KR20080073061A - Coating composition, coating method thereof, coated substrate and terminal comprising the same - Google Patents

Abstract

The present invention relates to a coating composition having improved antifouling-moisture-proof, anti-fingerprint and washability, a coating method thereof, a coated substrate, and a terminal comprising the same, including a photocurable hard coating agent including a colloidal inorganic oxide, a water-dispersible conductive polymer, and an organic It is composed of a solvent and a photopolymerization initiator, and includes at least one additive selected from the group consisting of a UV stabilizer, a UV absorber, a wetting agent, an antifouling-moisture-proofing agent, and silica, such as surface resistance, diffuse reflection, scratch resistance and strength and hardness. While maintaining physical properties, antifouling moisture-proof, anti-fingerprint and washability are improved, so that the final product can be used in a clean state, thereby improving user convenience and extending the service life.

Description

A coating composition, a coating method thereof, a coated substrate and a terminal comprising the same {A composite for coating, coating method for it, a coated substrate and electronic unit having the same}

1 is a cross-sectional view of a substrate for a mobile communication terminal window coated with a coating composition according to an embodiment of the present invention;

2 is a perspective view of a mobile communication terminal including a substrate coated with a coating composition according to an embodiment of the present invention.

<Explanation of symbols for the main parts of the drawings>

10 ... substrate, 11 ... base plastic,

12,13 ... coated composition, 30 ... keypad,

100 ... mobile communication terminal.

The present invention relates to a coating composition, a coating method thereof, a coated substrate, and a terminal including the same, and more particularly, to a coating composition having improved antifouling, moisture-proof, anti-fingerprint, and washability, a coating method thereof, a coated substrate, and the same. It is about the terminal.

With the high integration of electronic components and semiconductors, the problem of product defects caused by static electricity has emerged, and many efforts have been made to minimize the damage caused by static electricity. Static electricity, which affects parts in assembling or using electronic parts, is generated by workers, packaging materials, work spaces, and parts themselves during assembly, packaging, and transportation processes.

Therefore, there is a need for an antistatic function of materials used for storing and transporting completed electronic components, substrates for displays and the like.

The manufacture of an antistatic electronic component case, a tray, or a display substrate uses an antistatic sheet obtained by coating an antistatic composition on a base plastic surface, which is an insulator, and then drying it by thermosetting or photocuring.

The thermosetting method manufactures antistatic films and sheets using various coating methods such as gravure coating, roll coating, bar coating, and spray coating on the base plastic, so that the productivity is excellent and the surface is controlled by controlling the properties of the antistatic coating solution. Resistance (10 ² ~ 10 ¹⁰ Ω / ㎠) can be freely adjusted, there is an advantage that the liquid stability is excellent.

U.S. Patent Nos. 5,372,924 and 5,792,558, both of which are known as thermosetting antistatic coating compositions and sheet manufacturing methods using conductive polymer compositions, disclose an antistatic composition comprising conductive polythiophene as a main raw material, and Bayer Bayer Technical Information (HC Starck, Germany, 1996) introduces various compositions for easier use.

However, these thermoset coatings have the disadvantage of poor adhesion, solvent resistance and film hardness for some base plastics.

On the contrary, the photocurable coating method has the advantages of being able to cure at a low temperature and having a fast curing speed, and has excellent properties such as film hardness, solvent resistance, abrasion resistance, and adhesive strength, compared to the thermosetting coating method.

Method for producing a photocurable antistatic coating composition using a conductive polymer is known in the United States Patent Nos. 5,732,924 and 6,004,483 and the Republic of Korea Patent Publication No. 2001-69253 and 2001-58446 However, such a photocurable antistatic hard coating is only an antistatic hard coating composition using an organic compound, and is not provided with functionalities such as antifouling-moisture-proof, anti-fingerprint, and diffuse reflection.

On the other hand, in the case of a window substrate of a terminal such as a mobile communication terminal, flow coating, spin coating, etc. using a photocurable hard coating solution on an insulating base substrate such as polymethyl methacrylate (PMMA) or polycarbonate (PC). Hard coating substrates coated by various coating methods are used.

The substrate coated with the photocurable hard coating solution does not have a charging function and thus has a disadvantage in that foreign matter sticks to the substrate when it is cut. Even when using a product, ie, a mobile communication terminal, a hard-coated window substrate has excellent scratch resistance, strength, and hardness, but has a disadvantage in that it is inferior in detergency to organic substances such as anti-fouling and moisture proof, fingerprint, and cosmetics.

The present invention has been made to solve the above-mentioned problems, the coating composition having improved antifouling-moisture-proof, anti-fingerprint and washability, while maintaining the physical properties such as surface resistance, diffuse reflection, scratch resistance and strength and hardness, the coating thereof It is an object of the present invention to provide a method, a coated substrate and a terminal including the same.

In order to achieve the above object, the coating composition according to the present invention comprises a photocurable hard coating agent containing a colloidal inorganic oxide, a water dispersion conductive polymer, an organic solvent, and a photopolymerization initiator, and include a UV stabilizer, a UV absorber, a humectant, and an antifouling agent. At least one additive selected from the group consisting of a desiccant and silica.

In this case, the photocurable hard coating agent is 5 to 40% by weight, and may include at least one selected from the group consisting of an acrylic monomer, a colloidal inorganic oxide, an acrylate monomer or an oligomer, a silane compound, and a colloidal stabilizer. Can be.

Here, the acrylic monomer may contain 30 to 70% by weight, and may include a monomer including an acrylate group or a methacrylate group.

In addition, the acrylic monomer may include any one or more of a monofunctional monomer, a bifunctional monomer, and a polyfunctional monomer.

