KR20000021805A - Ultraviolet curable composition having improved printing characteristics and hard coat film utilizing it - Google Patents

Abstract

PURPOSE: An ultra violet curable composition is provided which has a good scratch resistance, chemical resistance, thermal resistance and solvent resistance and embossing durability, CONSTITUTION: The composition comprises 30-90 weight % of ultra violet curable acrylateoligomer, 1-30 weight % of ultra violet reactive diluent, 0.1-10 weight % of photopolymerization initiator, 0.05-20 weight % of leveling agent and residue of solvent. Thus, an ultra violet curable composition containing 70 weight % of 3-functional aliphatic urethane acrylate oligomer, 15.0 weight % of trimethylolpropane triacrylate, 3 weight % of methacrylated acidic compounds, 5 weight % of hydroxy ethyl acrylate, 6.0 weight % of alpha-hydroxy-ketone, 1.0 weight % of leveling agent and residue of isopropyl alcohol is coated on polyethylene terephthalate film, dried at 50°C for 20 seconds, and irradiated by ultra violet to give the title film.

Description

UV curable composition with improved printability and hard coat film using same

The present invention relates to an ultraviolet curable composition having improved printability and a hard coat film using the same, and more particularly, to an ultraviolet curable composition having improved printability and durability of an embossed portion and a hard coat film using the same.

As an example of the field where the printability of the film is required, a membrane touch switch (MTS) widely used in various electronic products including an electronic handbook, an electronic calculator, a remote controller, and a control panel of an industrial device may be mentioned. For MTS, the film material should not only have chemical resistance, solvent resistance, heat resistance, etc., but also printability for various inks and durability of the embossed portion during embossing. Currently, film materials used for MTS include polycarbonate and polyethylene terephthalate.

Plastic materials, including polyethylene terephthalate film, have the advantages of being lightweight, rigid, and good in workability, and their applications are widely spread in response to social demands such as productivity improvement and energy saving. However, such plastic materials have a lower surface hardness than other materials and are easy to be scratched, and since they are less durable, scratches and embossed edges may occur in the above-described applications, ie, MTS films, thereby increasing the value of the product. The problem of deterioration arises.

Therefore, a number of hard coating methods have been proposed for improving the surface hardness of plastic materials and providing scratch resistance. For example, a method of applying a thermosetting silicone resin having a polysiloxane structure by applying a melamine resin, a urethane resin, an acrylic resin, an alkyd resin, or the like, and a thermosetting silicone resin, a method of applying an inorganic silicone oxide, or a polyfunctional acrylic resin The method of hardening by irradiating an ultraviolet-ray, using as a main binder is known.

However, the thermal curing method of the above method has the following disadvantages.

That is, it is hardly used at high temperatures, so it cannot be used for materials that are weak to heat, and because of the use of solvents, environmental problems such as air pollution occur, a lot of energy is consumed to cure, and a large area is required to install a curing device. It takes a long time to cure, there is a problem that productivity is lowered.

On the other hand, the UV curing method can overcome the disadvantages of the above-mentioned thermosetting method, and has excellent storage stability and can be cured within a few seconds at room temperature compared to the thermosetting method, so that the productivity is high and the deformation of the cured film is small. In the case of the film produced through the wear resistance, water resistance, solvent resistance, heat resistance, weather resistance and the like has an advantage.

Therefore, it is desired to develop a composition for a hard coat film that can improve surface hardness by applying the ultraviolet curing method and excellent in printability for various inks and durability of embossing.

The technical problem to be achieved by the present invention is to provide an ultraviolet curable composition which can improve the printability and embossing durability of various inks while improving scratch resistance, chemical resistance, solvent resistance and heat resistance of the base film.

Another technical problem to be achieved by the present invention is to provide a hard coat film using the ultraviolet curable composition.

