling agent described above to an alcohol dispersion of silica-based fine particles, adding water thereto, and optionally adding a catalyst for hydrolysis of a silane coupling agent For example, a method of hydrolyzing an organosilicon compound by adding an acid or an alkali. When the hydrophobic multi-functional acrylic ester resin having hydrophobicity is used, the multi-functional acrylic ester resin is dispersed in the alcohol dispersion of the silica-based fine particles to attach the multi-functional acrylic ester to the surface of the low refractive index micro- Acrylic ester is polymerized to coat the particle surface of the low refractive index fine particles.

The organic solvent dispersion of the low refractive index fine particles surface-treated by substitution with an organic solvent can be obtained. As the organic solvent, the following solvents are preferably used.

At this time, the weight ratio (weight of the silane-based coupling agent or the weight of the low-refractive-index fine particles as the solid content of the polyfunctional acrylic ester resin having hydrophobicity) to the silane-based coupling agent or the polyfunctional acrylate ester resin having hydrophobicity But it is preferably in the range of 0.05 to 1, preferably 0.1 to 0.5, depending on the average particle size of the refractive index fine particles. When the weight ratio is smaller than the above range, the dispersibility and stability are low in a polar solvent, the stability of the coating becomes insufficient, and when the low refractive index fine particles aggregate in the paint to form a film, the film is whitened and the adhesion to the substrate and the hardness It can become insufficient. If the weight ratio is more than 1, the hydrophobic property increases depending on the kind of the matrix forming component to be used, so that the low refractive index fine particles surface-treated in the paint are aggregated and the film becomes whitened when the film is formed, so that the hardness of the adhesive film with the substrate becomes insufficient. On the other hand, when the amount of the surface treatment agent having a higher refractive index than that of the low refractive index fine particles is high, the refractive index of the surface treated low refractive index fine particles is increased, so that the refractive index of the obtained transparent coating film is increased and the antireflection performance and contrast are not improved.

The average particle size of the low refractive index fine particles after surface treatment is not substantially changed but slightly increased (depending on the throughput). When the average particle size of the low refractive index fine particles is remarkably increased as compared with the low refractive fine particles before the treatment, the throughput increases and the refractive index of the fine particles may be impaired.

The method for measuring the particle size of the low refractive index fine particles and the surface treated low refractive index particles used in the present invention is a method of measuring the low refractive index fine particles and the surface treated low refractive index fine particles by transmission electron microscope (TEM) And the particle size is calculated in consideration of the magnification, and the average value is obtained.

The refractive index of the low refractive index particle size after the surface treatment is in the range of 1.20 to 1.45, preferably in the range of 1.20 to 1.35.

The refractive index after the surface treatment tends to increase and it is difficult for the refractive index to become less than the lower limit of the above range. When the refractive index is high, the antireflection performance becomes insufficient as compared with the refractive index of the base material or the underlayer film, and the reflectance of the transparent film becomes high, so that the bright part contrast becomes insufficient.

The method of measuring the refractive index of the low refractive index fine particles and the surface treated low refractive index fine particles used in the present invention

(1) The dispersion medium is evaporated with a low refractive index fine particle or a surface treated low refractive index fine particle dispersion using an iveporator.

(2) Dry it at 120 ° C to make a powder.

(3) Drop the standard refraction solution whose refractive index is already known on a 2 or 3 drop glass plate, and mix the powder.

(4) The operation of the above (3) is performed on each standard refraction liquid, and the refractive index of the standard refraction liquid when the mixture becomes transparent becomes the refractive index of the particles.

The concentration of the low refractive index fine particles surface-treated in the coating film for forming a transparent coating film is preferably 0.1 to 1.0% by weight, preferably 0.2 to 5% by weight, more preferably 0.5 to 3.0% by weight in terms of solid content. Even if the concentration is low, a transparent coating film having a low refractive index is not obtained, so that the reflectance of the transparent coating film becomes high, the antireflection performance becomes insufficient and the bright part contrast becomes insufficient. Even when the concentration of the particles is increased, the coating property is lowered, and it becomes difficult to form a uniform transparent film, so that the flatness of the surface is lost or voids are formed in the transparent film, and the phase value of the transparent film due to scattering of light is increased, Resulting in insufficiency.

The matrix forming component

In the present invention, a silicone resin and / or an acrylic resin is used as a matrix forming component.

[Silicone resin]

Examples of the silicone resin include a copolymer of a (meth) acrylic resin with an organosilicon oxide having a functional group such as a glycidoxy group or a (meth) acryloyl group and a hydrolyzate thereof, or a mixture of radical polymerization and hydrolysis, Resin, a methylphenyl-based silicone resin, an acryl-modified silicone resin, and an epoxy-modified silicone resin may be used.

Examples of the organic silicon compound having the functional group include? -Glycidoxymethyltrimethoxysilane,? -Glycidoxymethyltriethoxysilane,? -Glycidoxyethyltrimethoxysilane,? -Glycidoxyethyltriethoxysilane, Glycidoxypropyltrimethoxysilane,? - (? - glycidoxyethoxy) propyltrimethoxysilane,? - (meth) acryloxy (Meth) acryloyloxyethyltriethoxysilane,? - (meth) acryloxyethyltriethoxysilane,? - (meth) acryloxyethyltrimethoxysilane, (Meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, and the like.

Among these silicone resins, a resin obtained by polymerizing a silicone resin monomer having three or less functional groups is preferable. Such a silicone resin has a large number of reactive functional groups (bonded water), and through this, bonding with low refractive index fine particles surface-treated between matrix resin components can be strongly bonded to form a transparent coating having excellent strength and abrasion resistance.

In the present invention, a silicone resin having a (meth) acryloyl group as a functional group is preferably used as a resin component for forming a matrix to strongly bond the surface-treated low refractive index fine particles in between.

As the silicone resin having a (meth) acryloyl group, a silicone solution (product name: X-12-2400, manufactured by Shin-Etsu Chemical Co., Ltd.) and a silicone coat solution (product name: UVHC1101 manufactured by GE Kogyo Silicone Co., Ltd.) . These are tetrafunctional silicone resins.

[Acrylic resin]

Examples of the acrylic resin include dipentaerythritol hexaacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetra (meth) acrylate , Dipentaerythritol hexaacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl acrylate , n-stearyl acrylate, 1,6-hexanediol dimethacrylate, perfluorooctylethyl methacrylate, trifluoroethyl methacrylate, and urethane acrylate.

The acrylic resin is preferably a resin obtained by polymerizing an acrylic resin monomer having three or more functional groups. Such an acrylic resin has a large number of reactive functional groups (bonded water), so that the bonding with the surface-treated low refractive index fine particles between the resins is strongly adhered to form a transparent coating excellent in strength and abrasion resistance.

In the present invention, among them, an acrylic resin having a (meth) acryloyl group as a functional group is a resin having high reactivity and is preferable for strongly bonding the surface-treated low refractive index fine particles between the resins.

As the acrylic resin having a (meth) acryloyl group, there can be used a publicly known phosphorescent agent: product name: Rid acrylate DPE-6A (dipentaerythritol hexaacrylate), a commercial phosphorescent agent: Product name: Rid acrylate DPE-4A Tetraacrylate) and the like.

The concentration of the matrix forming component contained in the coating film for forming a transparent film is preferably 0.5 to 20% by weight, and more preferably 0.8 to 10% by weight, in terms of solid content.

When the concentration of the matrix-forming component is decreased, the thickness of the transparent coating film becomes insufficient, and when it is repeatedly applied, a uniform film thickness is obtained and the appearance of the transparent coating film is scratched.