At this time, the monofunctional monomer is hydroxy ethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypentyl acrylate, hydroxyhexyl acrylate, hydroxy ethyl methacrylate, hydroxypropyl methacrylate. , At least one selected from the group consisting of hydroxybutyl methacrylate, hydroxypentyl methacrylate and hydroxyhexyl methacrylate, the bifunctional monomer is 1,6-hexanediol diacrylate, Triphenylglycol diacrylate, butanediol diacrylate, 1,3-butylene glycol dimethacrylate, neopentylglycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate Latex, polyethylene glycol diacrylate, deep Selected from the group consisting of ethylene glycol diacrylate, methoxylated neopentyl glycol diacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate and polyethylene glycol dimethacrylate Any one or more of the above-mentioned polyfunctional monomers may include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, and propylated trimethylolpropane triacryl. Latex, glycerylpropylated triacrylate, tris isocyanurate triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, dipentaerythritol hydroxypentaacrylate, trimethylolpropane methoxylation Triacrylate and twitch It is at least one selected from one group consisting of trimethylolpropane ethoxylated triacrylate.

In addition, the photocurable hard coating agent contains 20-50 weight% of colloidal inorganic oxides.

In this case, the colloidal inorganic oxide may include silica, and preferably colloidal silica dispersed in an aqueous solution.

Moreover, the colloidal inorganic oxide may comprise colloidal metal oxide.

The colloidal inorganic oxide is any one of powder, gel and sol, or a complex form, and it is preferable that the sol form is a hydrosol or an organosol.

In addition, the photocurable hard coating agent contains 5-20 weight% of a silane compound.

In this case, the silane compound includes a hydrolyzable silane residue and polymerizable residues other than the silane residue, and include methyltrimethoxysilane, dimethylmethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyl diethoxymethylsilane, 3-aminopropyltrimethoxysilane, vinyltris (β-methoxy) silane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and alkoxy The functional group may include at least one selected from the group consisting of substituted silicon.

In addition, the photocurable hard coating agent contains 5-20 weight% of colloidal stabilizers.

In this case, the colloidal stabilizer may be an acryloyl morpholine or acrylamide, and the acrylamide may be dimethyl acrylamide or dimethyl methacrylamide.

Preferably, the photocurable hard coating agent contains 30 to 70 wt% of an acrylic monomer, 20 to 50 wt% of a colloidal inorganic oxide, 5 to 20 wt% of a colloidal stabilizer, and 5 to 20 wt% of a silane compound.

In addition, the water dispersion conductive polymer may be 3 to 20% by weight.

Here, the water-dispersible conductive polymers include water-soluble polyaniline, water-soluble polypyrrole, water-soluble polythiophene, water-soluble poly (3,4-ethylenethiophene), water-soluble poly (3,4-ethylenedioxythiophene), derivatives and copolymers thereof. It may include at least one selected from the group consisting of π-conjugated electrically conductive polymer soluble in water-soluble and organic solvents.

In addition, the organic solvent may be 50 to 80% by weight.

Here, the organic solvent is dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N-methyl-2-pyrrolidinone (NMP), ethylene glycol (EG), propylene glycol methyl ether, 2-butanone, 4 Methyl-2-pentanone, ethyl cellosolve, methyl cellosolve, methyl alcohol, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, t-butyl alcohol, benzyl alcohol, di-acetone alcohol and ethylene It may include at least one selected from the group consisting of glycol.

In addition, the photopolymerization initiator may be in a content of 0.1 to 5% by weight.

Here, the photopolymerization initiator may be at least one selected from the group consisting of benzoin ether, substituted benzoin ether, substituted acetophenone, substituted α-ketol, aromatic sulfonyl chloride and photoactive oxime, and benzoin methyl ether , Benzoin isopropyl ether, anisolmethyl ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl- At least one selected from the group consisting of 2-hydroxypropiophenone, 2-naphthalenesulfonylchloride and 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime It may include.

In addition, the additive is preferably 0.01 to 15% by weight.

In this case, a silicone-based lubricant may be further added, and the silicone-based lubricant may be a siloxane copolymer or a modified polysiloxane.

In addition, the antifouling agent includes at least one or more selected from the group consisting of a perfluorine-urethane copolymer, a compound or oligomer having at least one or more fluorine-containing end groups, and a fluorine composition comprising a polymer which is a continuous unit thereof. The perfluorinated urethane copolymer may be prepared by polymerizing a perfluorinated alkyl alcohol and a functional isocyanate comonomer in a urethane reaction of a hydroxyl group and an isocyanate group by a free radical polymerization reaction in the form of a fluorine-urethane copolymer polymer. The urethane copolymer polymer may have n in the perfluorine group (CF ₃ (CF ₂ ) n functional functional group) 1 to 20 or a weight average molecular weight of 1,000 to 10,000.

In addition, the humectant is at least one selected from the group consisting of glycerin, propylene glycol, sorbitol, tricresyl phosphate, triphenyl phosphate and silica of gel type.

Preferably, 5 to 40% by weight of the photocurable hard coating agent containing a colloidal inorganic oxide, 3 to 20% by weight of the water-dispersible conductive polymer, 50 to 80% by weight of the organic solvent, and 0.1 to 5% by weight of the photopolymerization initiator. It consists of.

More preferably, the additive is 0.01 to 15% by weight.

The coating method of the coating composition according to the present invention comprises a photocurable hard coating agent containing a colloidal inorganic oxide, a water-dispersible conductive polymer, an organic solvent, and a photopolymerization initiator, and include a UV stabilizer, a UV absorber, a wetting agent, a lubricant, and an antifouling-moisture-proofing agent. And coating a coating composition comprising at least one additive selected from the group consisting of silica on a base substrate, thermosetting drying the substrate, and irradiating the substrate.

Here, the coating may be performed by any one of a flow coating, spray coating, spin coating, gravure coating, comma coating, roll coating, bar coating and dip coating or a combination method.

In addition, the thermosetting drying step is performed for 1 to 10 minutes in the temperature range of 60 ~ 90 ℃, the light irradiation step is performed by ultraviolet light of 250 to 600 mJ / cm 3 light amount.

