KR102036100B1 - Uv-curable composition for hard-coat paining - Google Patents

Abstract

The present invention relates to an ultraviolet curable hard coat coating composition. In one embodiment, the UV curable hard coating composition is (A) 100 parts by weight of an aliphatic urethane acrylate oligomer comprising at least 6 polymerizable functional groups, (B) 5 to 20 parts by weight of benzotriazole-modified urethane acrylate oligomer, (C) 5 to 15 parts by weight of a polycarbonate-modified urethane acrylate oligomer, (D) 0.01 to 2 parts by weight of an oxidation stabilizer, and (E) 1 to 10 parts by weight of a photopolymerization initiator, (F) 40 to 70 parts by weight of a polyfunctional acrylate monomer. Part, (G) 5 to 20 parts by weight of the ultraviolet absorber and (H) 1 to 10 parts by weight of the light stabilizer, wherein the (D) oxidative stabilizer is octadecyl-3- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate and tris (2,4-di-t-butyl phenyl) phosphite in a 1: 0.2 to 1: 0.8 weight ratio, wherein the (F) polyfunctional acrylate monomer is 1,6 -Hexanediol diacrylate and trimethylolpropane triacrylate in a weight ratio of 1: 1.5 to 2 It will be mixed.

Description

UV Curing Hard Coating Composition {UV-CURABLE COMPOSITION FOR HARD-COAT PAINING}

The present invention relates to an ultraviolet curable hard coat coating composition. More specifically, it is applied to the surface of plastic base materials such as polycarbonate, and it is excellent in the effect of preventing yellowing even if left in the outdoor environment for a long time, and excellent in reliability, adhesion, hardness, abrasion resistance and impact resistance, and can be applied to a hard coating layer for automotive headlamp lenses. An ultraviolet curable hard coat coating composition.

An automobile headlight (headlight) is a lamp that illuminates the front of a car to drive safely at night. The conventional automotive headlamp market uses glass having excellent transparency as a headlamp cover.

However, these glass headlamp covers are low in durability, heavy in weight, and have a high production cost. Therefore, the headlamp covers that are currently produced for weight reduction of materials for improving fuel efficiency of automobiles and cost reduction for production costs are improved. The plastics, which are excellent in transparency and formability, in particular polycarbonate materials are used.

However, polycarbonate materials generally applied to automotive headlamp lenses have excellent transparency and impact resistance, but have low scratch resistance, weather resistance, and chemical resistance. Therefore, in order to supplement the scratch resistance and weather resistance, which is a weak point of the polycarbonate material, there is a need for a hard coat coating process for coating with a coating composition having excellent weather resistance and scratch resistance.

An example of using a polyfunctional urethane acrylate oligomer for improving the scratch resistance of such a polycarbonate material is disclosed in Korean Patent Publication No. 10-0199908. However, in the case of this composition, when exposed to the outdoor environment for a long time due to the shrinkage stress between molecules in the coating film, the coating film is severely cracked and yellowed, causing damage to the appearance of the coating film, deterioration of adhesion and discoloration. It is urgent to develop a hard coating paint for this purpose.

In addition, the benzotriazole-modified aliphatic urethane acrylate oligomer included in the ultraviolet curable coating composition is produced by the reaction of a benzotriazole having a hydroxy group, an isocyanate, and an acrylate compound. Ingredients used. However, the benzotriazole-modified aliphatic urethane acrylate had a problem in that the film peeled off and discolored when irradiated with 3,500 kJ / m ² energy in the accelerated weather resistance evaluation (SAE J1960). This is known to be due to the dropping of benzotriazole due to ultraviolet irradiation.

In order to solve such coating defects (falling off the coating), polycarbonate-modified urethane acrylate resin was used to improve adhesion, but the situation where the heat resistance and yellowing were further improved.

Accordingly, the present inventors have continued to research, including excellent aliphatic urethane acrylate oligomer, benzotriazole-modified urethane acrylate oligomer, polycarbonate-modified aliphatic urethane acrylate oligomer and oxidative stabilizer, and excellent adhesion, scratch resistance, impact resistance, etc. The present invention has been completed by deriving the composition of the UV-curable hard coating composition used in automobile headlamp lenses having excellent yellowing prevention effect even in long time outdoor conditions.

It is an object of the present invention to provide an ultraviolet curable hard coating composition having excellent anti-yellowing effect and reliability.

Another object of the present invention is to provide an ultraviolet curable hard coat coating composition excellent in adhesion, hardness, wear resistance and impact resistance.

Still another object of the present invention is to provide an ultraviolet curable hard coat coating composition having excellent heat resistance, weather resistance and chemical resistance.

Still another object of the present invention is to provide a headlamp lens including the ultraviolet curable hard coat coating composition.

One aspect of the present invention relates to an ultraviolet curable hard coat coating composition. In one embodiment, the UV curable hard coating composition is (A) 100 parts by weight of an aliphatic urethane acrylate oligomer comprising at least 6 polymerizable functional groups, (B) 5 to 20 parts by weight of benzotriazole-modified urethane acrylate oligomer, (C) 5 to 15 parts by weight of a polycarbonate-modified urethane acrylate oligomer, (D) 0.01 to 2 parts by weight of an oxidation stabilizer, and (E) 1 to 10 parts by weight of a photopolymerization initiator.