When the concentration of the matrix-forming component is increased, the film thickness becomes thick, and a uniform film thickness is obtained, and the appearance of the transparent coating film is scratched. Particularly, in the case of forming a transparent film having antiglare property by using a base material having irregularities on the surface of the substrate or the underlayer film, it is preferable that the concentration of the matrix forming component in the transparent film-forming coating material is in the range of 1.0 to 3.0% by weight as solid content. Within this range, a transparent film having surface irregularities can be formed by reflecting irregularities on the surface of the substrate or the underlayer film.

On the other hand, the content of the matrix-forming component in the above-mentioned particles is in the range of 30 to 99% by weight, preferably 40 to 98% by weight, as the solid content of the matrix component in the obtained transparent coating film and the amount of the surface-treated low refractive index fine particles The content of the surface-treated low refractive index fine particles in the transparent coating film is from 1 to 70% by weight, preferably from 2 to 60% by weight, in terms of solid content.

With this weight ratio, for the purpose of the present invention, it is possible to form a transparent film of a low-refractive-index film excellent in adhesion to a matrix-forming substrate, strength, water repellency and whitening resistance, and a transparent film In this case, the surface of the transparent coating film is planarized, and a transparent film having the same concavity and convexity as that of the underlying film can be formed.

[Water repellent]

Preferably, in the present invention, it is preferable that the coating material contains a resin obtained by polymerizing a resin monomer having two or less functional groups as a water-repellent agent. It is preferable that the resin is at least one selected from a silicone resin having a (meth) acryloyl group, a fluorine resin having a (meth) acryloyl group, a long chain alkyl resin having a (meth) acryloyl group, and a siloxane- Do.

When such a resin is used, the compatibility with the matrix component is low and it appears to be located on the surface layer of the transparent film, whereby water repellency (contact angle of water drops of 90 degrees or more) is expressed on the surface layer of the transparent film and fingerprints, sebum, It is possible to prevent the contaminants from adhering to the surface, and to wipe off even if attached.

Examples of the silicone resin having a (meth) acryloyl group include a resin obtained by adhering a (meth) acryloyl group to one end of a polysiloxane, and for example, a modified silicone oil: X-24- 8201 (functional group equivalent 2100), X-22-174-DX (functional group equivalent 4600), X-24-8201, X-22-2426 (functional group equivalent 12000) and the like can be appropriately used.

NK Ester A-NOD-N (1,9-nonanediol diacrylate) manufactured by Shinkouchon Kogyo Co., Ltd .: NK Ester A- DOD (1,10-decanediol acrylate) and the like can be suitably used.

As the siloxane-based acrylic resin, a resin bonded to one end of a polysiloxane with an acrylic resin such as urethane acrylate, for example, an external curing type resin manufactured by Nippon Synthetic Chemical Industry Co., Ltd.: trade name: Zeror UT-3841) .

The content of the water-repellent agent in the coating film for forming a transparent film is preferably 0.1 to 10% by weight, and more preferably 0.5 to 5% by weight, based on the solid content of the matrix-forming component.

When the content of the water repellent agent is small, the antifouling effect such as water repellency, adhesion to fingerprint and the stability of magic ink is not obtained. On the other hand, even if the content is increased, it is exposed on the surface of the film (bleed out) Or more and the hardness of the film becomes insufficient (stress relieving agent).

It is also preferable to include a stress relaxation agent.

(I) when the matrix is a silicone-based resin, it is preferable to use a monomer having two or more functional groups and /

(Ii) When the matrix is an acrylic resin, it is preferable that the acrylic resin based on the bifunctional group contains an acrylic resin polymerized respectively.

Examples of the bifunctional acrylic resin include tricyclodecane dimethiol diacrylate, bisphenol diacrylate, isocyanyl diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol diacrylate, tetraethylene diacrylate 1,6-hexanediol diacrylate, 1,10-decanediol diacrylate, 1,6-hexanediol acrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, dimethyrol dicyclopentane diacrylate, modified bisphenol A diacrylate, Diethylene glycol dimethacrylate, hexanediol dimethacrylate, polyethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and bisphenol A ethoxydiemethacrylate.

On the other hand, examples of the trifunctional acrylic resin include pentaerythritol triacrylate, isocyanyl triacrylate, trimethylol propane triacrylate, trimethylol propane ethoxy triacrylate, and glycerin propoxy triacrylate.

The content of the stress relaxation agent in the coating film for forming a transparent film is preferably from 0.05 to 10% by weight, and more preferably from 0.1 to 4% by weight, based on the solid content of the matrix forming component. When the content of the stress relaxation agent is reduced, the substrate is warped in the case of a flexible film or the like, and if the content of the stress relaxation agent is increased, the hardness of the transparent coating becomes insufficient.

[Polymerization Initiator]

The coating film for forming a transparent film of the present invention includes a polymerization initiator.

The polymerization initiator is not particularly limited as long as it is capable of polymerizing and curing the above-mentioned matrix-forming component, and conventionally known polymerization initiators can be appropriately selected depending on the resin.

For example, cationic photopolymerization initiators such as acylphosphine oxides, acetophenols, propionphenols, benzyls, benzoins, benzophenols, thioxanthones and the like can be given. In the present invention, phosphinephosphine photopolymerization initiators such as acylphosphine oxides or photocatalyst polymerization initiators are suitably used. Among them, when a phosphine photopolymerization initiator is used, stability is not impaired even if the coating is preserved for a long period of time, and the coloring property is not lost and the transparent coating is not colored after curing. In this case, the phosphine photopolymerization initiator may be used in combination with a polymerization initiator such as acetophenols, propionphenols, benzyls, benzoins, benzophenols, thioxanthones and the like. Examples of phosphine photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucifer TPO manufactured by BASF Japan Co., Ltd.).

On the other hand, since the cationic photopolymerization initiator is not affected by oxygen different from the polymerization initiator, it is not necessary to perform UV irradiation in a nitrogen atmosphere, and can be appropriately selected from the viewpoint of UV irradiation in air. As the photo-cationic warming polymerization initiator, a photo-initiator such as Adekaoftma-SP-170 manufactured by Wuko Kogyo Co., Ltd., IRUGACURE 250 manufactured by Tiba-Sharp Corporation, product name: CI-1370 manufactured by Japan Proc .

The content of the polymerization initiator in the coating material varies depending on the kind of the matrix forming component, but it is preferably 0.1 to 20% by weight, and more preferably 5 to 10% by weight of the matrix forming component when the solid content of the matrix forming component and the polymerization initiator is Do.

If the content of the polymerization initiator is reduced, the hardening of the coating film becomes insufficient and the coating stability becomes insufficient even when the coating film is increased, resulting in insufficient hardness of the obtained transparent coating film [solvent].

The solvent used in the present invention is not particularly limited as far as it can dissolve or disperse the above components, and conventionally known solvents can be used.

Specific examples thereof include alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydroperfuryl alcohol, ethylene glycol, hexylene glycol and isopropyl glycol; Esters such as acetic acid methyl ester, acetic acid ethyl ester and butyl acetate; Ethers such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and propylene glycol monomethyl ether; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, and acetoacetic acid ester, methylsorbate, ethylcellosolve, butylcellosolve, toluene, cyclohexanone and isophorone.

Among them, a solvent having a carbonyl group such as esters and ketones can be suitably used. When a solvent having a carbonyl group is contained, the surface-treated low refractive index fine particles are uniformly dispersed to form a transparent coating film having excellent unevenness, uniformity, adhesion to a substrate or a coating film, Can be formed to have excellent reproducibility.

