KR101664735B1

KR101664735B1 - Anti-fingerprint hardcoating composition and anti-fingerprint hardcoating film using the same

Info

Publication number: KR101664735B1
Application number: KR1020150114522A
Authority: KR
Inventors: 조진주; 신국승; 임현빈
Original assignee: 롯데케미칼 주식회사
Priority date: 2015-08-13
Filing date: 2015-08-13
Publication date: 2016-10-12

Abstract

A hard coating composition for imparting high hardness to a fingerprint of a base film, the hard coating composition having a property of preventing curl of a film and improving durability of the film, A film is disclosed. The present invention provides a hard coating composition for imparting high hardness to fingerprints on a base film, wherein the binder resin comprises an ultraviolet curable polyurethane acrylate oligomer, wherein the binder resin comprises 10 to 35% by weight of at least two mixed binder resins; 5 to 30% by weight of an acrylate monomer; 0.01 to 5% by weight of inorganic fingerprint-coated inorganic nanoparticles; 25 to 80% by weight of at least two mixed solvents; And 0.01 to 10% by weight of a photoinitiator.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a hardcoat composition for preventing fingerprints, and an anti-fingerprint hardcoating composition using the same,

The present invention relates to a hardcoat composition for preventing fingerprints and a hardcoat film for preventing fingerprints using the same, and more particularly, to a hardcoat composition for preventing fingerprints from improving the hardness characteristics of fingerprints of a film laminated with a primer coating layer, Hard coating film.

Recently, the display field for processing and displaying a large amount of information has been rapidly developed as society has entered into a full-fledged information age. Recently, flat panel display devices having excellent performance such as thinning, light weight, and low power consumption have been developed Flat panel display devices such as liquid crystal displays have replaced CRTs.

In recent years, a touch-type display device, which allows the user to operate the touch panel by using the touch panel, is in the spotlight.

For example, a touch-type display device can be divided into a resistance film type and a capacitance type. All the touch-type display devices have a common point in which the user directly touches the outermost surface of the display device. Accordingly, the characteristics of the outermost surface layer of the touch-type display device (hereinafter, the inner fingerprint-hard coating film) are important factors in the life and quality of the device.

In the touch-type display device, since the user touches the inner fingerprint-hard coat film of the display device, the inner fingerprint-hard coat film requires excellent hardness characteristics. That is, when the hardness of the inner fingerprint-hard coating film is low, the damage caused by the touch of the user causes frequent repairs and shortens the life of the device.

Also, fingerprint-hardcoated films require excellent anti-fingerprint properties. This is because when the user operates the device by touching the fingerprint-hard coating film with a finger, the fingerprint-hard coating film must be prevented from being contaminated by the fingerprint.

In addition, fingerprint-hardcoated films require good slip properties.

1 and 2 are schematic views showing a process of forming an inner fingerprint-hard coating film of a conventional touch-type display device.

As shown in FIG. 1, a hard coat layer 20 made of polyfunctional acrylate is formed on a base substrate 10. Thereafter, as shown in FIG. 2, the inner fingerprint coating layer 30 is formed on the hard coat layer 20. At this time, the inner fingerprint coating layer 30 is formed by vapor-depositing or coating a non-curable fluorine compound.

However, in the conventional multi-layered film type, if the adhesion characteristics between the respective layers are poor, there is a problem of detachment of the coating film or deterioration of the characteristics of the coating film. Further, the manufacturing process becomes complicated due to the two-step process, and the manufacturing cost increases. In some cases, the hard coat layer 20 is formed by mixing a non-curable silicone material to form an inner fingerprint-hard coat layer. However, when the hard coat layer 30 material is not chemically bonded to the non-curable silicone material, The durability of the fingerprint property is deteriorated because the curable silicone material floats on the surface.

On the other hand, it may be considered to form a monolayer structure by mixing the non-curable fluorine compound with the material of the hard coat layer 30, but the permeability is degraded because of poor compatibility. Also, as in the case of the non-curable silicone material, since the non-curable fluorine material is not chemically bonded to the hard coat layer 30 material and the non-curable fluorine material floats on the surface, the durability of the fingerprint characteristic is lowered.