The coated substrate according to the present invention is composed of a photocurable hard coating agent containing a colloidal inorganic oxide, a water dispersion conductive polymer, an organic solvent, and a photopolymerization initiator, and includes an ultraviolet stabilizer, an ultraviolet absorber, a wetting agent, a lubricant, an antifouling-moisture-proofing agent, and silica. The coating composition comprising at least one additive selected from the group consisting of is coated on at least one side.

Here, the substrate is polymethyl methacrylate (PMMA), polycarbonate (PC), polyester (PET A, PET G, PET G-PET A-PET G triplet), styrene-butadiene copolymer, polystyrene, Polyimide, polyamide, polysulfonate, polyacrylate, polyvinyl chloride, polyethylene, polypropylene, modified polyphenylene oxide (MPPO), phenol resin, epoxy resin, urethane resin, ABS At least one or more selected from the group consisting of ABS) resins and polymer blends or copolymers thereof may be formed in one or two or more multilayers.

The terminal according to the present invention comprises a display device, a photocurable hard coating agent containing a colloidal inorganic oxide, through which information displayed therefrom is transmitted, a water dispersion conductive polymer, an organic solvent and a photopolymerization initiator, and an ultraviolet light stabilizer. Main body and body for supporting a window, window and display device coated with at least one side of the coating composition comprising at least one additive selected from the group consisting of a UV absorber, a wetting agent, a lubricant, an antifouling-moisture-reducing agent and silica. It includes an input means provided in.

At this time, the input means is composed of a photocurable hard coating agent containing a colloidal inorganic oxide, a water-dispersible conductive polymer, an organic solvent and a photopolymerization initiator, and is composed of an ultraviolet stabilizer, an ultraviolet absorber, a wetting agent, a lubricant, an antifouling-humidifying agent, and silica. The coating composition comprising at least one additive selected from the group may be coated on at least one side.

Hereinafter, a coating composition according to an embodiment of the present invention will be described in detail.

Coating composition according to an embodiment of the present invention, (1) 5 to 40% by weight of the photocurable hard coating agent containing a colloidal inorganic oxide, (2) 3 to 20% by weight of the water dispersion conductive polymer, (3) organic solvent 50 to 80% by weight and (4) 0.1 to 5% by weight of the photopolymerization initiator, and (5) at least one additive selected from the group consisting of UV stabilizers, UV absorbers, wetting agents, antifouling and desiccant agents and silica. do.

(1.Photocuring type hard  Coating agent)

The photocurable hard coating agent includes at least one selected from the group consisting of an acrylic monomer, a colloidal inorganic oxide, a silane compound, an acrylate monomer or an oligomer, and a colloidal stabilizer, and preferably, 30 to 70 weight of the acrylic monomer. %, 20 to 50% by weight of colloidal inorganic oxide, 5 to 20% by weight of colloidal stabilizer, 5 to 20% by weight of the silane compound.

When the photocurable hard coating agent is less than 5% by weight, wear resistance and abrasion resistance is inferior, and when it exceeds 40% by weight, the basic physical properties increase but the surface resistance decreases, so 5 to 40% by weight is preferable.

(1-1.acrylic monomer)

As the acrylic monomer, a monomer containing an acrylate group or a methacrylate group may be used, and hydroxy ethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypentyl acrylate, hydroxyhexyl acrylate, and hydroxy Monofunctional monomers such as hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxypentyl methacrylate, hydroxyhexyl methacrylate, 1,6-hexanediol diacrylate, tri Phenyl glycol diacrylate, butanediol diacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate , Polyethyleneglycol 2, such as diacrylate, dipropylene glycol diacrylate, methoxylated neopentyl glycol diacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, and polyethylene glycol dimethacrylate Functional monomers and trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, propylated trimethylolpropane triacrylate, glycerylpropyl ray Tide triacrylate, tris isocyanurate triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, dipentaerythritol hydroxypentaacrylate, trimethylolpropane methoxylated triacrylate, trimethylol Propane ethoxylate Among the polyfunctional monomer, such as acrylate it can be used in one or more select.

If the content of the acrylic monomer is less than 30% by weight, the viscosity increases during the preparation of the sol-gel, and thus the synthesis is not easy.If the content of the acrylic monomer exceeds 70% by weight, the synthesis by the viscosity is easy in the preparation of the photocurable hard coating agent, but the rubbing resistance may decrease. Can be.

(1-2. Colloidal  Inorganic oxide)

Silica may be used as the colloidal inorganic oxide and may be mixed with the colloidal metal oxide. The colloidal inorganic oxide may be in any form of powder, gel or sol, but is preferably in the form of a sol in which colloidal inorganic oxide particles are dispersed in a liquid medium, and may be a hydrosol or an organosol. More preferably, colloidal silica dispersed in aqueous solution is used.

When the content of the colloidal inorganic oxide is less than 20% by weight, wear resistance and abrasion resistance may decrease. When the content of the colloidal inorganic oxide exceeds 50% by weight, the physical properties increase but the viscosity increases, so that the synthesis is not easy.

(1-3. Silane  compound)

The crosslinkable silane compound contains a hydrolyzable silane moiety and a polymerizable moiety other than the silane moiety, and may be methyltrimethoxysilane, dimethylmethoxysilane, 3-aminopropyltriethoxysilane, or 3-aminopropyl diethoxymethylsilane. , 3-aminopropyltrimethoxysilane, vinyltris (β-methoxy) silane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and the like Silicon substituted with an alkoxy functional group.

(1-4.colloid stabilizer)

As a colloidal stabilizer, acryloyl morpholine and acrylamide-based dimethyl (meth) acrylamide (N, N'-dimethyl (meta) acrylamide: DMA) can be used. It can improve the scratch resistance.

In the case of colloidal stabilizers and silane compounds, the content is less than 5% by weight may result in aggregation and precipitation of sol-gel state, and when the content exceeds 20% by weight, the sol-gel state may be stabilized but may affect physical properties. have.