These may be used alone or in combination of two or more. In the present invention, it is preferable to use a mixture of two or more kinds of solvents having different boiling points.

In the present invention, in the solvent, a mixed solvent of a solvent (A) having a boiling point at 50 to 100 ° C and a solvent (B) having a boiling point of 100 seconds to 200 □, wherein the ratio of the solvent (A) By weight and the ratio of bainite (B) is in the range of 10 to 50% by weight.

Examples of the solvent (A) include alcohols such as methanol, ethanol, propanol and 2-propanol (IPA); Esters such as acetic acid methyl ester, acetic acid ethyl ester and butyl acetate; Ketones such as acetone and methyl ethyl ketone, and toluene. These may be used alone or in combination of two or more.

Examples of the solvent (B) include alcohols such as butanol, diacetone alcohol, furfuryl alcohol, tetrahydroperfuryl alcohol, ethylene glycol, hexylene glycol and isopropyl glycol; Ethers such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and propylene glycol monomethyl ether; Ketones such as methyl isobutyl ketone, acetyl acetone and acetoacetic acid ester, methyl orthosorb, ethyl orthosorb, butyl orthosorb, toluene, cyclohexanone and isophorone. These may be used alone or in combination of two or more.

When the ratio of the solvent (A) in the mixed solvent is increased, the coating film is dried faster, the transparent film is not dense, and the hardness and scratch resistance are insufficient. When the paint contains a water-repellent agent, the water-repellent agent migrates to the upper layer of the transparent film in a state in which the water-repellent agent is dissolved in the solvent (B), and the water-repellent effect becomes insufficient.

When the proportion of the solvent (A) in the mixed solvent is decreased, the other solvent (B) is increased and the drying of the coating film is delayed to be flattened, so that a transparent film having irregularities that sufficiently reflect the unevenness of the surface of the substrate or the lower layer can not be formed to be.

Preferably, the ratio of the solvent (B) in the mixed solvent is in the range of 20 to 40% by weight. The proportion of the solvent in the coating film for forming a transparent coating film is preferably about 70 to 99% by weight, and more preferably 80 to 98% by weight.

Conventionally known methods can be selected as a method for forming a transparent coating film using the coating film for forming a transparent film according to the present invention.

Specifically, the coating material for forming a transparent film is applied to a substrate by a known method such as a dipping method, a spray method, a spinner method, a roller coating method, a bar coating method, a gravure printing method, a micro gravure printing method, , A heat treatment, or the like, so that a transparent coating film can be formed.

On the other hand, in order to form a transparent film having antiglare property with antireflection performance, it is possible to form a transparent film having a light-shielding property by using a conventionally known substrate or a lower layer film substrate having concavo- It is preferable that the coating liquid is formed from a mixed solvent of the low boiling point solvent and the high boiling point solvent, and the concentration of the matrix forming component in the solid content is in the range of 1 to 3 wt%, and the coating is applied, dried and cured by irradiation with ultraviolet rays. At this time, the micro gravure printing method is preferable.

Transparent Coating Substrate

The transparent coated substrate according to the present invention is characterized by comprising a transparent coating formed by using the above-mentioned transparent coating film-forming coating material between the substrate and the substrate.

materials

Examples of the base material include cellulose base materials such as triacetylcellulose film, diacetylcellulose film and acetate butyrate cellulose film, polyester base materials such as polyethylene terephthalate and polyethylene naphthalate, polyethylene film, polypropylene film, cyclic polyolefin Polyolefin-based materials such as nylon-6 and nylon-66, polyacrylic-based films such as nylon-6 and nylon-66, polyurethane-based films, polycarbonate films, polyether films, polyethersulfone films, polystyrene films, , A polyether ketone film, and an acrylonitrile film. In addition, a film-coated substrate on which a film is formed may be used.

Other coatings include a hard coat film, a conductive film, a high-refractive-index film, or a conventionally known film having these functions. On the other hand, if necessary, a transparent substrate with antiglare property can be obtained by using a substrate having a surface with irregularities and a film-coated substrate having a film formed thereon.

Transparent coating

The transparent coating is formed from the surface-treated low refractive index fine particles formed from the coating material, the matrix component, the polymerization initiator and, if necessary, the water repellent agent and the stress relieving agent.

The surface-treated low refractive index fine particles are the same as those described above.

The matrix component is obtained by polymerizing and solidifying the silicone resin and / or the acrylic resin.

The content of the low refractive index fine particles surface-treated in the transparent coating film is preferably 5 to 70% by weight, preferably 10 to 60% by weight, particularly preferably 30 to 50% by weight in terms of solid content. Within this range, the refractive index increases, the antireflection performance increases, and a transparent partial film having excellent bright partial contrast can be formed. Further, the film becomes uniform, the surface flatness is excellent, the light scattering does not occur, It is possible to form a transparent film having excellent scratch resistance.

The content of matrix formation in the transparent coating film is preferably in the range of 30 to 95% by weight, preferably 40 to 90% by weight, in terms of solid content. When the content of the matrix formation is within this range, the adhesion and scratch resistance with a substrate are increased, and a transparent film having a reduced refractive index and excellent antireflection performance can be formed.

Since the water-repellent agent is low in compatibility with the matrix component, it is positioned on the surface layer of the transparent coating film, and water repellency (a contact angle of water droplet of 90 degrees or more) is developed on the surface of the transparent coating film to adhere contaminants such as fingerprints, sebum, Can be prevented, and even if it is attached, it can be wiped easily.

The content of the water-repellent agent in the transparent film is preferably in the range of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the matrix component. Within this range, sufficient water repellency is imparted, and the effect of antifouling property such as adhesion of fingerprints on the surface of the fingerprint and the anti-magic ink is enhanced, and the appearance abnormality such as bleed-out, scratches and whitening and the hardness of the coating are insufficient.

The stress relieving agent contained in the transparent coating film is a polymer of the above-mentioned two functional groups and / or the trifunctional (meth) acrylic resin.

The content of the stress relaxation agent in the transparent film is preferably in the range of 0.05 to 10% by weight, preferably 0.1 to 4% by weight, based on the solid content of the matrix-forming component. Within this range, warping of the substrate is suppressed, and the hardness of the transparent coating film can be increased.

The transparent coating film includes the polymerization initiator. Such a polymerization initiator is used by polymerizing the matrix component and the stress relaxation agent. And remains in the transparent film after polymerization.

The amount of the polymerization initiator remaining in the transparent coating film varies depending on the kind of the polymerization initiator, the amount of the polymerization initiator, the kind of the matrix component, and the like, but is preferably as small as possible and is preferably 20% by weight or less, more preferably 10% And preferably 5% by weight or less. Within this range, the color tone of the transparent coating film is not affected.

The thickness of the transparent coating film according to the present invention varies depending on the use, but is preferably in the range of about 10 to 500 nm, preferably 20 to 300 nm, particularly 50 to 200 nm.

When the film thickness of the transparent coating film is reduced, the antireflection performance, the strength and the like are insufficient. On the other hand, the film thickness of the transparent coating increases. It is deviated from the Fresnel principle, the antireflection performance becomes insufficient, and the bright room contrast is lowered, so that white may appear on the screen. On the other hand, warpage may occur in a substrate such as a pet film.

The transparent coated substrate according to the present invention can be prepared by coating the above-mentioned transparent coating film forming coating material on a substrate, followed by drying and curing.