In order to achieve the above technical problem, in the present invention, 30 to 90% by weight of the ultraviolet curable acrylate oligomer, 1 to 30% by weight of UV reactive diluent, 0.1 to 10% by weight of photopolymerization initiator, 0.05 to An ultraviolet curable composition comprising 20% by weight of a leveling agent and a residual amount of a solvent,

The oligomer is a trifunctional aliphatic urethane acrylate, the ultraviolet reactive diluent is a monofunctional or polyfunctional acrylate monomer or a mixture thereof, and the leveling agent is an ultraviolet curable non-silicone compound, the printability is improved An ultraviolet curable composition is provided.

In order to achieve the above another technical problem, the present invention provides a hard coat film using the composition.

Hereinafter, the present invention will be described in more detail.

In general, the oligomer is a compound having a molecular weight of 500 to 5000 may be diluted with each monomer according to the viscosity and physical properties, it is also a component that determines the main characteristics of the final product. The oligomers contained in the ultraviolet curable composition according to the present invention are composed of acrylates or methacrylates at the ends thereof, and urethane acrylate, epoxy acrylate, polyester acrylate, acrylic acrylate, and silicone acrylate depending on the structure of the main chain. Or amino acrylates and the like. Specifically, the characteristics of each oligomer are as follows.

Urethane acrylates include urethane bonds as repeating units and typically have flexible physical properties. There are many different types, and depending on the type of isocyanate, it is divided into aliphatic urethane acrylate and aromatic urethane acrylate. Aliphatic urethane acrylates are of the yellowing type and have 2 to 6 functional groups. Aromatic urethane acrylates are yellowing type and have fast reactivity. Epoxy acrylate contains an epoxy bond in the main chain and causes yellowing, but has excellent hardness, solvent resistance and curability. Polyester acrylate is low in viscosity and excellent in weather resistance. Acrylic acrylate has good weather resistance and water resistance, in particular good adhesion to all materials. Amino acrylate is used as a curing accelerator to improve the surface hardening and has the disadvantage of causing yellowing. Silicone acrylates are used as wetting agents, slip agents or release agents.

According to a preferred embodiment of the present invention, tri-functional aliphatic urethane for the purpose of maximizing the surface hardness by improving the crosslinking density without causing yellowing of the oligomer and excellent durability, and does not cause edge cracking during embossing Acrylate was used. The content is preferably 30 to 90% by weight based on the total weight of the composition. If the content is less than 30% by weight, the surface hardness is not sufficient, and if the content exceeds 90% by weight, the viscosity increases, and when applied to the substrate, the smoothness of the coating film or the cured film decreases, making it difficult to obtain a uniform cured film and the flexibility of the cured film. It is unfavorable because it falls and a crack arises at the time of embossing.

In the present invention, the ultraviolet reactive diluent is a monomer having a molecular weight of 500 or less, and is mainly used for the purpose of lowering the viscosity of the ultraviolet curable composition. These monomers exhibit the following characteristics depending on the number of functional groups.

First, while monofunctional (monofunctional) monomers have excellent adhesion and flexibility to the substrate, they have a disadvantage of low viscosity and viscosity when used in excess. In the present invention, as the monofunctional monomer, hydroxy ethyl acrylate having excellent curability is preferably used to enhance adhesion to the substrate.

In addition, bifunctional monomers are most commonly used because of their proper viscosity, reactivity and flexibility, and trifunctional monomers have the advantage of high hardness and reactivity. In addition, the 4 to 6 functional monomers have excellent reactivity and high crosslinking density, and thus have excellent hardness, but have disadvantages of low flexibility.

According to the present invention, it is preferable to mix and use two or more acrylate monomers among the various monomers in order to improve the crosslinking density and the curing rate within a range that does not impair flexibility. For example, trifunctional pentaerythritol triacrylate and tetrafunctional pentaerythritol tetraacrylate are mixed or trifunctional trimethylol propane triacrylate is added to the mixture. By using such a mixture of mono / polyfunctional monomers, the crosslinking density and curing rate of the hard coating can be preferably maintained.

At this time, the mono / polyfunctional acrylate monomer is preferably in the content of 1 to 30% by weight based on the total composition. If the content is less than 1% by weight, there is almost no dilution effect, resulting in a problem of high viscosity. When the content is more than 30% by weight, flexibility decreases, shrinkage of the cured layer occurs, and adhesion to the substrate decreases.