(2. water dispersion conductive polymer)

Water dispersible conductive polymers include water-soluble polyaniline, water-soluble polypyrrole, water-soluble polythiophene, water-soluble poly (3,4-ethylenethiophene), water-soluble poly (3,4-ethylenedioxythiophene), derivatives and copolymers thereof, and water-soluble water. And π-conjugated electrically conductive polymers soluble in organic solvents, and the surface resistance is reduced when the content of the water-dispersible conductive polymer is less than 3% by weight, and when the content is more than 20% by weight, the surface resistance is excellent, but the permeability, It may lead to a decrease in physical properties of wear resistance and abrasion resistance.

(3. Organic Solvent)

In the case of an organic solvent, when the content is less than 50 wt%, it may cause difficulty in permeability and workability, and when it exceeds 80 wt%, physical properties such as wear resistance and scratch resistance may be reduced.

Such organic solvents include dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N-methyl-2-pyrrolidinone (NMP), ethylene glycol (EG), propylene glycol methyl ether, 2-butanone, 4 Methyl-2-pentanone, ethyl cellosolve, methyl cellosolve, methyl alcohol, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, t-butyl alcohol, benzyl alcohol, di-acetone alcohol and ethylene Glycol etc. can be used individually or in mixture. Preferably, dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidinone (NMP), ethylene glycol, isopropyl alcohol and methyl cellosolve are used.

(4. Photopolymerization Initiator )

Examples of the photopolymerization initiator include benzoin ethers such as benzoin methyl ether and benzoin isopropyl ether, and substituted benzoin ethers such as anisole methyl ether, 2,2-diethoxyacetophenone, and 2,2-dimethoxy-2-phenyl. Aromatic sulfonyl chlorides such as substituted acetophenones such as acetophenone, substituted α-ketols such as 1-hydroxycyclohexyl-phenyl-ketone, and 2-methyl-2-hydroxypropiophenone, and 2-naphthalenesulfonyl chloride And photoactive oximes such as 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime and the like can be used.

When the photopolymerization initiator is added at less than 0.1% by weight, the photopolymerization reaction is insignificant or not initiated. When the photopolymerization initiator is more than 5% by weight, the amount required for the photopolymerization reaction is saturated, so 0.1 to 5% by weight is added.

(5. additives)

Such coating compositions may further include additives such as UV stabilizers or UV absorbers.

UV stabilizers or ultraviolet absorbers improve the weatherability of the coating composition and reduce yellowing and diffuse reflection by ultraviolet light over time, and can be used alone or in combination.

The ultraviolet absorber may include cinnamate, and the like, and the ultraviolet stabilizer may include a benzophenol-based or benzotriazole-based.

In addition, a lubricant, an antifouling | moisture-proof agent, a silica, etc. may be added to a coating composition individually or in mixture.

As the lubricant, a silicone-based material may be generally used, and a siloxane copolymer, a modified polysiloxane, or the like may be used.

The antifouling-moisture-proofing agent is a perfluorine-urethane copolymer prepared by polymerizing a perfluorinated alkyl alcohol and a functional isocyanate comonomer in the form of a fluorine-urethane copolymer polymerized by a free radical polymerization reaction in a urethane reaction of a hydroxyl group and an isocyanate group. It may include a fluorine composition comprising a compound or oligomer having a fluorine-containing end group or a polymer that is a continuous unit thereof. In this case, a fluorine-scavenging perfluorinated copolymer of a urethane polymer, or CF ₃ (CF ₂₎ n wherein n is from 1 to 20 functional groups in a functional, preferably a weight average molecular weight of 1,000 to 10,000.

As the humectant, at least one or more of glycerin, propylene glycol, sorbitol, tricresyl phosphate, triphenyl phosphate, and gel type silica may be used.

When silica is added, the coating composition can be coated on the base plastic with better adhesion.

In the case of at least one functional additive selected from such a lubricant, a wetting agent, an antifouling-moisture-proofing agent, and a silica, it may have a disadvantage of deteriorating its function when it is less than 0.01% by weight, and when it is more than 15% by weight, such as abrasion resistance and abrasion resistance due to uncuring It may lead to a decrease in physical properties.

Hereinafter, a coating method of the coating composition according to an embodiment of the present invention will be described.

The coating composition is coated on a variety of base substrates by flow coating, spray coating, spin coating, gravure coating, comma coating, roll coating, bar coating, dip coating, etc., and then heat for 1 to 10 minutes in a temperature range of 60 to 90 ° C. Curing and drying removes the organic solvent in the coating composition. At this time, when the temperature is less than 60 ℃ or less than 1 minute of drying time, the organic solvent is not removed and remains, which may adversely affect the physical properties, the temperature of more than 90 ℃ thermal degradation of the organic residue occurs, 10 Exceeding minutes can result in lower production yields due to excessive drying time.

After removing the organic solvent as described above, ultraviolet ray of 250 to 600 mJ / cm 3 light amount can be irradiated and cured to produce a functional antistatic hard coating substrate. If the amount of light is less than 250 mJ / cm 3, sufficient curing may not be achieved. If the amount of light exceeds 600 mJ / cm 3, the organic material may be denatured due to excessive light energy supply. The amount of light to be irradiated is preferably 250 to 600 mJ / cm 3.

At this time, the base substrate may be a polymer synthetic resin, such as plastic, polymethyl methacrylate (PMMA), polycarbonate (PC), polyester (PET A, PET G, PET G-PET A- PET G triplet), styrene-butadiene copolymer, polystyrene, polyimide, polyamide, polysulfonate, polyacrylate, polyvinyl chloride, polyethylene, polypropylene, modified polyphenylene oxide (MPPO; Modified-Polyphenylene Oxide) ), Phenol resins, epoxy resins, urethane resins, ABS resins and polymer blends thereof, or one or two or more layers selected from copolymers thereof.

Hereinafter, a substrate coated with a coating composition according to an embodiment of the present invention and a mobile communication terminal including the same will be described with reference to the accompanying drawings.