Japanese Patent Application Laid-Open No. 2004-114355 discloses that the wettability is adjusted by containing a nonionic surfactant, thereby improving the wettability. However, the lipophilicity of the hard coat layer is also so low that the fingerprint cleaning property is insufficient, and the durability is also insufficient. Further, if a surfactant is contained, adhesion between the hard coat layer and the substrate film is not sufficient and there is a problem of peeling.

Korean Patent Laid-Open Publication No. 2014-0085073 discloses an inner fingerprint-hard coat resin composition composed of a high hardness ultraviolet curable resin containing a hexahedral siloxane compound or a urethane acrylate compound, a fluorinated acrylate compound, a photoinitiator and an acrylic monomer. However, when a high-hardness ultraviolet curable resin is used in a large amount, the crosslinking density is increased to cause shrinkage of the coating layer, curl phenomenon and cracking of the film may occur, thereby deteriorating adhesion to the substrate and peeling. In addition, when fluorine-based acrylate or hexahedral siloxane compound is used, haze may occur on the surface of the film, and there is a problem of durability, and there is a problem that the effect of preventing fingerprints is reduced when the wiping is repeated.

Korean Patent No. 1385031 discloses a hard coat film comprising a hard coat layer containing a silicone-modified polyacrylate and a defoaming agent. However, when the antifoaming agent is used, there is a problem that the physical properties of the hard coating solution and the coating film are deteriorated as well as appearance due to the generation of foreign matter even though the processability is improved.

SUMMARY OF THE INVENTION Accordingly, the present invention has been made to solve the above problems, and it is an object of the present invention to provide a hard coating composition for imparting high hardness to fingerprints on a substrate film, which has a curl preventing property of the film and improves durability To provide a hard fingerprint hard coating composition and an anti-fingerprint hard coat film using the hard fingerprint hard coating composition.

In order to solve the above problems, the present invention provides a hard coating composition for imparting high hardness to fingerprints on a base film, wherein the binder resin comprises an ultraviolet curable polyurethane acrylate oligomer, 35% by weight; 5 to 30% by weight of an acrylate monomer; 0.01 to 5% by weight of inorganic fingerprint-coated inorganic nanoparticles; 25 to 80% by weight of at least two mixed solvents; And 0.01 to 10% by weight of a photoinitiator.

Also, the mixed binder resin includes a multifunctional polyurethane acrylate oligomer having at least six functional groups at its ends and a low functional polyurethane acrylate oligomer having at least five functional groups at its terminals .

Also, the polyfunctional polyurethane acrylate oligomer and the low-functionality polyurethane acrylate oligomer are mixed at a weight ratio of 1: 1 to 10: 1.

In addition, the inorganic fingerprint-coated inorganic nanoparticles are included as a colloidal dispersion in which two inorganic nanoparticles having different particle diameters are mixed, and the colloidal dispersion is prepared by dispersing an aqueous solution of nano-sized silica (SiO ₂ ), titanium (TiO ₂ ) or alumina (Al ₂ O ₃ ) oxide coated with a siloxane-based compound containing a fluorine group is dispersed.

Also, the above-mentioned two or more mixed solvents include one selected from the group consisting of an aromatic solvent, a ketone solvent and an alcohol solvent, and one selected from the group consisting of an ester solvent and a glycol ether solvent To provide a hard fingerprint hard coat composition.

Also, the photoinitiator is a hydroxyketone-based photoinitiator or an amino ketone-based photoinitiator.

Wherein the hard coating layer has a contact angle of water of 90 to 120 ° and a contact angle of diodomethane of 60 to 110 ° when the hard coat layer is formed on the substrate film, Coating composition.

And the entire hard coating layer is a primer coating layer coated on the base film.

According to the present invention, as a binder resin containing an ultraviolet ray-curable polyurethane acrylate oligomer, two or more mixed binder resins, an acrylate monomer, inorganic nanoparticles coated with an inner fingerprint additive, a mixed solvent of two or more kinds, and a photoinitiator In particular, the mixing ratio of the polyfunctional polyurethane acrylate oligomers having at least six functional groups at the ends and the low functional polyurethane acrylates having at least five functional groups at the terminals is controlled to reduce shrinkage of the coating layer, the curl phenomenon and the cracking are suppressed. By using two or more kinds of mixed solvents, it is possible to control the viscosity, improve the curing rate and to control the drying speed to prevent the coating layer from being uneven in thickness, Helps improve smoothness.