The photopolymerization initiator is responsible for initiating the reaction by absorbing ultraviolet rays to generate free radicals, and the kind thereof is not particularly limited. The initiator has different wavelength ranges absorbed according to its type, and there are yellow type and low yellow type. In general, to absorb a wavelength of 300 to 360nm, and to absorb various wavelengths to promote reactivity, two or more initiators are used together. In addition, when the coating thickness is thin, the higher the content, the better the reactivity, and when the coating thickness is thick, the total curing rate increases as the content decreases.

In the present invention, an α-hydroxyalkylphenone-based material is preferable for improving reactivity among commonly used low yellowing type initiators. Specifically, 1-Hydroxy-cyclohexyl-phenyl Ketone or α, α-dimethoxy-α-hydroxyacetophenone (α, α-Dimethoxy-α-hydroxyacetophenone) Preference is given to mixtures of one or two substances. The content of the photopolymerization initiator is preferably 0.1 to 10% by weight based on the total composition, but when the content is less than 0.1% by weight, the reactivity is slow. On the other hand, when the content is more than 10% by weight, the reactivity is increased but the surface hardness is decreased. there is a problem.

Meanwhile, the UV curable composition may include a leveling agent for increasing the smoothness of the paint, a wetting agent for reducing the surface tension of the paint, and a wetting agent for improving the wettability to the base film, an ultraviolet stabilizer, or other materials. have.

The ultraviolet curable composition of this invention is characterized by including the ultraviolet curable non-silicone compound. This material acts to give good wettability and leveling properties without migration to the film surface due to the property of direct curing reaction with the oligomer backbone. In addition, the non-silicone-based printing aptitude for the ultraviolet curable ink is excellent. The use of the silicone system lowers the surface tension of the cured coating film, so that the printing ink is not sufficiently wetted, and the adhesive strength between the printing ink and the cured coating film is deteriorated. As for the ultraviolet curing non-silicone type compound used for the composition of this invention, an acryl-styrene copolymer is preferable. The content is preferably 0.05 to 20% by weight based on the total weight of the composition, the side effect of lowering the surface hardness occurs when used in excess.

On the other hand, the ultraviolet curing method has a disadvantage in that the adhesive strength between the composition for hard coating layer and the plastic substrate such as polyethylene terephthalate film cannot be maintained at a desirable level. Typically this problem has been solved by subjecting the film surface to a primer. However, it is unavoidable to lower productivity and increase production cost due to the addition of the primer layer forming process.

Therefore, according to another embodiment of the present invention, a so-called adhesion enhancer may be used to enhance the adhesion of the composition for a hard coating layer to the base film. Due to the addition of the adhesion promoter, the composition according to the present invention can exhibit excellent adhesion to the base film without forming a primer layer. As the adhesion promoter, a methacrylated acidic compound having an acid value of 270 to 330 mgKOH / g is preferable. The content of the material is preferably 1 to 30% by weight, since the methacrylated acidic compound is added in excess of 30% by weight, which may cause stickiness of the surface.

According to another embodiment of the present invention, an antistatic agent may be used in order to prevent dust in the air due to static electricity generation on the film surface and to be contaminated. The antistatic agent should be selected in consideration of compatibility, solubility, etc. with each component of the composition. However, the antistatic agent of the surfactant system has a problem of causing whitening when the water is transferred to the surface and absorbs moisture over time. As an antistatic agent contained in the ultraviolet curable composition of this invention, the ammonium acrylate salt excellent in weatherability is preferable. The addition amount is preferably 0.1 to 5% by weight based on the total weight of the composition, if it exceeds 5% by weight because it absorbs moisture in high humidity conditions causing whitening.

The solvent contained in the ultraviolet curable composition of the present invention is generally selected in the art as a solvent used for film coating in consideration of compatibility and solubility with the composition components, and is not limited to any particular kind.

Hereinafter, the manufacturing method of the hard coat film using the ultraviolet curable composition by this invention is demonstrated.