As the coating method, the coating material is applied to a base material by a known method such as dipping method, spraying method, spinner method, roller coating method, bar coating method, gravure printing method and micro gravure printing method and dried, and in the case of a thermosetting resin May be cured and then heat-treated. In the case of an ultraviolet-cured resin, the ultraviolet ray may be irradiated at about 400 mJ / cm 2 and cured.

Preferably, in the transparent-film sub-substrate of the present invention, a film different from the transparent film may be provided on the gap between the substrate and the transparent film and / or on the transparent film. The transparent coating film may be provided on the substrate on the opposite side of the coating film.

On the other hand, it is preferable that the base film or the undercoat film of the transparent coating film has irregularities on the surface thereof because it is imparted with antiglare performance.

Examples of other coatings include conventionally known hard coat films, high refractive index films, conductive films, antifogging films, infrared ray blocking films, ultraviolet ray blocking films, and the like.

The transparent coating film formed on the substrate using the coating film for forming a transparent film according to the present invention is excellent in antireflection performance, antiglare performance and bright part contrast because it has a low refractive index and can have irregularities on the surface if necessary, By providing a conductive film, antistatic performance and electromagnetic wave shielding performance can be imparted. Accordingly, it is possible to provide a transparent-coated sub-substrate which can be appropriately used for an LCD display, a plasma display, a projection display, an EL display, a CRT display, and the like.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples.

(Example 1)

Preparation of antistatic film-forming coating material (EC-1)

To 100 g of an antimony pentoxide pentoxide dispersion (ELCOM V-4560, average particle size 20 nm, Sb ₂ O ₅ concentration 30.5% by weight, dispersion medium: isopropanol, particle refractive index 1.60, manufactured by Catalysts of Kagoshin Kagaku Kogyo K.K.), γ-methacryloxypropyl 1.88 g of trimethoxysilane (KBM-503, manufactured by Shin-Etsu Silicone Co., Ltd., and 81.2% of SiO ₂ component) were mixed, and 3.1 g of ultrapure water was added thereto and stirred at 50 ° C for 20 hours to obtain a surface-treated antimony pentoxide pentoxide sol Solid content 30.5%). 29.51 g of the surface-treated antimony pentoxide pentoxide sol, 18.9 g of dihexaerythritol triacetone (DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.) and 1.6 g of 1.6-hexane diol diacrylate 8.4 g of a photopolymerization initiator (lucyllum TPO, manufactured by BASF Japan Ltd.) dissolved in a solid content concentration of 10%) and 2.1 g of a polyoxyalkylene polyoxyalkylene polyol To prepare an antistatic film-forming coating (EC-1) having a high refractive index hard coat function.

Production of a transparent coating film-forming coating material (ARL-1)

Preparation of surface-treated low refractive index fine particle dispersion (LP-1)

(100 g) of hollow silica fine particle dispersion (Catalyst special product, average particle size 60 nm, solid content 20.5 wt%, IPA dispersion, particle refractive index 1.20) manufactured by Catalysts of Kagoshin Kagaku Kogyo KK) was added with methacrylate trimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd., 81.2% by weight of SiO ₂ component) was added and the mixture was heated and stirred at 50 ° C for 15 hours to prepare a surface- treated low refractive index fine particle dispersion (LP- 1). The obtained surface-treated low refractive index fine particles had a refractive index of 1.24 and an average particle size of 60 nm.

4.74 g of a silicone resin (silicone-based resin A (hereinafter the same), X-12-2400, Shin-Wol Chemistry Co., Ltd., solid concentration 28.5 wt%) and 6.74 g of a stress relieving agent 0.3 g of Light Acrylate 1.6 HX-A (the stress relaxation agent a (hereinafter the same), manufactured by Kobunshi Chemical Co., Ltd.) and 1 g of a photopolymerization initiator (produced by BASF Japan Co., Ltd.) : Dissolve in 10% by weight of solid concentration of losylline TPO: IPA (polymerization initiator a-p system)), 58.24 g of isopropyl alcohol, 15 g of methyl isobutyl ketone, 9 g of isopropyl glycol, 5 g of ethylene glycol monobutyl ether (Mixed solvent a) were mixed to prepare a transparent coating film-forming coating material (ARF-1) having a solid content concentration of 3.0% by weight.

Preparation of transparent coated secondary substrate (ARF-1)

(# 10) on a TAC film (80 占 퐉 thick) and dried at 80 占 폚 for 120 seconds and irradiated with ultraviolet rays of 600 mJ / cm2 to prepare a cured electrification Barrier film. The film thickness of the antistatic film was 3 m.

Subsequently, the transparent film-forming coating material (ARL-1) was applied by a bar coating method (# 4) and baked at 80 ° C. for 120 seconds. Then, ultraviolet light of 600 mJ / 1) was prepared. At this time, the thickness of the transparent coating film was 100 nm.

The surface resistance of the resultant transparent coated sub-base material (ARF-1) was measured with a surface resistance meter (Mitsubishi Chemical Corporation: Hiresta) and the results are shown in Table 1. On the other hand, a part of the transparent coating film was vertically cut and the average film thickness was measured with respect to the cross section using a laser microscope (VE-3000, manufactured by Keyence Corporation: VE-3000).

All the light transmittance and phase were measured by Phasmeta (1325A, Japan). The results are shown in Table 1.

The reflectance and the integral reflectance were measured with a spectrophotometer (U-vest, manufactured by Nippon Gosei Co., Ltd.), and the bottom reflectance at wavelengths of 400 to 700 nm was shown in Table 1.

The pencil hardness, scratch resistance and adhesiveness were evaluated by the following methods and permission standards, and the results are shown in Table 1.

Measurement of pencil hardness

And measured by a pencil hardness tester in accordance with JIS-K-5400.

Measurement of scratch resistance

# 0000 Steel wool, scratching 10 times at a load of 500 g / cm < 2 >, and the surface of the film was visually observed and evaluated according to the following criteria.

Evaluation standard:

Cotton scratches are not recognized: ◎

Some scratches on the face are recognized: ○

Many scratches on the face are recognized: △

The surface is entirely damaged: ×

Measurement of adhesion

And measured by a pencil hardness tester in accordance with JIS-K-5400.

(Example 2)

Preparation of a transparent coating film-forming coating material (ARL-2)

Preparation of surface-treated low refractive index fine particle dispersion (LP-2)

To 100 g of a hollow silica fine particle dispersion (Cataroide special product, average particle size 60 nm, solid content 20.5% by weight, IPA dispersion, particle refractive index 1.20, manufactured by Catalysts of Kagoshin Kagaku Kogyo K.K.), γ-methacryloxypropyltrimethoxysilane (Surface treatment agent A, KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd., 81.2% by weight of SiO ₂ component) was added and the mixture was heated and stirred at 50 ° C for 15 hours to obtain a surface- treated low refractive index fine particle dispersion -2). The obtained surface-treated low refractive index fine particles had a refractive index of 1.22 and an average particle size of 60 nm.

4.74 g of a silicone resin (silicone resin A, X-12-2400; manufactured by Shin-Etsu Chemical Co., Ltd., solid content concentration 28.5% by weight) and 6.74 g of acrylic resin 1, 6-diacrylate were added to 6.98 g of the surface-treated low refractive index fine particle dispersion (LP- 0.15 g of hexane diol diacrylate (a stress relieving agent a, light acrylate 1.6 HX-A, manufactured by Kobunshi Chemical Co., Ltd.) and 0.15 g of a reactive silicone oil (water repellent agent A, Shinwol Chemical Co., X-22-174DX, IPA Dissolved in a solid content concentration of 10% by weight) and a photopolymerization initiator (BASF Japan Co., Ltd.); 0.9 g of isopropyl alcohol, 15 g of methyl isobutyl ketone, 7 g of isopropyl glycol, and 7 g of ethylene glycol monobutyl ether (mixed solvent a) were mixed to obtain a solid content A transparent coating film-forming coating material (ARL-2) having a concentration of 3.0% by weight was prepared.