The inorganic nanoparticles coated with the fluorine group-containing siloxane-based compound have a role of lowering the surface tension of the fluorine group-containing siloxane compound, and serve to improve the wettability of the material, increase the surface slip property and gloss, The inorganic nanoparticles serve to impart resistance to the coating film, and the inorganic nanoparticles are useful for the anti-scratching property, thereby exhibiting the long-term and the mobility characteristics and the surface strength. Thus, the anti-fingerprint hard coating composition and the fingerprint It is possible to provide a hard coat film for preventing adhesion.

Hereinafter, preferred embodiments of the present invention will be described in detail. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. Throughout the specification, when an element is referred to as "including " an element, it means that it can include other elements, not excluding other elements, unless specifically stated otherwise.

The present invention provides a hard coating composition for imparting high hardness to fingerprints on a base film, wherein the binder resin comprises an ultraviolet curable polyurethane acrylate oligomer, wherein the binder resin comprises 10 to 35% by weight of at least two mixed binder resins; 5 to 30% by weight of an acrylate monomer; 0.01 to 5% by weight of inorganic fingerprint-coated inorganic nanoparticles; 25 to 80% by weight of at least two mixed solvents; And 0.01 to 10% by weight of a photoinitiator.

The material to be used as the base film on which the coating layer is formed by the coating composition according to the present invention is not particularly limited, but examples thereof include polymethyl methacrylate (PMMA), polycarbonate (PC), methyl methacrylate-styrene copolymer MS), polyester, styrene-butadiene copolymer, polyimide, polyamide, polysulfonate and the like can be used.

The ultraviolet curable polyurethane acrylate oligomer used as the binder resin in the present invention is ultraviolet curable and has a terminal of (meth) acrylate and has a weight average molecular weight of 1,000 to 50,000, preferably 2,000 to 30,000, more preferably Is generally from 2,500 to 25,000, and in general, ultraviolet-curable oligomers may be diluted with respective monomers and solvents depending on viscosity and physical properties.

The UV-curable polyurethane acrylate oligomer contains a urethane bond as a repeating unit, and usually has flexible properties. The polyurethane acrylate oligomer is variously classified into aliphatic urethane acrylate and aromatic urethane acrylate depending on the type of isocyanate used. The aliphatic urethane acrylate oligomer is of the non-yellowing type, usually has 2 to 20 functional groups, the aromatic urethane acrylate oligomer is yellowish type, and has a fast reactivity.

The ultraviolet ray curable polyurethane acrylate oligomer used in the present invention is free from yellowing, has a high hardness and excellent durability, has instant curing performance, imparts excellent abrasion resistance to various plastic substrates, Urethane acrylate oligomer was used.

The ultraviolet-curable polyurethane acrylate oligomer has 2 to 10 functional groups. The number of the functional groups is determined by the interaction with the solvent and the photoinitiator used in the present invention, and the desired surface hardness and adhesion to the plastic substrate Is the most desirable value.

In the present invention, the ultraviolet ray-curable polyurethane acrylate oligomer uses two or more different compounds. Preferably, the polyfunctional polyurethane acrylate oligomer having at least six functional groups and the low functional polyurethane acrylate having at least five functional groups at the ends are introduced at a feed ratio of 1: 1 to 10: 1, preferably 2: 1 to 4: 1, the crosslinking density can be controlled, thereby reducing the shrinkage of the coating layer and curling the film and preventing cracking.

Examples of the functional group include urethane acrylate, epoxy acrylate, carboxylic acid, carboxylic acid anhydride, acrylate-based functional groups (for example, methacrylate and acrylate) having C═C double bonds, (For example, aminotriethanolate, amino diethanolate, acetylacetonate, ethylacetoacetate, lactate, etc.), an amine group, an amide group, Amide, oxazoline, carbamate, etc., may be used alone or in combination of two or more.

On the other hand, although conventional thermosetting (polyether modified) acrylate oligomers may be used as the binder resin, in the present invention, it is possible to provide a hard coating composition which is superior in hardness, abrasion resistance, UV-curable polyurethane acrylate oligomer is selected.

The binder resin is contained in the hard coating composition in an amount of 10 to 35% by weight, preferably 20 to 30% by weight. If the content of the binder resin is less than 10% by weight, the binder resin content is too low to uniformly form a thin coating layer upon film coating, resulting in a lot of unevenness in the appearance and deterioration of the hardness and adhesion of the coating film. %, The coating layer becomes excessively thick due to an excessive amount of the binder resin, the viscosity of the coating solution increases, and the shrinkage rate increases during curing, resulting in cracking of the coating film, and uneven coating may occur in the coating layer.