The method for applying the ultraviolet curable composition according to the present invention to a substrate can be adopted without particular limitation as long as it is a method commonly known in the art. For example, the shape of the base film in the air knife method, the gravure method, the reverse roll method, the kiss roll method, the spray method or the blade method And can be used arbitrarily selected according to the material. As for the thickness of a coating film, about 1-10 micrometers is suitable. If the thickness of the coating film is less than 1 µm, it is difficult to obtain a sufficient cured coating film. If the thickness of the coating film is more than 10 µm, it is difficult to use due to the disadvantage that the flexibility of the coating film is poor and brittle.

After applying the ultraviolet curable composition to the base film using the method described above, the cured coating film is formed by irradiating ultraviolet rays after heating and drying by irradiating hot air, infrared rays, far infrared rays, or the like, or irradiating ultraviolet rays immediately without such a drying process. . The type of ultraviolet lamp used for ultraviolet irradiation is also not particularly limited as long as it is commonly used. For example, a high pressure mercury lamp, an ultra high pressure mercury lamp, an electrodeless lamp, a metahalide lamp and the like can be used. The output of the lamp is preferably 60 to 240 W / cm, and the cured coating film is formed by irradiating ultraviolet rays while moving the film coated with the ultraviolet curable composition by a belt conveyor. The ultraviolet curable composition according to the present invention is hardly affected by oxygen, and thus can be cured in air without the need for an inert environment such as nitrogen. The distance between the ultraviolet lamp and the base film is used to adjust the amount of light at 30 to 300mm.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples are merely examples given to show the effects of the present invention, and the scope of the present invention is not limited by the following examples.

In the following Examples and Comparative Examples, the physical properties of the prepared scratch-resistant film was evaluated by the following method.

(1) pencil hardness

Under the conditions of Japanese Industrial Standards (JIS) JIS-K5400, evaluation was made using a pencil made by Steadler with a pencil hardness meter of Sheen. Pencil specifications used were 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, 9H.

(2) scratch resistance

Rubbing the coating film with a steel wool of 10 µm in diameter to visually observe whether scratches occurred was evaluated as defective or good.

(3) chemical resistance

After immersion in a 5% aqueous sodium hydroxide solution and a 5% aqueous hydrochloric acid solution at room temperature for 4 hours, the result was evaluated as poor or good according to the change of physical properties of the coating film.

(4) solvent resistance

After immersion for 48 hours in toluene, acetone, methyl ethyl ketone, methanol, isopropyl alcohol, butyl acetate and the like at room temperature, it was evaluated as poor or good according to the change of physical properties of the coating film.

(5) heat resistance

When the film on which the ultraviolet cured film was formed was pressed for 2 seconds by applying a load of 1 kg with a heat gradient, the temperature at which the cured film was melted was measured.

(6) printability

After printing UV curable printing ink (Dongyang Ink, 4700 or 4500) on the film with UV cured film, cross-hatch the coating film at 1 mm intervals and grasp the number of cells remaining without peeling when the cellophane tape was attached and peeled off. Was evaluated as poor or good.

(7) adhesion

After cross hatching the coating film at intervals of 1 mm, the cellophane tape was attached and then peeled off to grasp the number remaining without peeling, and evaluated as defective or good.

(8) surface resistance

The surface resistance of the film was used as a measure of stain resistance. Under the conditions of ASTM D257-92, the measurement was performed at 23 ± 2 ° C. and relative humidity of 50 ± 5% using a resistance measuring instrument (DSM-8103) manufactured by East Japan Radio Wave.

<Example 1>

The UV curable composition having the composition shown below was coated on a 100 μm thick untreated polyethylene terephthalate film (Skyrol, SKC Co., Ltd.) using a 0.05 mm Meyer Bar, dried at 50 ° C. for 20 seconds, and then irradiated with an ultraviolet ray irradiation device (manufactured by Fusion, USA). , F450) and an ultraviolet lamp (US Fusion company, electrodeless H-bulb) was irradiated with ultraviolet light on the film surface. The ultraviolet irradiation distance was 50 mm, and the belt speed was adjusted so that accumulated light amount might be 200 mJ / sq.cm. The coating film thickness of the ultraviolet curable resin layer formed in this way was 3 micrometers. The physical properties of the film produced as described above are measured and shown in Table 1.