Production of transparent coated secondary substrate (ARF-2)

(# 10) on a TAC film (80 占 퐉 thick) and dried at 80 占 폚 for 120 seconds in the same manner as in Example 1, and then exposed to ultraviolet light of 600 mJ / To form a cured antistatic film.

Subsequently, the transparent coating film-forming coating material (ARL-2) was coated by a bar coating method (# 4) and baked at 80 ° C. for 120 seconds. Thereafter, the cured transparent coating film substrate (ARF- 2) was produced. At this time, the thickness of the transparent coating film was 100 nm.

The surface resistance, the total light transmittance, the phase, the reflectance, the integral reflectance, the contact angle, the film thickness, the pencil hardness, the scratch resistance and the adhesion were measured for the obtained transparent coated sub-base material (ARF-2) Respectively.

(Example 3)

Production of a transparent coating film-forming coating material (ARL-3)

Preparation of surface-treated low refractive index fine particle dispersion (LP-3)

To 100 g of a hollow silica fine particle dispersion (Cataroide special product, average particle size 60 nm, solid content 20.5% by weight, IPA dispersion, particle refractive index 1.20, manufactured by Catalysts of Kagoshin Kagaku Kogyo K.K.), γ-methacryloxypropyltrimethoxysilane (Surface treatment agent A; KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd., 81.2% by weight of SiO ₂ component) was added and the mixture was heated and stirred at 50 ° C for 15 hours to prepare a surface- treated low refractive index fine particle dispersion (LP- 3). The obtained surface-treated low refractive index fine particles had a refractive index of 1.28 and an average particle size of 60 nm.

4.74 g of a silicone resin (silicone resin A, X-12-2400; manufactured by Shin-Etsu Chemical Co., Ltd., solid concentration 28.5% by weight) and 6.1 g of acrylic resin tripropylene 0.15 g of diacrilate (stress relieving agent b, Aronikkus M-220, manufactured by Donga Synthetic Co., Ltd.) and 0.15 g of a reactive silicone oil (water repellent agent a, Shinwol Chemical Co., X-22-174DX, 10 wt%) and 0.3 g of a photopolymerization initiator (BASF Japan); (Dissolved in a solid content concentration of 10% by weight with TPA: luciferin TPA), 58.81 g of isopropyl alcohol, 15 g of methyl isobutyl ketone, 9 g of isopropyl glycol and 5 g of ethylene glycol monobutyl ether were mixed A transparent coating film-forming coating material (ARL-3) having a concentration of 3.0% by weight was prepared.

Production of transparent coated secondary substrate (ARF-3)

(# 10) on a TAC film (80 占 퐉 thick) and dried at 80 占 폚 for 120 seconds in the same manner as in Example 1, and then exposed to ultraviolet light of 600 mJ / To form a cured antistatic film.

Subsequently, the transparent coating film-forming coating material (ARL-3) was coated by a bar coating method (# 4) and baked at 80 ° C. for 120 seconds. Then, the cured transparent coating film substrate (ARF-3 ). At this time, the thickness of the transparent coating film was 100 nm.

The surface resistance, the total light transmittance, the phase, the reflectance, the integral reflectance, the contact angle, the film thickness, the pencil hardness, the scratch resistance and the adhesion were measured for the obtained transparent coated sub-base material (ARF-3) Respectively.

(Example 4)

Production of a transparent film-forming coating material (ARL-4)

2.21 g of a silicone resin (silicone resin A, X-12-2400; manufactured by Shin-Etsu Chemical Co., Ltd., solid concentration 28.5% by weight) and 1.21 g of an acrylic-based resin 0.07 g of resin tripropylene diacrylate (stress relieving agent b, Aronikkus M-220, manufactured by Donga Synthetic Co., Ltd.) and 0.07 g of reactive silicone oil (water repellent agent b, Shinwol Chemical Co., Ltd .; X-22-2426, IPA Dissolved in a solid concentration of 10 wt%) and 0.28 g of a photopolymerization initiator (BASF Japan); (Mixed solvent a), 0.7 g of isopropyl alcohol, 15 g of methyl isobutyl ketone, 9 g of isopropyl glycol, and 5 g of ethylene glycol monobutyl ether were mixed to obtain a solid content A transparent coating film-forming coating material (ARL-4) having a concentration of 1.0% by weight was prepared.

Preparation of transparent coated secondary substrate (ARF-4)

(# 10) on a TAC film (80 占 퐉 thick) and dried at 80 占 폚 for 120 seconds in the same manner as in Example 1, and then exposed to ultraviolet light of 600 mJ / To form a cured antistatic film.

Subsequently, the transparent coating film forming material (ARF-3) was applied by a bar coating method (# 4) and baked at 80 ° C. for 120 seconds, and then irradiated with ultraviolet rays of 600 mJ / 4) were produced. At this time, the thickness of the transparent coating film was 100 nm.

The surface resistance, the total light transmittance, the phase, the reflectance, the integral reflectance, the contact angle, the film thickness, the pencil hardness, the scratch resistance and the adhesion were measured for the obtained transparent coated sub-base material (ARF-4) Respectively.

(Example 5)

Production of a transparent coating film-forming coating material (ARL-5)

(X-12-2400; manufactured by Shin-Etsu Chemical Co., Ltd., solid concentration 28.5% by weight) and 15.56 g of the low refractive index fine particle dispersion (LP-1) prepared in the same manner as in Example 1, 0.15 g of diol diacrylate (stress relieving agent a, Light Acrylate 1.6 HX-A, manufactured by Kobunshi Chemical Co., Ltd.) and 0.15 g of a reactive silicone oil (water repellent agent b, Shinwol Chemical Co., X-22-2426, Dissolved in a solid concentration of 10% by weight) and a photopolymerization initiator (manufactured by BASF Japan Ltd.); 0.45 g of luciferin TPO dissolved in IPA at a solid concentration of 10% by weight), 50.25 g of isopropyl alcohol, 15 g of methyl isobutyl ketone, 9 g of isopropyl glycol and 5 g of ethylene glycol monobutyl ether were mixed (mixed solvent a) A transparent coating film-forming coating material (ARL-5) having a concentration of 5.0% by weight was prepared.

Production of transparent coated secondary substrate (ARF-5)

(# 10) on a TAC film (80 占 퐉 thick) and dried at 80 占 폚 for 120 seconds in the same manner as in Example 1, and then exposed to ultraviolet light of 600 mJ / To form a cured antistatic film.

Subsequently, the transparent coating film-forming coating material (ARL-5) was applied by a bar coating method (# 4) and baked at 80 ° C. for 120 seconds, ). At this time, the thickness of the transparent coating film was 100 nm.

The surface resistance, the total light transmittance, the phase, the reflectance, the integral reflectance, the contact angle, the film thickness, the pencil hardness, the scratch resistance and the adhesiveness were measured for the obtained transparent coated sub-base material (ARF-5) Respectively.

(Example 6)

Production of a transparent coating film-forming coating material (ARL-6)

A transparent coating film-forming coating material (ARL-5) was prepared in the same manner as in Example 1 except that 0.3 g of the reactive silicone oil for the water-repellent agent was changed to 0.3 g of isopropyl alcohol.