In the present invention, the acrylate monomer is used as a medium for a hard coating composition to function as a solvent in the toning process to reduce the viscosity of the hard coating composition to improve the coating workability, and to react with the polyurethane acrylate oligomer itself, And the transparency, hardness and abrasion resistance of the cured hard coat layer can be improved. In addition, the crosslinking density can be lowered in the cured hard coating layer, thereby improving the flexibility and reducing the hardening shrinkage rate, thereby reducing curling of the hard coating film.

As such acrylate monomers, monofunctional acrylate monomers or polyfunctional acrylate monomers may be used singly or in combination, without any particular limitation. Examples of the monofunctional acrylate monomer include monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (Meth) acrylate, stearyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and hydroxyethyl Examples of the rate monomer include hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, propyl trimethylol propane triacrylate, glyceryl propyl triacrylate, (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol tetra Methacrylate, di-trimethylolpropane and the like can be used propane tetraacrylate, dipentaerythritol hydroxy pentaacrylate, dipentaerythritol hexaacrylate.

Here, since the refractive index of the cured resin by the monofunctional acrylate monomer is too high, it is more preferable to use a polyfunctional acrylate monomer in the ultraviolet ray hardening resin composition for hard coating in order to control the refractive index in the hard coat layer. The use of a polyfunctional acrylate monomer causes the polyfunctional acrylate monomer to be polymerized by photopolymerization (curing) due to crosslinking between acryloyl groups, thereby imparting smoothness to the hard coat layer and improving scratch resistance (scratch resistance) To balance hardness and curl generation.

Such acrylate monomers are included in the hard coating composition in an amount of 5 to 30% by weight, preferably 10 to 20% by weight. If the content of the acrylate monomer is less than 5% by weight, the coating workability, hardness and transparency of the hard coat layer may be deteriorated, and if it exceeds 30% by weight, curling may occur.

In the present invention, the inorganic fingerprint-coated inorganic nanoparticles improve the wettability of the material, increase the surface slip property and gloss, and provide the hard coating film with transparency. Particularly, the inorganic nano particles coated with the fingerprint- For example, the inorganic nanoparticles coated with the following formula (1) are preferably used because the fluoro group-containing siloxane-based compound lowers the surface tension, and the inorganic nanoparticles are also useful for scratch resistance, This helps to increase the surface strength.

The inorganic fingerprint additive coated inorganic nanoparticles are included as a colloidal dispersion in which two kinds of inorganic nanoparticles having different particle diameters are mixed. The colloidal dispersion is prepared by mixing nano-sized silica (SiO ₂ ), Titanium (TiO ₂ ), or alumina (Al ₂ O ₃ ) oxide coated with a fluorine group-containing siloxane compound is dispersed. More preferably, the colloidal inorganic oxide may be a colloidal metal oxide. Such a colloidal inorganic oxide may be any one of powders, gels, and sols or a complex form, and it is preferable that the sol form is a hydrosol or an organosol. More preferably, it may be colloidal titanium oxide nanoparticles dispersed in an organic solvent.

The organic solvent is not particularly limited as long as it does not impair the dispersibility of the inorganic nanoparticles. Examples of the organic solvent include alcohols such as ethanol, isopropanol, ethylene glycol and glycerin, ethyl cellosolve, t-butyl cellosolve, and propylene glycol Ethers of monomethyl ether, and ethers of monomethyl ether. Of these, alcohols such as ethanol may be preferably used.

The inorganic fingerprint-coated inorganic nanoparticles may be included in the hard coating composition in an amount of 0.01 to 5 wt%, preferably 0.1 to 2 wt% based on the coated inorganic nano-particles excluding the organic solvent. It is preferable in terms of improving the anti-dirt property of the hard coating film by giving the hard coating film to the hard coating film in the above-mentioned content range, and also improving the scratch resistance by imparting slidability. In addition, the conventional hard coating of the inner fingerprint loses its characteristic expression due to surface scratches and oil exposure, but the addition of the inorganic nanoparticles coated with the fluorine group-containing siloxane compound helps to improve the fingerprint and the scratch resistance .