Trifunctional aliphatic urethane acrylate oligomer 70.0 parts by weight

(Ebecryl 264, manufactured by UCB Chemicals)

15.0 parts by weight of trimethylolpropane triacrylate

(SR 350, product of Sartomer)

3.0 parts by weight of methacrylated acidic compound

(Ebecryl 169, manufactured by UCB Chemicals)

5.0 parts by weight of hydroxyethyl acrylate

(HEA, manufactured by UCB Chemicals)

6.0 parts by weight of α-hydroxy ketone

(Irgacure 184, manufactured by Ciba-geigy)

1.0 part by weight of leveling agent

(HS-70, manufactured by UCB Chemicals)

50.0 parts by weight of isopropyl alcohol

<Example 2>

The UV curable composition having the following composition was applied onto an untreated polyethylene terephthalate film having a thickness of 25 μm using a 200-mesh gravure roll, dried at 50 ° C. for 20 seconds, and then irradiated with an ultraviolet irradiation device (F450, manufactured by Fusion, USA) and output 80 W. Ultraviolet rays were irradiated to the surface of the coated film using an ultraviolet lamp composed of four high-pressure mercury lamps / cm. The ultraviolet irradiation distance was 150 mm, and the belt speed was adjusted so that accumulated light amount might be 200 mJ / sq.cm. The coating film thickness of the ultraviolet curable resin layer formed in this way was 2 micrometers. The physical properties of the film produced as described above are measured and shown in Table 1.

Trifunctional aliphatic urethane acrylate oligomer 70.0 parts by weight

(Ebecryl 1259, manufactured by UCB Chemicals)

10.0 parts by weight of trimethylolpropane triacrylate

(TMPTA, manufactured by UCB Chemicals)

10.0 parts by weight of pentaerythritol tri / tetra acrylate mixture

(PETA, manufactured by UCB Chemicals)

3.0 parts by weight of methacrylated acidic compound

(Ebecryl 169, manufactured by UCB Chemicals)

6.0 parts by weight of α-hydroxyalkyl phenone

(Darocure 1173, manufactured by Ciba-geigy)

1.0 part by weight of leveling agent

(HS-70, manufactured by UCB Chemicals)

50.0 parts by weight of isopropyl alcohol

<Example 3>

The UV curable composition having the composition shown below was applied onto an untreated polyethylene terephthalate film having a thickness of 100 μm using three reverse rolls and dried at 50 ° C. for 20 seconds, followed by an ultraviolet irradiation device (F450, manufactured by Fusion, USA), and output 120 W / Ultraviolet rays were irradiated onto the surface of the coated film using an ultraviolet lamp composed of 4 cm high-pressure mercury lamps. The ultraviolet irradiation distance was 150 mm, and the belt speed was adjusted so that accumulated light amount might be 200 mJ / sq.cm. The coating film thickness of the ultraviolet curable resin layer formed in this way was 3 micrometers. The physical properties of the film produced as described above are measured and shown in Table 1.

Trifunctional aliphatic urethane acrylate oligomer 70.0 parts by weight

(Ebecryl 5129, manufactured by UCB Chemicals)

5.0 parts by weight of trimethylolpropane triacrylate

(TMPTA, manufactured by UCB Chemicals)

10.0 parts by weight of pentaerythritol tri / tetra acrylate mixture

(PETA, manufactured by UCB Chemicals)

3.0 parts by weight of methacrylated acidic compound

(Ebecryl 169, manufactured by UCB Chemicals)

5.0 parts by weight of hydroxyethyl acrylate

(HEA, manufactured by UCB Chemicals)

α-hydroxy-ketone 3.0 parts by weight

(Irgacure 184, manufactured by Ciba-geigy)

α-hydroxy-alkyl phenone 3.0 parts by weight

(Darocure 1173, manufactured by Ciba-geigy)