1 is a cross-sectional view of a substrate for a mobile communication terminal window coated with a coating composition according to an embodiment of the present invention, Figure 2 is a perspective view of a mobile communication terminal including a substrate coated with a coating composition according to an embodiment of the present invention. .

The substrate 10 for the mobile communication terminal window is coated with the coating composition 12 according to the present invention on at least one side of the base sheet 11 which is an insulator. In this case, the base sheet 11 may be any one of PMMA, PC, and multiple layers of these base polymers. In addition, the coating composition 13 may be coated on the other surface of the base sheet 11.

When such a substrate 10 is used as a window of a mobile communication terminal 100 that is covered with a protective device and simultaneously housed in a main body as shown in FIG. 2, the mobile communication terminal 100 is being manufactured. The failure rate can be reduced by preventing the occurrence of static electricity, and failure rate can be reduced by preventing it even when using the final product.

In addition, when the antifouling-moisture-proof function is added, it is possible to effectively block the dust and moisture flowing through the gap between the window substrate 10 and the main body of the mobile communication terminal 100 in use, and prevents graffiti or fingerprint In this case, the fingerprint may be prevented from remaining due to the user's operation, thereby further extending the service life of the mobile communication terminal 100.

In addition, when the function is given to the input means 30 of the mobile communication terminal 100, that is, a button-type keypad or a touch screen, that is, the coating composition according to an embodiment of the present invention on a keypad composed of a polymer resin material, etc. In the case of coating, it is possible to reduce static electricity, antifouling-moisture-proof and improve graffiti resistance or anti-fingerprint, thereby improving the service life of the product.

In particular, when the input means 30 is a touch screen type and the window substrate 10 covers the input means 30, that is, when the display device and the input means are integrated, the window substrate 10 is a display device. And the input means at the same time can be effectively protected.

Hereinafter, experimental examples and comparative experimental examples of the present invention will be described.

Experimental Example 1

Acrylic monomer (40% by weight of dipentaerythritol hexaacrylate, 20% by weight of Pentaerythritol triacrylate, 60% by weight of Unwon Corporation), 25% by weight of water-dispersed silica sol (Nalco 2327, NALCO Co.) as an inorganic oxide, silane compound (3-methacrylocxa propyl trimethoxy silane , 5% by weight of Shin-etsu chemical Co.) and 10% by weight of a colloidal stabilizer (acryloyl morpholine, SATOMER Co.) were vacuum-reduced at 50 ° C. to complete the reaction to prepare a photocurable hard coating composition.

To 25 wt% of the photocurable hard coating composition prepared, 5 wt% of poly (3,4-ethylenedioxythiophene) (Baytron PH, Bayer Co.), an aqueous dispersion, and 1 wt% of a photocuring agent (Igacure 184, Ciba Geigy Co.) %, Lubricant (UV-333, BYK Co.) 0.2 wt%, Fluorine-based antifouling agent (OPTOOL-DSX, Daikin Chemical Division) 0.3 wt%, Organic solvent (Isopropyl alcohol 30 wt%, Methyl cellosolve 20 wt% 10 wt% propylene glycol methyl ether, 8.5 wt% ethylene glycol) 68.5 wt% was added to prepare a coating composition.

The coating composition was coated on a 0.8 mm polymethyl methacrylate (PMMA) base plastic by flow coating, followed by thermosetting drying at a temperature of 60 to 65 ° C. for 2 minutes to remove the solvent in the coating composition, followed by 400 mJ / cm 3 light quantity. Ultraviolet rays were irradiated to prepare a substrate.

Experimental Example 2

The photocurable hard coating composition of Experimental Example 1 was carried out in the same manner as in Experimental Example 1 except that 0.8 mm polycarbonate (PC) base plastic was coated.

Experimental Example 3

25 wt% of the photocurable hard coating composition of Experimental Example 1, 5 wt% of poly (3,4-ethylenedioxythiophene) (Baytron PH, Bayer Co.) as a water-soluble dispersion, a photocuring agent (Igacure 184, Ciba Geigy Co. ) 1% by weight, lubricant (UV-333, BYK Co.) 0.2% by weight, fluorine-based anti-fouling agent (OPTOOL-DSX, Daikin Chemical Division) 0.3% by weight, silica (2 μm spherical) 0.1% by weight, organic solvent (iso) Except that 30% by weight propyl alcohol, 20% by weight methyl cellosolve, 10% by weight propylene glycol methyl ether, ethylene glycol 8.4% by weight) 68.4% by weight was carried out in the same manner as in Experiment 1.

Experimental Example 4

25 wt% of the photocurable hard coating composition of Experimental Example 1, 5 wt% of poly (3,4-ethylenedioxythiophene) (Baytron PH, Bayer Co.) as a water-soluble dispersion, a photocuring agent (Igacure 184, Ciba Geigy Co. ) 1% by weight, lubricant (UV-333, BYK Co.) 0.2% by weight, anti-scribing agent (protect-5000, Tego Co.) 0.3% by weight, organic solvent (isopropyl alcohol 30% by weight, methyl cellosolve 20% %, Propylene glycol methyl ether 10% by weight, ethylene glycol 8.5% by weight) was carried out in the same manner as in Experiment 1 except that 68.5% by weight.

Experimental Example 5

25 wt% of the photocurable hard coating composition of Experimental Example 1, 5 wt% of poly (3,4-ethylenedioxythiophene) (Baytron PH, Bayer Co.) as a water-soluble dispersion, a photocuring agent (Igacure 184, Ciba Geigy Co. ) 1% by weight, lubricant (UV-333, BYK Co.) 0.2% by weight, fluorine-based anti-fouling agent (OPTOOL-DSX, Daikin Chemical Division) 0.5% by weight, organic solvent (isopropyl alcohol 30% by weight, methyl cellosolve 20% by weight, 10% by weight of propylene glycol methyl ether, 8.5% by weight of ethylene glycol) 68.5% by weight was added in the same manner as in Experimental Example 1.