Production of transparent coated secondary substrate (ARF-6)

An antistatic film-forming coating material (EC-1) was applied to a TAC film (thickness 80 占 퐉) by the bar coating method (# 10) and dried at 80 占 폚 for 120 seconds in the same manner as in Example 1. Thereafter, And an external wire was irradiated to form a cured antistatic film.

Subsequently, the transparent coating film-forming coating material (ARL-6) was coated by a bar coating method (# 4) and baked at 80 ° C. for 120 seconds, ). At this time, the thickness of the transparent coating film was 100 nm.

The surface resistance, the total light transmittance, the phase, the reflectance, the integral reflectance, the contact angle, the film thickness, the pencil hardness, the scratch resistance and the adhesion were measured for the obtained transparent coated sub-base material (ARF-6) Respectively.

(Example 7)

Preparation of a transparent coating film-forming coating material (ARL-7)

A transparent coating film-forming coating material (ARL-7) was prepared in the same manner as in Example 1 except that 0.15 g of the acrylic resin as the stress relaxation agent was changed to 0.15 g of isopropyl alcohol in Example 1.

Preparation of transparent coated secondary substrate (ARF-7)

(# 10) on a TAC film (80 占 퐉 thick) and dried at 80 占 폚 for 120 seconds in the same manner as in Example 1, and then exposed to ultraviolet light of 600 mJ / To form a cured antistatic film.

Subsequently, the transparent coating film-forming coating material (ARL-7) was coated by a bar coating method (# 4) and baked at 80 ° C. for 120 seconds, ). At this time, the thickness of the transparent coating film was 100 nm.

The surface resistance, the total light transmittance, the phase, the reflectance, the integral reflectance, the contact angle, the film thickness, the pencil hardness, the scratch resistance and the adhesion were measured for the obtained transparent coated sub-base material (ARF-7) Respectively.

(Example 8)

Production of a transparent film-forming coating material (ARL-8)

A transparent coating film-forming coating material (ARL-8) was prepared in the same manner as in Example 1 except that 0.3 g of the reactive silicone oil for the water-repellent agent and 0.15 g of the acrylic resin for the stress relaxation agent in Example 1 were changed to 0.45 g of isopropyl alcohol .

Preparation of transparent coated secondary substrate (ARF-8)

(# 10) on a TAC film (80 占 퐉 thick) and dried at 80 占 폚 for 120 seconds in the same manner as in Example 1, and then exposed to ultraviolet light of 600 mJ / To form a cured antistatic film.

Subsequently, the transparent coating film-forming coating material (ARL-8) was applied by a bar coating method (# 4) and baked at 80 ° C for 120 seconds. Thereafter, the cured transparent coating film substrate (ARF- 7) were produced. At this time, the thickness of the transparent coating film was 100 nm.

The surface resistance, the total light transmittance, the phase, the reflectance, the integral reflectance, the contact angle, the film thickness, the pencil hardness, the scratch resistance and the adhesion were measured for the obtained transparent coated sub-base material (ARF-8) Respectively.

(Example 9)

Preparation of surface-treated low refractive index fine particle dispersion (LP-4)

(100 g) having a mean particle size of 60 nm, a solid content of 20% by weight, an IPA dispersion, a particle refractive index of 1.20) was dispersed in a dispersion medium of hollow silica fine particles (manufactured by Catalysts & (Surface treatment agent B, KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd., 81.2% by weight of SiO ₂ component) was added and the mixture was heated and stirred at 50 ° C for 15 hours to obtain a surface- treated low refractive index fine particle dispersion ). The obtained surface-treated low refractive index fine particles had a refractive index of 1.24 and an average particle size of 60 nm.

Preparation of transparent coating film-forming coating material (ARL-9)

1.35 g of an acrylic resin dipentaerythritol hexane acrylate (matrix forming component; DPE-6A, manufactured by Kobunshi Chemical Co., Ltd.) and 6.35 g of an acrylic resin 1.6-hexanediol di 0.15 g of acrylate (Stress Relaxation Agent A, Light Acrylate 1.6-HX-A, manufactured by Kobunshi Chemical Co., Ltd.) and 0.15 g of a reactive silicone oil (water repellent agent a, X-22-174DX, (Dissolved in a concentration of 10% by weight) and 0.6 g of a photopolymerization initiator (BASF Japan: Lucirin TPO: dissolved in toluene at a solid concentration of 10% by weight) and 0.6 g of a primer , Dissolved in toluene, solid content concentration of 10% by weight), 60.64 g of isopropyl alcohol, 10 g of methyl isobutyl ketone, 10 g of propylene glycol monopropyl ether and 10 g of ethylene glycol monobutyl ether were mixed (mixed solvent b) To prepare a coating film for forming a transparent film (ARL-9) in weight%.

Preparation of transparent coated secondary substrate (ARF-9)

(# 10) on a TAC film (80 占 퐉 thick) and dried at 80 占 폚 for 120 seconds in the same manner as in Example 1, and then exposed to ultraviolet light of 600 mJ / To form a cured antistatic film.

Subsequently, the transparent coating film-forming material (ARL-9) was applied by a bar coating method (# 4) and baked at 80 ° C. for 120 seconds and then irradiated with ultraviolet light of 600 mJ / ). At this time, the thickness of the transparent coating film was 100 nm.

The surface resistance, the total light transmittance, the phase, the reflectance, the integral reflectance, the contact angle, the film thickness, the pencil hardness, the scratch resistance and the adhesion were measured for the obtained transparent coated sub-base material (ARF-9) Respectively.

(Example 10)

Preparation of Coating Solution (AG-1) for Lower Layer Film Formation

40 g of silica fine particles (silica microbead P-400, average particle size 1.5 占 퐉, manufactured by Catalysts of Chemical Industries, Ltd.) was dispersed in 160 g of a mixed solvent of water / methanol = 1: 1, to which methacrylate trimethoxysilane (KBM-503), and the mixture was heated and stirred at 50 占 폚 for 15 hours, followed by separation and drying at 100 占 폚 to obtain surface-treated silica fine particles.

Subsequently, 1 g of the fine silica particles surface-treated in 9 g of dipentaerythrityl hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light acrylate DPE-6A), 0.36 g of a photopolymerization initiator (TIBA Specialty Chemicals: Ilgacure 184) 39.64 g of propanol / propylene glycol monoethyl ether = 9/1 was added and dispersed in an ultrasonic disperser for 15 minutes to obtain a coating liquid for forming a lower layer film (AG-1) having antifogging properties.

Production of Lower Layer Film Substrate (AGF-1)

Coating solution (AG-1) for forming a lower layer film was applied to a TAC film (thickness 80 占 퐉) by a bar coating method (# 8), dried at 80 占 폚 for 120 seconds, irradiated with ultraviolet rays of 600 mJ / (AGF-1) having unevenness on its surface was formed.

A part of the coating film was vertically cut with respect to the lower film member base material AGF-1 and the average film thickness and the height (T ₁ ) of the convex portion were measured using a laser microscope (VE-3000, manufactured by Keyence Corporation) , And the height of the concave portion (T ₂ ) were measured, and the results are shown in Table 1.

Production of transparent coated secondary substrate (ARF-10)

(ARL-1) prepared in the same manner as in Example 1 was applied onto the lower layer film substrate (AGF-1) by the bar coating method (# 3) so that the average film thickness of the transparent coating film was 100 nm After drying at 80 DEG C for 120 seconds, ultraviolet light of 600 mJ / cm < 2 > was irradiated to prepare a cured transparent coated secondary substrate (ARF-10).