1.0 part by weight of leveling agent

(HS-70, manufactured by UCB Chemicals)

50.0 parts by weight of isopropyl alcohol

<Example 4>

The UV curable composition having the composition shown below was applied onto an untreated polyethylene terephthalate film having a thickness of 100 μm using a Mayer bar of 0.05 mm and dried at 50 ° C. for 20 seconds, followed by an ultraviolet irradiation device (F450, manufactured by Fusion, USA) and output 120 W / Ultraviolet rays were irradiated onto the surface of the coated film using an ultraviolet lamp composed of 4 cm high-pressure mercury lamps. The ultraviolet irradiation distance was 150 mm, and the belt speed was adjusted so that accumulated light amount might be 200 mJ / sq.cm. The coating film thickness of the ultraviolet curable resin layer formed in this way was 5 micrometers. The physical properties of the film produced as described above are measured and shown in Table 1.

53.0 parts by weight of trifunctional aliphatic urethane acrylate oligomer

(Ebecryl 1259, manufactured by UCB Chemicals)

10.0 parts by weight of trimethylolpropane triacrylate

(TMPTA, manufactured by UCB Chemicals)

10.0 parts by weight of pentaerythritol tri / tetra acrylate mixture

(PETA, manufactured by UCB Chemicals)

10.0 parts by weight of methacrylated acidic compound

(Ebecryl 169, manufactured by UCB Chemicals)

10.0 parts by weight of hydroxyethyl acrylate

(HEA, manufactured by UCB Chemicals)

α-hydroxy-ketone 3.0 parts by weight

(Irgacure 184, manufactured by Ciba-geigy)

α-hydroxy-alkyl phenone 3.0 parts by weight

(Darocure 1173, manufactured by Ciba-geigy)

1.0 part by weight of leveling agent

(HS-70, manufactured by UCB Chemicals)

50.0 parts by weight of isopropyl alcohol

Example 5

The ultraviolet curable composition having the following composition was treated in the same manner as in Example 1, and then the physical properties of the film were measured and shown in Table 1.

69.2 parts by weight of trifunctional aliphatic urethane acrylate oligomer

(Ebecryl 264, manufactured by UCB Chemicals)

15.0 parts by weight of trimethylolpropane triacrylate

(SR 350, product of Sartomer)

3.0 parts by weight of methacrylated acidic compound

(Ebecryl 169, manufactured by UCB Chemicals)

5.0 parts by weight of hydroxyethyl acrylate

(HEA, manufactured by UCB Chemicals)

6.0 parts by weight of α-hydroxy ketone

(Irgacure 184, manufactured by Ciba-geigy)

1.0 part by weight of leveling agent

(HS-70, manufactured by UCB Chemicals)

0.8 weight part of antistatic agent

(HS-600, manufactured by UCB Chemicals)

50.0 parts by weight of isopropyl alcohol

<Example 6>

The ultraviolet curable composition having the following composition was treated in the same manner as in Example 2, and then the physical properties of the film were measured and shown in Table 1.

69.2 parts by weight of trifunctional aliphatic urethane acrylate oligomer

(Ebecryl 1259, manufactured by UCB Chemicals)

10.0 parts by weight of trimethylolpropane triacrylate

(TMPTA, manufactured by UCB Chemicals)

10.0 parts by weight of pentaerythritol tri / tetra acrylate mixture

(PETA, manufactured by UCB Chemicals)

3.0 parts by weight of methacrylated acidic compound

(Ebecryl 169, manufactured by UCB Chemicals)

6.0 parts by weight of α-hydroxyalkyl phenone

(Darocure 1173, manufactured by Ciba-geigy)

1.0 part by weight of leveling agent

(HS-70, manufactured by UCB Chemicals)

0.8 weight part of antistatic agent

(HS-600, manufactured by UCB Chemicals)

50.0 parts by weight of isopropyl alcohol

<Example 7>

The UV curable composition having the following composition was treated in the same manner as in Example 3, and then the film was measured to show physical properties.