The solvent used in the present invention is required for controlling viscosity and fluidity when properly coated on a substrate such as a plastic or a film. Examples of the solvent include an ether solvent, an aromatic solvent, an ester solvent, a ketone solvent, an alcohol solvent Solvents or solvents in which these are mixed can be used.

Here, the solvent is at least two of toluene, methyl ethyl ketone, diacetone alcohol, n-butanol, methanol, butyl cellosolve, ethyl acetate and butyl acetate to control viscosity and improve curing speed with oligomer addition, And more preferably the solvent is a mixture of one kind selected from the group consisting of an aromatic solvent, a ketone type solvent and an alcohol type solvent, and one kind selected from the group consisting of an ester type solvent and a glycol ether type solvent May be used.

In particular, aromatic solvents, ketone-based solvents and alcohol-based solvents are advantageous in controlling the viscosity and improving the curing rate, and ester solvents and glycol ether solvents tend to have a tendency to slow the drying rate at the time of coating composition coating, And prevents unevenness on the coated surface and helps to improve surface smoothness.

As the aromatic solvent, for example, toluene and xylene may be used alone or in combination. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., As the solvent, diacetone alcohol (DAA), n-butanol, methanol, ethanol, isopropyl alcohol, etc. may be used alone or in combination.

Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, isopropyl acetate, isobutyl acetate and isopentyl acetate. These solvents may be used alone or in combination. The glycol ether solvent Include, for example, propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethyl glycol monoethyl Ether, diethyl glycol monopropyl ether, diethyl glycol monobutyl ether, diethylene glycol-2-ethylhexyl ether, ethylene glycol monoethyl ether acetal, etc. may be used alone or in combination.

The solvent is contained in the hard coating composition in an amount of 25 to 80 wt%, and preferably in an amount of 45 to 60 wt%. If the content of the solvent is less than 25% by weight, the effect of improving the coating property and transparency of the coating liquid may be insufficient. When the content of the solvent is more than 80% by weight, the coating may be uneven and thin, The hardness and adhesiveness of the film may be deteriorated.

In the present invention, when the hard coat composition according to the present invention is coated with a liquid on the surface of a plastic substrate and photo-cured using ultraviolet (UV) light, the reaction is initiated by absorbing ultraviolet light to generate free radicals, And serves to rapidly polymerize and cure the applied coating composition.

Depending on the type of photoinitiator, the wavelength range to be absorbed varies, and most do not participate in the reaction. In general, a wavelength of 300 to 360 nm is absorbed, and two or more photoinitiators may be used together to absorb various wavelengths and promote reactivity. When the coating thickness is thin, the reactivity is improved as the content is high. When the coating thickness is thick, the total curing speed is increased as the content is decreased.

Preferred examples of the photoinitiator used in the present invention include 2-benzyl-2- (dimethylamino) -1- [4-hydroxyquinone - (4-morpholinyl) phenyl] -1-butanone, Irgacure 369), alpha-amino acetophenone ( (2,4,6-trimethylbenzoyl) (phenyl bis (2,4,6-trimethylbenzoyl) benzyl dimethyl ketal such as benzyldimethyl ketal and Irgacure-651) Bis-acyl phosphine series such as 2,4,6-trimethyl benzoyl and Irgacure 819, and mono-acyl groups such as 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide (TPO) Mono-acyl phosphine series photoinitiators may be used alone or in combination. More preferably, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184) and al And par-aminoacetophenone (Irgacure 907) can be used in combination.

The photoinitiator is contained in the hard coating composition in an amount of 0.01 to 10 wt%, preferably 0.1 to 5 wt%.

In the present invention, additives such as a leveling agent, a UV stabilizer, and a surfactant may be added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the hard coat composition, if necessary. In order to add an antistatic function, conductive polymers, metal particles, inorganic oxides, metal oxides, etc. may be used alone or in a mixture and dispersed in the composition.

The method of forming the hard coating layer on the substrate film using the hard coating composition according to the present invention is not particularly limited as long as it is known in the art and includes, for example, dip coating, flow coating, Coating can be carried out by a suitable method such as spray coating, roll coating, gravure coating or micro-gravure coating. After the coating, the film is dried or IR-heated at 60 to 120 ° C for 1 to 20 minutes to completely remove the solvent in the coating solution, and then irradiated with ultraviolet light at an appropriate light quantity to obtain a completely cured coating film. Suitable lamps are mercury lamps or metal halide lamps.