Experimental Example 6

25 wt% of the photocurable hard coating composition of Experimental Example 1, 5 wt% of poly (3,4-ethylenedioxythiophene) (Baytron PH, Bayer Co.) as a water-soluble dispersion, a photocuring agent (Igacure 184, Ciba Geigy Co. ) 1% by weight, lubricant (UV-333, BYK Co.) 0.2% by weight, fluorine-based antifouling agent (OPTOOL-DSX, Daikin Chemical Division) 1.0% by weight, organic solvent (isopropyl alcohol 30% by weight, methyl cellosolve 20% by weight, 10% by weight of propylene glycol methyl ether, 8.5% by weight of ethylene glycol) 67.8% by weight was added in the same manner as in Experimental Example 1.

Experimental Example 7

25 wt% of the photocurable hard coating composition of Experimental Example 1, 5 wt% of poly (3,4-ethylenedioxythiophene) (Baytron PH, Bayer Co.) as a water-soluble dispersion, a photocuring agent (Igacure 184, Ciba Geigy Co. ) 1% by weight, lubricant (UV-333, BYK Co.) 0.2% by weight, fluorine-based antifouling agent (OPTOOL-DSX, Daikin Chemical Division) 2.0% by weight, organic solvent (isopropyl alcohol 30% by weight, methyl cellosolve 20 wt%, 10 wt% propylene glycol methyl ether, 8.5 wt% ethylene glycol) 66.8 wt% was added in the same manner as in Experiment 1.

Experimental Example 8

25 wt% of the photocurable hard coating composition of Experimental Example 1, 5 wt% of poly (3,4-ethylenedioxythiophene) (Baytron PH, Bayer Co.) as a water-soluble dispersion, a photocuring agent (Igacure 184, Ciba Geigy Co. ) 1% by weight, lubricant (UV-333, BYK Co.) 0.2% by weight, fluorine-based antifouling agent (OPTOOL-DSX, Daikin Chemical Division) 3.0% by weight, organic solvent (isopropyl alcohol 30% by weight, methyl cellosolve 20% by weight, 10% by weight of propylene glycol methyl ether, 8.5% by weight of ethylene glycol) 65.8% by weight was added in the same manner as in Experimental Example 1.

Experimental Example 9

25 wt% of the photocurable hard coating composition of Experimental Example 1, 5 wt% of poly (3,4-ethylenedioxythiophene) (Baytron PH, Bayer Co.) as a water-soluble dispersion, a photocuring agent (Igacure 184, Ciba Geigy Co. ) 1% by weight, lubricant (UV-333, BYK Co.) 0.2% by weight, fluorine-based anti-fouling agent (OPTOOL-DSX, Daikin Chemical Division) 0.001% by weight, organic solvent (isopropyl alcohol 30% by weight, methyl cellosolve 20% by weight, propylene glycol methyl ether 10% by weight, ethylene glycol 8.5% by weight) was carried out in the same manner as in Experiment 1 except that 68.799% by weight.

Experimental Example 10

25 wt% of the photocurable hard coating composition of Experimental Example 1, 5 wt% of poly (3,4-ethylenedioxythiophene) (Baytron PH, Bayer Co.) as a water-soluble dispersion, a photocuring agent (Igacure 184, Ciba Geigy Co. ) 1% by weight, lubricant (UV-333, BYK Co.) 0.2% by weight, fluorine-based antifouling agent (OPTOOL-DSX, Daikin Chemical Division) 15% by weight, organic solvent (isopropyl alcohol 30% by weight, methyl cellosolve 20% by weight, 10% by weight of propylene glycol methyl ether, 8.5% by weight of ethylene glycol) 53.8% by weight was added in the same manner as in Experiment 1.

Comparative Example 1

25 wt% of the photocurable hard coating composition in Experimental Example 5, 5 wt% of poly (3,4-ethylenedioxythiophene) (Baytron PH, Bayer Co.) as an aqueous dispersion, and a photocuring agent (Igacure 184, Ciba Geigy Co. ) 1% by weight, lubricant (UV-333, BYK Co.) 0.2% by weight, organic solvent (30% by weight isopropyl alcohol, 20% by weight methylcellosolve, 10% by weight propylene glycol methyl ether, 8.8% by weight ethylene glycol Except for adding 68.8% by weight was carried out in the same manner as in Experiment 1.

Physical property test results of the substrates prepared by Experimental Examples 1 to 10 and Comparative Experimental Example 1 are shown in Table 1 below.

Experimental Example 1 Experimental Example 2 Experimental Example 3 Experimental Example 4 Experimental Example 5 Experimental Example 6 Experimental Example 7 Experimental Example 8 Experimental Example 9 Experimental Example 10 Comparative Experiment 1 Additives and Additions [wt%] Fluorine-based Antifouling Agent 0.3 Fluorine-based Antifouling Agent 0.3 Silica 0.1 Anti Graffiti 0.3 Fluorine-based Antifouling Agent 0.5 Fluorine-based antifouling agent 1.0 Fluorine Antifouling Desiccant 2.0 Fluorine-based Antifouling Agent 3.0 Fluorine Antifouling-Dehumidifier 0.001 Fluorine-based antifouling agents 15 - Board PMMA PC PMMA PMMA PMMA PMMA PMMA PMMA PMMA PMMA PMMA Surface resistance [Ω / sq.] 10 ^{8 ~ 9} 10 ^{8 ~ 9} 10 ^{8 ~ 9} 10 ^{8 ~ 9} 10 ^{8 ~ 9} 10 ^{8 ~ 9} 10 ^{8 ~ 9} 10 ⁹ 10 ^{8 ~ 9} 10 ^10-11 10 ^{8 ~ 9} transparency[%] 91 91 91 91 91 91 91 91 91 89 91 Turbidity [%] 0.2 0.2 2.0 0.2 0.2 0.2 0.2 0.3 0.2 0.6 0.1 Film Hardness [H] 5 ~ 6 2 ~ 3 5 5 ~ 6 5 ~ 6 5 5 4 ~ 5 5 ~ 6 3 ~ 4 5 ~ 6 Contact angle [˚] Distilled water 116 110 111 115 116 118 121 120 87 121 87 Diiodethane 92 89 90 92 92 95 97 97 51 97 50 Fingerprint O O O O O O O O X O X Adhesive force [B] 5 5 5 5 5 5 5 5 5 4 ~ 5 4 Constant temperature and humidity No change No change No change No change No change No change No change No change No change No change Micro change

In Table 1, haze and haze were measured using COH-300A (Nippon Denshoku), UV-vis./NIR spectrometer (Shimadzu). The coated side of the substrate was then placed in the direction of the metrology section and averaged at five different points.