69.2 parts by weight of trifunctional aliphatic urethane acrylate oligomer

(Ebecryl 5129, manufactured by UCB Chemicals)

5.0 parts by weight of trimethylolpropane triacrylate

(TMPTA, manufactured by UCB Chemicals)

10.0 parts by weight of pentaerythritol tri / tetra acrylate mixture

(PETA, manufactured by UCB Chemicals)

3.0 parts by weight of methacrylated acidic compound

(Ebecryl 169, manufactured by UCB Chemicals)

5.0 parts by weight of hydroxyethyl acrylate

(HEA, manufactured by UCB Chemicals)

α-hydroxy-ketone 3.0 parts by weight

(Irgacure 184, manufactured by Ciba-geigy)

α-hydroxy-alkyl phenone 3.0 parts by weight

(Darocure 1173, manufactured by Ciba-geigy)

1.0 part by weight of leveling agent

(HS-70, manufactured by UCB Chemicals)

0.8 weight part of antistatic agent

(HS-600, manufactured by UCB Chemicals)

50.0 parts by weight of isopropyl alcohol

<Example 8>

The ultraviolet curable composition having the composition as described below was treated in the same manner as in Example 4, and the physical properties of the pyramid were shown in Table 1 below.

53.0 parts by weight of trifunctional aliphatic urethane acrylate oligomer

(Ebecryl 1259, manufactured by UCB Chemicals)

10.0 parts by weight of trimethylolpropane triacrylate

(TMPTA, manufactured by UCB Chemicals)

9.5 parts by weight of pentaerythritol tri / tetra acrylate mixture

(PETA, manufactured by UCB Chemicals)

10.0 parts by weight of methacrylated acidic compound

(Ebecryl 169, manufactured by UCB Chemicals)

10.0 parts by weight of hydroxyethyl acrylate

(HEA, manufactured by UCB Chemicals)

α-hydroxy-ketone 3.0 parts by weight

(Irgacure 184, manufactured by Ciba-geigy)

α-hydroxy-alkyl phenone 3.0 parts by weight

(Darocure 1173, manufactured by Ciba-geigy)

1.0 part by weight of leveling agent

(HS-70, manufactured by UCB Chemicals)

0.5 part by weight of antistatic agent

(HS-600, manufactured by UCB Chemicals)

50.0 parts by weight of isopropyl alcohol

Comparative Example 1

An ultraviolet curable composition having the composition described below was applied onto an untreated polyethylene terephthalate film (Skyrol, SKC Co., Ltd.) having a thickness of 100 μm using a Mayer bar of 0.05 mm, and cured at 160 ° C. for 1 minute to form a 5 μm thick coating film. . The physical properties of the prepared film were measured and shown in Table 1.

Solvent 79.6 wt%

(Methylethylketone)

Thermosetting Acrylic Resin 15% by weight

(Acryloid AT746, Rohm & Haas)

5% by weight of melamine curing agent

(Uformite MM83, product of Rohm Chemical)

0.3% by weight of acid catalyst

(Trifluoro acetic acid, manufactured by Akros)

0.1 wt% wetting agent

(Disperbyk 110, manufactured by BYK)

Comparative Example 2

Using the ultraviolet curable composition having the composition described below, the physical properties of the film prepared in the same manner as in Comparative Example 1 was measured and shown in Table 1.

Solvent 51.9 wt%

(Methylethylketone)

Thermosetting Urethane Resin 45% by weight

(US210, SK Chemicals)

Isocyanate Curing Agent 3% by weight

(Konnate L75, manufactured by Fine Chemical)

0.1 wt% wetting agent

(Disperbyk 103, manufactured by BYK)

Comparative Example 3

The UV curable composition having the following composition was applied onto a 100 μm thick polyethylene terephthalate film (Skyrol, SKC) using a 0.15 mm Meyer Bar, dried at 50 ° C. for 20 seconds, and then irradiated with an ultraviolet ray irradiation device (manufactured by Fusion, USA) UV light was irradiated on the surface of the coated film using an ultraviolet lamp composed of F450) and four high-pressure mercury lamps having an output power of 120 W / cm. The ultraviolet irradiation distance was 50 mm, and the belt speed was adjusted so that accumulated light amount might be 200 mJ / sq.cm. The coating film thickness of the ultraviolet curable resin layer formed in this way was 5 micrometers. The physical properties of the film produced as described above are measured and shown in Table 1.