The hard coating film obtained through the coating process can be applied to a protective panel for various displays such as a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescence display (LED) have.

On the other hand, the production of the base film is not particularly limited and can be carried out by a method generally known in the art to which the present invention belongs. For example, polyethylene terephthalate is melt-extruded on a rotary cooling drum maintained at 15 to 25 ° C to prepare an unstretched film (sheet), subjected to 2 to 5 times of longitudinal stretching at 100 to 130 ° C, A biaxially stretched PET base film produced by performing 2 to 5 times transverse stretching at 150 ° C and then heat setting at 200 to 260 ° C may be used.

Hereinafter, a specific embodiment of the present invention will be described.

Example One

20 parts by weight of a polyurethane acrylate oligomer having a 10-terminal end (MU9800, MWC, Korea), 10 parts by weight of a polyurethane acrylate oligomer having a bifunctional end (PU2560, Mi Won Company, Korea) , 16.4 parts by weight of trimethylolpropane tri (meth) acrylate (M300, MWC, Korea) as a monomer, 40 parts by weight of methyl ethyl ketone (MEK) as a ketone solvent, 10 parts by weight of ethyl acetate (EA) 2 parts by weight of 1-hydroxycyclohexyl phenyl ketone (Irgacure 184) as a photoinitiator, 0.1 part by weight of inorganic nanoparticles coated with a fluorine group-containing siloxane compound prepared by the following method, silicone leveling agents BYK349 and BYK378 1.0 part by weight and 0.5 part by weight were uniformly mixed to prepare a hard coating composition.

[Process for producing inorganic nanoparticles coated with fluorine group-containing siloxane compound]

A fingerprint-inhibiting agent X-71-1203M (Shin-Etsu Chmical Co., Ltd.) was added to two TiO ₂ nanoparticles dispersed in ethanol having different sizes of 60 to 200 nm and 21 nm Was prepared.

Example 2

A hard coat composition was prepared in the same manner as in Example 1, except that 11.5 parts by weight of the acrylate monomer and 5 parts by weight of the coated inorganic nanoparticles in Example 1 were used.

Example 3

A hard coat composition was prepared in the same manner as in Example 1, except that 15.5 parts by weight of the acrylate monomer and 1 part by weight of the coated inorganic nanoparticles in Example 1 were used.

Example 4

A hard coat composition was prepared in the same manner as in Example 3, except that PU2300C (MWC, Korea) was used instead of PU2560 as a polyurethane acrylate oligomer having a bifunctional end in Example 3.

Example 5

Except that a polyurethane acrylate oligomer (PU610, manufactured by Mi Won Co., Ltd., Korea) having a 6-terminal end was used instead of the bifunctional polyurethane acrylate oligomer in Example 3, a hard coating A composition was prepared.

Example 6

The same procedure as in Example 3 was carried out except that 24 parts by weight of a polyurethane acrylate oligomer (MU9800) having a 10-terminal end in Example 3 and 6 parts by weight of a polyurethane acrylate oligomer having a bifunctional end (PU2560) Hard coating compositions were prepared.

Example 7

The same procedure as in Example 3 was carried out except that 15 parts by weight of a polyurethane acrylate oligomer (MU9800) having a 10-terminal end in Example 3 and 15 parts by weight of a polyurethane acrylate oligomer having a bifunctional end (PU2560) Hard coating compositions were prepared.

Comparative Example One

A hard coat composition was prepared in the same manner as in Example 1 except that 6.5 parts by weight of the acrylate monomer and 10 parts by weight of the coated inorganic nanoparticles in Example 1 were used.

Comparative Example 2

The same procedure as in Example 3 was carried out except that polyurethane acrylate oligomer (PU2560) having a bifunctional terminal was removed and 30 parts by weight of a polyurethane acrylate oligomer (MU9800) To prepare a hard coating composition.

Comparative Example 3

The same procedure as in Example 3 was carried out except that 30 parts by weight of a polyurethane acrylate oligomer (PU2560) having a bifunctional end except for the polyurethane acrylate oligomer (MU9800) having a 10-terminal end in Example 3 was quantified To prepare a hard coating composition.