The contact angle was measured using a dynamic contact angle meter (Phoenix 450) using two types of contact liquids, distilled water and diiomethane at 25 ± 1 ℃. The droplet diameter at this time was 2 mm, and it measured at five different points and averaged it.

Contamination and anti-fingerprint properties were assessed for ease of wiping the fingerprint with a dry cloth after leaving the fingerprint by pressing it on the coated side of the substrate for 5 seconds using ninjin. At this time, even if fingerprints are easily wiped well, 0 is difficult to wipe, but when no trace remains, △, difficult to wipe, and marks are left as ×.

The surface resistance was averaged by five measurements using four-terminal ammeter surface resistance (MCP-T600) and two-terminal measurement method (SIMCO TRUSTAT).

Constant temperature and humidity were measured at 80 ° C, 80%, and RH (Relative Humidity) for 5 hours after 48 hours of treatment.

The adhesive force is cut by cutting the surface of the substrate into a grid of 1 mm intervals using a blade, and then strongly adhered to the three ends using 3M Magic Scotch Tape®, and then quickly separated and peeled off the surface of the coated surface. The state was measured 5 times and the average value was calculated | required.

As shown in Table 1, the substrates of Experimental Examples 1 to 8 and Experimental Example 10 are similar in physical properties such as transparency and film hardness as compared to Comparative Experimental Example 1, but have better antifouling and moisture-proof effects, and It can be seen that the washability is excellent.

That is, the contact angle with respect to distilled water in Experimental Examples 1 to 8 and Experimental Example 10 is 110 degrees or more, and has a larger value than the contact angle of 87 degrees in Comparative Experimental Example 1, so that in Experimental Examples 1 to 8 and Experimental Example 10 It can be seen that the surface energy of the coated surface is lower and the surface is hydrophobic so that the antifouling-moisture resistance is better.

As the antifouling-moisture-proof agent increases, the contact angle increases, but in Experimental Example 10 to which 15 wt% of the anti-fouling-moisture-based agent is added, the contact angle no longer increases, the film hardness and transparency decrease, and the surface resistance increases. It is preferable to add an antifouling | moisture-proof agent not to exceed 15 weight%.

In addition, in the case of Experimental Example 9 in which a trace amount of the anti-moisture desiccant was added in an amount of 0.001% by weight, it can be seen that no special physical properties appeared in comparison with Comparative Example 1. Therefore, it is preferable to add at least 0.001% by weight or more of the antifouling-humidifying agent.

In Table 2, Experimental Example 1 and Comparative Experimental Example 1 were respectively coated with fingerprints and oily magic, and the photographs before and after washing were shown.

Experimental Example 1 Comparative Experimental Example 1 Before cleaning After washing Before cleaning After washing Fingerprint

Oily magic

As shown in Table 2, it was found that the anti-fingerprint in Experimental Example 1 was superior to the fingerprint in Comparative Example 1, and the cleaning power was also excellent when comparing the state after washing. Can be.

In addition, when comparing the case of the anti-scribing using oily magic, in Comparative Experiment 1, the graffiti by the oily magic is easy and difficult to wash, while in Experimental Example 1, it was found that the anti-scratching property is excellent and the washability is also excellent. have.

Although the technical spirit of the present invention has been described in detail according to the above-described preferred embodiment, it should be noted that the above-described embodiment is for the purpose of description and not of limitation. In addition, those skilled in the art will understand that various embodiments are possible within the scope of the technical idea of the present invention.

As described above, by the coating composition according to the present invention, a coating method thereof, a coated substrate, and a terminal including the same, antifouling-moisture-proof and anti-fingerprint, while maintaining physical properties such as surface resistance, diffuse reflection, scratch resistance and strength and hardness And since the washability is improved, it is possible to use the final product in a clean state to improve the user's ease of use and extend the service life.

Claims (29)