54.7 parts by weight of trifunctional aliphatic urethane acrylate oligomer

(Ebecryl 1259, manufactured by UCB Chemicals)

20 parts by weight of trimethylolpropane triacrylate

(SR 350, product of Sartomer)

20 parts by weight of n-vinylpyrrolidone

(NVP, ISP company product)

0.3 weight part wetting agent

(HS-300, manufactured by UCB Chemicals)

α-hydroxy-ketone 5.0 parts by weight

(Irgacure 184, manufactured by Ciba-geigy)

50.0 parts by weight of isopropyl alcohol

<Comparative Example 4>

Polyethylene terephthalate film (Skyrol, SKC) was not tested with UV curable composition.

division Pencil hardness Scratch resistance Chemical resistance Solvent resistance Heat resistance Printability Adhesion Surface resistance (Ω / ㎠) Example 1 2H Good Good Good More than 240 ℃ Good Good - Example 2 2H Good Good Good More than 240 ℃ Good Good - Example 3 2H Good Good Good More than 240 ℃ Good Good - Example 4 2H Good Good Good More than 240 ℃ Good Good - Example 5 2H Good Good Good More than 240 ℃ Good Good 10 ¹² Example 6 2H Good Good Good More than 240 ℃ Good Good 10 ¹² Example 7 2H Good Good Good More than 240 ℃ Good Good 10 ¹² Example 8 2H Good Good Good More than 240 ℃ Good Good 10 ¹² Comparative Example 1 F Bad - - - Bad Good 10 ¹⁴ Comparative Example 2 F Bad - - - Bad Good 10 ¹⁴ Comparative Example 3 H Good - - - Bad Bad 10 ¹⁴ Comparative Example 4 HB Bad - - - Bad - 10 ¹⁴

In Table 1, in the case of Comparative Examples 1-4, the pencil hardness was not sufficient as the F level and the scratch resistance and the printability were poor, so it was not meaningful to evaluate the other characteristics, so that evaluation of solvent resistance, heat resistance, and chemical resistance was made. Did not.

As can be seen from the above, the hard coat film prepared by applying the ultraviolet curable composition according to the present invention to a polyethylene terephthalate film and irradiating with ultraviolet rays has a good scratch resistance, solvent resistance, chemical resistance, heat resistance and the like. In addition, despite the absence of a primer layer, not only the adhesion is excellent, but also the surface hardness is high to 2H level, suitable for use in various applications of the film. In particular, it has excellent printability for UV curable inks and does not generate cracks at the edges of embossing after embossing, so it is suitable as the outermost film material for MST of battery electronic products. There is almost no contamination caused by this.

Claims (6)

30 to 90% by weight of UV curable acrylate oligomer, 1 to 30% by weight of UV reactive diluent, 0.1 to 10% by weight of photopolymerization initiator, 0.05 to 20% by weight of leveling agent and remaining amount of solvent As an ultraviolet curable composition comprising: The oligomer is a trifunctional aliphatic urethane acrylate, the ultraviolet reactive diluent is a monofunctional or polyfunctional acrylate monomer or a mixture thereof, and the leveling agent is an ultraviolet curable non-silicone compound, the printability is improved UV curable composition. The ultraviolet curable composition according to claim 1, wherein the ultraviolet curable non-silicone compound is an acrylic-styrene copolymer. The ultraviolet curable composition of claim 1, further comprising 1 to 30% by weight of a methacrylated acidic compound as an adhesion promoter. The ultraviolet curable composition according to claim 1, further comprising 0.1 to 5% by weight of an ammonium acrylate salt as an antistatic agent. Hard coat film comprising a coating layer formed by applying the ultraviolet curable composition of any one of claims 1 to 4 on one or both sides of the base film. The hard coat film of claim 5, wherein the UV curable coating layer has a thickness of 1 to 10 μm.