Comparative Example 4

A hard coat composition was prepared in the same manner as in Example 3 except that 50 parts by weight of methyl ethyl ketone (MEK) except for ethyl acetate (EA) was quantified in Example 3.

Comparative Example 5

A hard coat composition was prepared in the same manner as in Example 3, except that methyl ethyl ketone (MEK) was removed in 50 parts by weight of ethyl acetate (EA).

Comparative Example 6

A hard coat composition was prepared in the same manner as in Example 3, except that the fluorine group-containing siloxane compound (X-71-1203M) was used instead of the inorganic nanoparticles coated in Example 3.

Comparative Example 7

A hard coat composition was prepared in the same manner as in Example 2, except that the fluorine group-containing siloxane compound (X-71-1203M) was used in place of the inorganic nanoparticles coated in Example 2.

The composition (unit: parts by weight) of the hard coating composition prepared according to the above Examples and Comparative Examples is shown in Table 1 below.

Test Example

For the evaluation of the substrate film with the hard coat layer formed from the hard coat composition according to the present invention, a hard coat composition prepared according to the Examples and Comparative Examples was used to apply a 4 탆 thick hard coat composition to a 100 탆 PET film The PET film was heat-treated for 60 seconds in a heat treatment zone of 100 占 폚 to be completely dried, and irradiated with ultraviolet rays at a light quantity of 600 mJ / cm2 with a high-pressure mercury lamp to cure the hard film, . The produced films were evaluated according to the following measurement methods, and the results are shown in Table 2 below.

[Measurement and evaluation method]

(1) Appearance

The backside of the hardcoat was treated with matte black ink at room temperature (23 캜, relative humidity 65% RH) and observed at an angle of 15 degrees. &Quot; o "indicates no staining," DELTA "indicates that the stain is weak, and" X "

(2) Cross cuts

100 squares of 1 mm 2 of squares were placed on the hard coat layer of the hard coat film at room temperature (23 ° C., relative humidity 65% RH), cellophane tape (manufactured by Nichiban Co., Ltd.) was stuck thereon, 19.6 N, and peeled in the direction of 90 DEG, and evaluated in five steps according to JIS K 5400 according to the number of the hard coat layer remaining. 5B and 4B were evaluated as good adhesiveness.

- 5B: remaining number of hard coating layer 100%

- 4B: 95% or more

- 3B: 85% or more

- 2B: 55% or more

- 1B: 54% or less

(3) Pencil hardness

5 mm was drawn 5 mm at a speed of 0.5 mm / sec at a load of 500 kg / cm 2 using a pencil hardness tester (Toyoseki Co.) with a Mitsubishi evaluation pencil (UNI), and the number of scratches The hardness was evaluated.

(4) Print fingerprint

The fingerprints of all the samples were processed by the matte black ink on the back side of the hard coating, and the finger was slowly pressed against the surface of the hard coating layer to judge whether the fingerprints of the samples could be seen. "◯" indicates that there is no visible fingerprint, "△" indicates that the fingerprint is weak, and "X" indicates that the fingerprint is visible.

(5) Fingerprints

Fingerprints were applied to the surface of the hard coating layer of the hard coating film, and fingerprints were applied to the surface of the hard coating layer. The fingerprints were polished 5 times using a toilet paper, and then fingerprints were visually observed. "◯" indicates that there is no visible fingerprint, "△" indicates that the fingerprint is weak, and "X" indicates that the fingerprint is visible.

Further, in order to confirm the durability of the effect of preventing fingerprints, the specimens were immersed in methanol for 24 hours and left at room temperature for 24 hours. Thereafter, the surface was observed after performing the above method.

(6) Contact angle

The contact angle was measured with respect to the hard coat film in order to confirm the degree of wetting of the surface of the film formed by curing the anti-fingerprint hard coat composition. The contact angle of water and diiodomethane (DIM) was measured using phoenix-300 (SEO, Inc.), and the amount of solvent was 2 μl at room temperature. The contact angle is determined by the surface free energy, and the higher the contact angle, the lower the surface energy.

(7) Curl

A sample cut into a size (10x10 cm) shape was placed on a flat glass plate with the hard coating layer of the film facing up, and the distance from the four glass plates was measured at 25 DEG C and 50% RH.