At least one selected from the group consisting of a photocurable hard coating agent containing a colloidal inorganic oxide, a water dispersible conductive polymer, an organic solvent, and a photopolymerization initiator, and consisting of an ultraviolet stabilizer, an ultraviolet absorbent, a wetting agent, an antifouling and desiccant agent, and a silica. Coating composition comprising an additive. The coating composition of claim 1, wherein the photocurable hard coating agent is present in an amount of 5 to 40 wt%. The method of claim 1, wherein the photocurable hard coating agent comprises at least one selected from the group consisting of an acrylic monomer, a colloidal inorganic oxide, an acrylate monomer or an oligomer, a silane compound and a colloidal stabilizer. Coating composition. According to claim 1, wherein the photocurable hard coating agent, 30 to 70% by weight of the acrylic monomer, 20 to 50% by weight of colloidal inorganic oxide, 5 to 20% by weight of the colloid stabilizer and 5 to 20% by weight of the silane compound Characterized in that the coating composition. The coating composition of claim 1, wherein the water dispersion conductive polymer is in an amount of 3 to 20 wt%. The method of claim 1, wherein the water-dispersible conductive polymer is water-soluble polyaniline, water-soluble polypyrrole, water-soluble polythiophene, water-soluble poly (3,4-ethylenethiophene), water-soluble poly (3,4-ethylenedioxythiophene), these Coating composition comprising at least one selected from the group consisting of a derivative or copolymer of π-conjugated electrically conductive polymer soluble in water-soluble and organic solvents. The coating composition of claim 1, wherein the organic solvent is present in an amount of 50 to 80 wt%. The organic solvent according to claim 1, wherein the organic solvent is dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N-methyl-2-pyrrolidinone (NMP), ethylene glycol (EG), propylene glycol methyl ether, 2 Butanone, 4-methyl-2-pentanone, ethyl cellosolve, methyl cellosolve, methyl alcohol, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, t-butyl alcohol, benzyl alcohol, di A coating composition comprising at least one selected from the group consisting of acetone alcohol and ethylene glycol. The coating composition of claim 1, wherein the photopolymerization initiator is present in an amount of 0.1 to 5 wt%. The photopolymerization initiator of claim 1, wherein the photopolymerization initiator comprises at least one selected from the group consisting of benzoin ether, substituted benzoin ether, substituted acetophenone, substituted α-ketol, aromatic sulfonyl chloride, and photoactive oxime. Coating composition. The photopolymerization initiator according to claim 1, wherein the photopolymerization initiator is benzoin methyl ether, benzoin isopropyl ether, anisole methyl ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1 -Hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-2-hydroxypropiophenone, 2-naphthalenesulfonylchloride and 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl Coating composition comprising at least one selected from the group consisting of oxime. The coating composition of claim 1, wherein the additive is present in an amount of 0.01 to 15% by weight. The coating composition of claim 1, wherein the lubricant is silicone-based. The coating composition of claim 13, wherein the silicone lubricant is a siloxane copolymer or a modified polysiloxane. The antifouling agent according to claim 1, wherein the antifouling agent is selected from the group consisting of a perfluorine-urethane copolymer, a compound or oligomer having at least one or more fluorine-containing end groups, and a fluorine composition comprising a polymer which is a continuous unit thereof. Coating composition comprising at least one. The method of claim 15, wherein the perfluoro-urethane copolymer is prepared by polymerizing a perfluorinated alkyl alcohol and a functional isocyanate comonomer in the form of a fluorine-urethane copolymer polymer by a free radical polymerization reaction by a urethane reaction of a hydroxyl group and an isocyanate group. Coating composition, characterized in that. The coating composition according to claim 16, wherein n is 1 to 20 in the perfluorine group (CF ₃ (CF ₂ ) n functional functional group) of the fluorine-urethane copolymer polymer. The coating composition according to claim 16, wherein the fluorine-urethane copolymer polymer has a weight average molecular weight of 1,000 to 10,000. The coating composition of claim 1, wherein the humectant comprises at least one selected from the group consisting of glycerin, propylene glycol, sorbitol, tricresyl phosphate, triphenyl phosphate, and gel type silica. The photocurable hard coating agent containing the colloidal inorganic oxide is 5 to 40% by weight, the water dispersion conductive polymer is 3 to 20% by weight, the organic solvent is 50 to 80% by weight, the photopolymerization initiator The coating composition is 0.1 to 5% by weight. The coating composition according to claim 1 or 20, wherein the additive is 0.01 to 15% by weight. It consists of a photocurable hard coating agent containing a colloidal inorganic oxide, a water dispersion conductive polymer, an organic solvent and a photopolymerization initiator, and at least one selected from the group consisting of an ultraviolet light stabilizer, an ultraviolet absorbent, a wetting agent, a lubricant, an antifouling-moisture-proofing agent, and silica. Coating a coating composition comprising at least one additive on a base substrate; Thermosetting drying the substrate; And Irradiating the substrate with light; Coating method of the coating composition comprising a. The coating according to claim 22, wherein the coating is performed by any one or a combination of flow coating, spray coating, spin coating, gravure coating, comma coating, roll coating, bar coating, and dip coating. Way. The coating method according to claim 22, wherein the thermosetting drying step is performed for 1 to 10 minutes in a temperature range of 60 to 90 ° C. The coating method according to claim 22, wherein the light irradiation step is performed with ultraviolet light having a light amount of 250 to 600 mJ / cm 3. It consists of a photocurable hard coating agent containing a colloidal inorganic oxide, a water dispersion conductive polymer, an organic solvent and a photopolymerization initiator, and at least one selected from the group consisting of an ultraviolet light stabilizer, an ultraviolet absorbent, a wetting agent, a lubricant, an antifouling-moisture-proofing agent, and silica. A substrate coated on at least one side with a coating composition comprising at least one additive. 27. The method of claim 26, wherein the substrate is polymethylmethacrylate (PMMA), polycarbonate (PC), polyester (PET A, PET G, PET G-PET A-PET G triplet), styrene-butadiene air Copolymer, Polystyrene, Polyimide, Polyamide, Polysulfonate, Polyacrylate, Polyvinyl Chloride, Polyethylene, Polypropylene, Modified-Polyphenylene Oxide (MPPO), Phenolic Resin, Epoxy Resin, Urethane Resin At least one selected from the group consisting of ABS resins and polymer blends or copolymers thereof is formed of one or two or more multilayers. Display device; It consists of a photocurable hard coating agent containing a colloidal inorganic oxide, a water-dispersible conductive polymer, an organic solvent, and a photopolymerization initiator which coats the display device and transmits the information displayed therefrom, and includes an ultraviolet stabilizer, an ultraviolet absorber, a wetting agent, a lubricant, and an antifouling agent. A window coated on at least one side of the coating composition comprising at least one additive selected from the group consisting of a desiccant and silica; A main body supporting the window and the display device; And Input means provided in the main body; Terminal comprising a. 29. The method of claim 28, wherein the input means comprises a photocurable hard coating agent containing a colloidal inorganic oxide, a water-dispersible conductive polymer, an organic solvent and a photopolymerization initiator, UV stabilizer, UV absorber, wetting agent, lubricant, antifouling-moisture-proof agent And at least one side of the coating composition comprising at least one additive selected from the group consisting of silica.

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