The average film thickness, the height of the convex portion (T ₃ ), and the height of the concave portion (T ₄ ) were measured for the resultant transparent coated sub-base material (ARF-10) by the above method.

On the other hand, surface resistance, total light transmittance, phase, reflectance, integral reflectance, pencil hardness, scratch resistance, adhesiveness and antistatic property were measured in the same manner as in Example 1 and the results are shown in Table 1.

Measurement of the repulsive property

The coated surface was applied to black with a non-glossy black spray, and the reflected light of the fluorescent light was visually observed 1 m away and evaluated with the following criteria.

Evaluation standard:

No fluorescent lights visible at all: ◎

Fluorescent light is slightly visible: ○

Fluorescent light is visible but outline is blurred: △

Fluorescent lamp clearly visible: ×

(Example 11)

Production of transparent coated secondary substrate (ARF-11)

(ARL-9) prepared in Example 9 was applied onto the lower layer film base material (AGF-1) prepared in the same manner as in Example 10 by the bar coating method (a) to make the average film thickness of the transparent coating film 100 nm # 3), dried at 80 DEG C for 120 seconds, and then irradiated with ultraviolet light of 600 mJ / cm < 2 > to prepare a cured transparent coated secondary substrate (ARF-11).

The reflectance, the integral reflectance, the average film thickness, the height of the convex portion (T ₃ ), the height of the concave portion (T ₄ ), Pencil hardness, scratch resistance, adhesion and antifogging properties were measured, and the results are shown in Table 1.

(Comparative Example 1)

Preparation of a transparent coating film-forming coating material (ARL-R1)

(A silicon-containing resin, a silicone-based resin, and a silicone-based resin) was added to 7.32 g of a hollow silica fine particle dispersion (Catalyst special product; average particle size 60 nm, solid content 20.5% by weight, IPA dispersion, particle refractive index 1.20) 4.74 g of acrylic resin for stress relieving agent: 1.6-hexane diol diacrylate (stress relieving agent a, manufactured by Kyoeisha Chemical Co., Ltd., light acrylic resin (trade name: X-12-2400, solid content concentration 28.5% 0.3 g of a reactive silicone oil for a water-repellent agent (Shinwol Chemical Co., Ltd .; X-22-174DX, dissolved in a solid concentration of 10% by weight by IPA) and 0.1 g of a photopolymerization initiator (BASF Japan) My; 0.9 g of isopropyl alcohol, 15 g of methyl isobutyl ketone, 9 g of isopropylglycoll, and 5 g of ethylene glycol monobutyl ether were mixed to prepare a solution having a solid concentration of 3.0% by weight To thereby prepare a transparent coating film-forming coating material (ARL-R1).

Production of transparent coated secondary substrate (ARF-R1)

(# 10) on a TAC film (80 占 퐉 thick) and dried at 80 占 폚 for 120 seconds in the same manner as in Example 1, and then exposed to ultraviolet light of 600 mJ / To form a cured antistatic film.

Subsequently, the transparent coating film-forming coating material (ARL-R1) was coated by a bar coating method (# 4) and baked at 80 ° C. for 120 seconds, ). At this time, the thickness of the transparent coating film was 100 nm.

The surface resistance, the total light transmittance, the phase, the reflectance, the integral reflectance, the contact angle, the film thickness, the pencil hardness, the scratch resistance and the adhesion were measured for the obtained transparent coated sub-base material (ARF-R1) Respectively.

(Comparative Example 2)

Preparation of coating material for transparent coating film (ARL-R2)

(ARL-R2) was prepared in the same manner as in Comparative Example 1 except that 0.3 g of the reactive silicone oil for the water-repellent agent and 0.15 g of the acrylic resin for the stress relaxation agent were changed to 0.45 g of the isopropyl alcohol, .

Preparation of transparent coated secondary substrate (ARF-R2)

(# 10) on a TAC film (80 占 퐉 thick) and dried at 80 占 폚 for 120 seconds in the same manner as in Example 1, and then exposed to ultraviolet light of 600 mJ / To form a cured antistatic film.

Subsequently, the transparent coating film-forming coating material (ARL-R2) was applied by a bar coating method (# 4) and baked at 80 ° C for 120 seconds. Thereafter, the cured transparent film substrate (ARF- R2). At this time, the thickness of the transparent coating film was 100 nm.

The surface resistance, the total light transmittance, the phase, the reflectance, the integral reflectance, the contact angle, the film thickness, the pencil hardness, the scratch resistance and the adhesion were measured for the obtained transparent coated sub-base material (ARF-R2) Respectively.

(Comparative Example 3)

Production of coating material for transparent coating film (ARL-R3)

(Acrylic acid resin) was added to 7.32 g of a hollow silica fine particle dispersion (Cataroide special product, average particle size 60 nm, solid content 20.5% by weight, IPA dispersion, particle refractive index 1.20, manufactured by Catalysts of Japan) 1.25 g of acrylic resin 1.6-hexane diol diacrylate (Stress Relief a, Light Acrylate 1.6HX-A, manufactured by Kyoeisha Chemical Industry Co., Ltd.) 0.3 g of a reactive silicone oil (X-22-174DX, dissolved in a solid content concentration of 10% by weight with IPA) 0.3 g and a photopolymerization initiator (BASF Japan); (Luciferin TPO: dissolved in toluene at a solid concentration of 10% by weight), 0.3 g of a photopolymerization initiator (dissolved in toluene, a solid content concentration of 10% by weight) and isopropyl alcohol (ARL-R3) having a solid content concentration of 3.0% by weight was prepared by mixing 59.98 g of methyl ethyl ketone, 10 g of methyl isobutyl ketone, 10 g of propylene glycol monopropyl ether, and 10 g of ethylene glycol monobutyl ether.

Preparation of transparent coated secondary substrate (ARF-R3)

(# 10) on a TAC film (80 占 퐉 thick) and dried at 80 占 폚 for 120 seconds in the same manner as in Example 1, and then exposed to ultraviolet light of 600 mJ / To form a cured antistatic film.

Subsequently, the transparent coating film-forming coating material (ARL-R3) was coated by a bar coating method (# 4) and baked at 80 ° C for 120 seconds, ). At this time, the thickness of the transparent coating film was 100 nm.

The surface resistance, the total light transmittance, the phase, the reflectance, the integral reflectance, the contact angle, the film thickness, the pencil hardness, the scratch resistance and the adhesion were measured for the obtained transparent coated sub-base material (ARF-R3) Respectively.

(Comparative Example 4)

Preparation of coating material for transparent coating (ARL-R4)

(Matrix forming component, polyester, Bayeron MD-1200, manufactured by Toyo Kagaku Kogyo Co., Ltd., solid content concentration: 34 wt%) was added to 6.67 g of the low refractive index fine particle dispersion (LP- ) And 0.3 g of a reactive silicone oil (water repellent agent a, Shinwol Chemical Co., Ltd .; X-22-2426, dissolved in IPA at a solid content concentration of 10% by weight) and a leveling agent (ARL-4R) having a solid content concentration of 3.0% by weight was prepared by mixing 0.5 g of polyvinyl alcohol, RON NSH-8430HF, solid concentration 10% by weight), 78.12 g of isopropyl alcohol and 10 g of ethylene glycol monoethyl ether.

Production of transparent coated secondary substrate (ARF-R4)

Subsequently, the transparent coating film-forming coating material (ARL-4R) was applied by a bar coating method (# 4) and baked at 80 ° C for 120 seconds, and then irradiated with ultraviolet rays at 600 mJ / ). At this time, the thickness of the transparent coating film was 100 nm.