- Very good: 0-15mm

- Good: over 15mm ~ 30mm

- Poor: more than 30mm to less than 50mm

- very poor: more than 50mm

Referring to Table 2, TiO ₂ nanoparticles coated with an appropriate amount of anti-fading agent were added to the hard coat layer according to the present invention, and the mixture ratio of oligomer and solvent was selected at an appropriate ratio (Examples 1 to 7) Hard coat film having excellent appearance and fingerprint proof durability and having low croquette, pencil hardness and curl was obtained.

However, in the case of Comparative Example 1, the use of an excess amount of the TiO ₂ nanoparticle coated with the anti-fingerprint agent was superior in the fingerprints and scrub resistance, but the manufacturing cost was increased and the appearance was inhibited as the particle content was increased .

In addition, in Comparative Examples 2 and 3, the polyfunctional polyurethane acrylate oligomers having a 6-functional or more terminal and the terminal were not charged at a proper ratio of the polyfunctional acrylate having 5 or less functionalities, The surface hardness is increased due to the polyfunctional oligomer. However, due to the brittleness of the coating layer, peeling occurs at the time of cross-cutting due to the tape, and when the functional group is hardened at the time of curing, It was found that the physical properties required of the surface protective film could not be obtained because the Curl value was increased, and in Comparative Example 3, the hardness was lowered.

Also, referring to Comparative Examples 4 and 5, when using a solvent composed of one kind of an aromatic solvent, a ketone type solvent, an alcohol type solvent and an ester type solvent and a glycol ether type solvent, optimum surface characteristics are obtained, It was found that the use of only the ketone solvent as in Example 4 was effective in controlling the viscosity of the solvent and improving the curing rate but the surface smoothness was deteriorated due to the excessively fast drying rate and when the ester solvent as in Comparative Example 5 was used alone, , The drying speed of the coating composition was delayed and the curing did not occur smoothly, so that the cross-cut value slightly decreased and the appearance was uneven.

In the case of Comparative Examples 6 and 7, the grass fingerprints were excellent in sound and fingerprint clearing, but they were washed in methanol for 24 hours, and when the fingerprint was evaluated, the fingerprints were weakened or lost.

The preferred embodiments of the present invention have been described in detail above. It will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Accordingly, the scope of the present invention is defined by the appended claims rather than the foregoing detailed description, and all changes or modifications derived from the meaning, range, and equivalence of the claims are included in the scope of the present invention Should be interpreted.

Claims

A hard-coating composition for imparting a high hardness to fingerprint in a base film,
A binder resin comprising an ultraviolet curable polyurethane acrylate oligomer, wherein the binder resin comprises 10 to 35% by weight of at least two mixed binder resins;
5 to 30% by weight of an acrylate monomer;
0.01 to 5% by weight of inorganic fingerprint-coated inorganic nanoparticles;
25 to 80% by weight of at least two mixed solvents; And
0.01 to 10% by weight of a photoinitiator;
, &Lt; / RTI &
The mixed binder resin is a mixture of a polyfunctional polyurethane acrylate oligomer having at least six functional groups at the end and a low functional polyurethane acrylate oligomer having at least five functional groups at a weight ratio of 1: 1 to 2: 1,
The inorganic fingerprint additive coated inorganic nanoparticles are contained as a colloidal dispersion in which two kinds of inorganic nanoparticles having different particle diameters of 60 to 200 nm and 21 nm or less are mixed and the colloidal dispersion is dispersed in an organic solvent silica nano-sized (SiO _2), titanium (TiO ₂₎ or alumina (Al ₂ O ₃₎ within a fingerprint high-hardness hard coat composition as oxides fluorine group characterized in that containing the siloxane-based compound is coated with the nano-particles are dispersed in.

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The method according to claim 1,
Wherein the two or more mixed solvents include one selected from the group consisting of an aromatic solvent, a ketone solvent and an alcohol solvent, and an ester solvent and a glycol ether solvent. Fingerprint hardness hard coating composition.

The method according to claim 1,
Wherein the photoinitiator is a hydroxyketone-based photoinitiator or an amino ketone-based photoinitiator.

The method according to claim 1,
Wherein the hard coating layer has a contact angle of water of 90 to 120 ° and a contact angle of diodomethane of 60 to 110 ° on the surface of the hard coat layer when the hard coat layer is formed on the base film, Composition.

8. The method of claim 7,
Wherein the entire hard coating layer is a primer coating layer coated on the base film.