The surface resistance, the total light transmittance, the phase, the reflectance, the integral reflectance, the contact angle, the film thickness, the pencil hardness, the scratch resistance and the adhesion were measured for the obtained transparent coated sub-base material (ARF-4R) Respectively.

(Comparative Example 5)

Production of transparent coated secondary substrate (ARF-R5)

The lower layer film base material (AGF-1) was produced in the same manner as in Example 10. A portion of this film 1 was vertically cut with respect to this lower layer film base material AGF-1 and the average film thickness and the height of the convex portions were measured using a laser microscope (VE-3000, manufactured by Keyence Corporation) T ₁ ) and the height of the concave portion (T ₂ ) were measured, and the results are shown in Table 1.

Subsequently, the transparent coating film-forming coating material (ARL-R1) prepared in the same manner as in Comparative Example 1 was applied by a bar coating method (# 3) so that the average film thickness of the transparent coating film was 100 nm, (ARF-R5) was prepared by irradiating ultraviolet light of 600 mJ / cm < 2 >.

A part of the obtained coating film was vertically cut in the same manner as in the above-mentioned lower layer film base material (AGF-1), and a laser microscope (VE-3000 manufactured by CHIENCE Co., Ltd.) The average thickness, the height of the convex portion (T ₃ ), and the height of the concave portion (T ₄ ) were measured, and the results are shown in Table 1.

On the other hand, in the same manner as in Example 10, the surface resistance, the total light transmittance, the phase, the reflectance, the integral reflectance, the average film thickness, the height of the convex portion (T ₃ ), the height of the concave portion (T ₄ ), the pencil hardness, And the results are shown in Table 1.

(Comparative Example 6)

Preparation of transparent coated secondary substrate (ARF-R6)

The lower layer film base material (AGF-1) was produced in the same manner as in Example 10. A portion of the coating film 1 was vertically cut with respect to the lower film part base material AGF-1 and the average film thickness, the height of the convex portion, and the like were measured using a laser microscope (VE-3000, manufactured by KEYENCE CORPORATION) (T ₁ ) and the height of the concave portion (T ₂ ) were measured, and the results are shown in Table 1.

Subsequently, the transparent coating film-forming coating material (ARL-R3) prepared in Comparative Example 3 was applied by a bar coating method (# 3) so that the average film thickness of the transparent coating film was 100 nm and dried at 80 ° C for 120 seconds, / Cm < 2 > to produce a cured transparent coated secondary substrate (ARF-R6).

A part of the obtained coating film was vertically cut in the same manner as in the case of the lower layer film base material (AGF-1), and a laser microscope (VE-3000 manufactured by Keyen Co., Ltd.) The average thickness, the height of the convex portion (T ₃ ), and the height of the concave portion (T ₄ ) were measured, and the results are shown in Table 1.

On the other hand, in the same manner as in Example 10, the surface resistance, the total light transmittance, the phase, the reflectance, the integral reflectance, the average film thickness, the height of the convex portion (T ₃ ), the height of the concave portion (T ₄ ), the pencil hardness, And the results are shown in Table 1.

(Comparative Example 7)

Production of transparent coated secondary substrate (ARF-R7)

The lower layer film base material (AGF-1) was produced in the same manner as in Example 10. A portion of this film 1 was vertically cut with respect to this lower layer film base material AGF-1 and the average film thickness and the height of the convex portions were measured using a laser microscope (VE-3000, manufactured by Keyence Corporation) T ₁ ) and the height of the concave portion (T ₂ ) were measured, and the results are shown in Table 1.

(# 3) so that the average film thickness of the transparent coating film of the transparent film-forming coating material (ARL-R4) produced in Comparative Example 4 was 100 nm, dried at 80 ° C for 120 seconds, / Cm < 2 > to produce a cured transparent coated secondary substrate (ARF-R7).

A part of this coating film was vertically cut in the same manner as in the above-mentioned lower layer film base material (AGF-1), and a laser microscope (VE-3000 manufactured by Keyent Co., Ltd.) The average thickness, the height of the convex portion (T ₃ ), and the height of the concave portion (T ₄ ) were measured, and the results are shown in Table 1.

On the other hand, in the same manner as in Example 10, the surface resistance, the total light transmittance, the phase, the reflectance, the integral reflectance, the average film thickness, the height of the convex portion (T ₃ ), the height of the concave portion (T ₄ ), the pencil hardness, And the results are shown in Table 1. In addition, square of surface resistance means square inch.

The effect of the present invention is that it is possible to form a transparent film having a low refractive index that is excellent in adhesion to a substrate, strength, water repellency and whitening resistance, and in the case of forming a transparent film on a substrate or a lower film having concavo- It is possible to provide a coating liquid for forming a transparent film which is capable of forming a transparent film having a flat surface and having the same concavity and convexity as that of the lower unevenness. On the other hand, the transparent coating formed on the substrate using the coating material for forming a transparent coating film has low refractive index and can have irregularities on the surface if necessary. Thus, it has excellent antireflection performance, antiglare performance and bright part contrast, , A plasma display, a projection display, an EL display, a CRT display, and the like.

Claims (9)

(I) the low refractive index fine particles are treated with a silane coupling agent, the refractive index of the surface treated low refractive index particles is in the range of 1.20 to 1.45, the concentration of the low refractive index fine particles is in the range of 0.1 to 10% by weight as solid content; (Ii) the matrix-forming component is a silicone-based resin and / or an acrylic-based resin and the concentration of the matrix-forming component is in the range of 0.5 to 20% by weight as solids; A matrix forming component, a polymerization initiator, and a mixed solvent, wherein the low refractive index fine particles, (a) the silicon-based resin in the matrix-forming component is a resin obtained by polymerizing a silicone-based resin monomer having a trifunctional or higher functional group having a (meth) acryloyl group, and the acrylic-based resin is a trifunctional or more acrylic-based resin monomer having a (meth) acryloyl group Is a polymerized resin; (b) wherein the matrix forming component further comprises a resin having a bifunctional or smaller resin monomer polymerized as a water repellent agent, the resin being a silicone resin having a (meth) acryloyl group, a fluororesin having a , A long chain acrylic resin having a (meth) acryloyl group, and a siloxane-based acrylic resin; (c) The matrix-forming component is a stress-relieving agent which is a bifunctional and / or trifunctional acrylic resin monomer when the matrix-forming component is a silicone resin, and (ii) a bifunctional acrylic- Further comprising an acrylic resin polymerized with a resin monomer; (d) the water repellent agent content relative to the matrix forming component is from 0.1 to 10 wt%, the stress relieving agent content is from 0.05 to 10 wt%; (e) the mixed solvent is a mixed solvent of a solvent (A) having a boiling point of 50 to 100 캜 and a solvent (B) having a boiling point of 100 to 200 캜, and the content of the solvent (A) By weight and the content of the solvent (B) is in the range of 10 to 50% by weight; A transparent coating film-forming coating material delete delete delete delete The transparent coating film forming coating material according to claim 1, wherein the polymerization initiator is a phosphine-based polymerization initiator or a cationic photopolymerization initiator delete The method according to claim 1, wherein the silane-based coupling agent having the surface treated with the low refractive index fine particles is a silane-based coupling agent having at least one functional group selected from a (meth) acryloyl group, an epoxy group (glycidyl group), a urethane group, Transparent film-forming paint characterized by a coupling agent A transparent film-forming substrate comprising a transparent film formed by using the transparent film-forming coating material of claim 1 on a substrate