In one embodiment, (A) the aliphatic urethane acrylate oligomer comprising at least six polymerizable functional groups is a reaction product of a bifunctional aliphatic isocyanate compound and a hydroxy acrylate monomer containing at least three polymerizable unsaturated groups. It features.

In one embodiment, the (A) aliphatic urethane acrylate oligomer comprising at least six polymerizable functional groups is characterized by a weight average molecular weight of 1,000 to 2,000 g / mol.

In one embodiment the (D) oxidative stabilizer is octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and tris (2,4-di-t-butyl phenyl) It is characterized by including the phosphite in a 1: 0.2 to 1: 0.8 weight ratio.
In one embodiment, (A) 40 to 70 parts by weight of the polyfunctional acrylate monomer (F) based on 100 parts by weight of the aliphatic urethane acrylate oligomer including at least six polymerizable functional groups.

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In one embodiment, the (F) multifunctional acrylate monomer is characterized in that it comprises 1,6-hexanediol diacrylate and trimethylolpropane triacrylate.

In one embodiment, (A) 5 to 20 parts by weight of the ultraviolet absorber and (H) 1 to 10 parts by weight of the light stabilizer, based on 100 parts by weight of the aliphatic urethane acrylate oligomer including at least six polymerizable functional groups. Characterized in that.

Another aspect of the invention relates to a headlamp lens comprising an ultraviolet curable hard coating coating composition. In one embodiment the headlamp lens comprises a plastic substrate; And a hard coating layer formed on one surface of the plastic substrate, wherein the hard coating layer may include the above-mentioned UV curable hard coating composition.

In one embodiment, the thickness of the hard coating layer is characterized in that 5 ~ 25㎛.

In one embodiment the plastic substrate is polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), triacetyl cellulose (TAC), polycarbonate (PC), polyimide (PI), Polyethylene (PE), polypropylene (PP), polyether sulfone (PES), polyvinyl alcohol (PVA) and polyvinyl chloride (PVC) is selected from.

UV-curable hard coating composition according to the present invention is excellent in preventing the yellowing even when left in the outdoor environment for a long time, excellent in reliability, adhesion, hardness, wear resistance and impact resistance, excellent heat resistance, weather resistance and chemical resistance It may be suitable for automotive headlamp lenses.

1 (a) is a result of the accelerated weather resistance evaluation of the specimen of the comparative example for the present invention, Figure 1 (b) is a photograph showing the result of the accelerated weather resistance of the specimen prepared in the embodiment of the present invention.

In the following description of the present invention, when it is determined that detailed descriptions of related well-known technologies or configurations may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted. The terms to be described below are terms defined in consideration of functions in the present invention, and may be changed according to intentions or customs of users or operators, and the definitions should be made based on the contents throughout the specification for describing the present invention.

One aspect of the present invention relates to an ultraviolet curable hard coat coating composition. In one embodiment, the UV-curable hard coating composition is (A) aliphatic urethane acrylate oligomer comprising at least six polymerizable functional groups, (B) benzotriazole modified urethane acrylate oligomer, (C) polycarbonate modified urethane acrylic Late oligomers, (D) oxidation stabilizers, and (E) photopolymerization initiators.

In one embodiment, the UV curable hard coating composition is (A) 100 parts by weight of an aliphatic urethane acrylate oligomer comprising at least 6 polymerizable functional groups, (B) 5 to 20 parts by weight of benzotriazole-modified urethane acrylate oligomer, 5 to 15 parts by weight of (C) polycarbonate-modified urethane acrylate oligomer, 0.01 to 2 parts by weight of (D) oxidation stabilizer, and (E) 1 to 10 parts by weight of photopolymerization initiator. When included in the above range may be excellent in the yellowing prevention effect, reliability, heat resistance, weather resistance and chemical resistance.

Hereinafter, the configuration of the ultraviolet curable hard coat coating composition will be described in more detail.

(A) six or more Polymerizable A functional group  Aliphatic urethane containing Acrylate  Oligomer

The aliphatic urethane acrylate oligomer (A) including the six or more polymerizable functional groups may be included for the purpose of improving the hardness, crack resistance and scratch resistance when forming the hard coat layer.

In one embodiment, an aliphatic urethane acrylate oligomer (A) containing at least six polymerizable functional groups may be used. For example, the reaction product may be a reaction product with a bifunctional aliphatic isocyanate compound and a hydroxy acrylate monomer including three or more polymerizable unsaturated groups.

In one embodiment, the bifunctional aliphatic isocyanate compound may include one or more of hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate, and the hydroxy acrylate monomer may be pentaerythritol tri It may include one or more of acrylate, dipentaerythritol triacrylate.

In one embodiment, the weight average molecular weight of the aliphatic urethane acrylate oligomer (A) including the six or more polymerizable functional groups may be 1,000 to 2,000 g / mol. Preferably it may be 1,500 ~ 2,000 g / mol. In the above range, in the process of forming the hard coating layer of the UV-curable hard coating composition, the adhesion to the substrate for the headlamp, UV curability and workability may be excellent.

(B) Benzotriazole  Modified urethane Acrylate  Oligomer

The benzotriazole-modified urethane acrylate oligomer (B) may be included for the purpose of improving the chemical resistance of the present invention.

In one embodiment, the benzotriazole-modified urethane acrylate oligomer (B) may be conventional. For example, those obtained by reacting an aliphatic urethane acrylate oligomer and a benzotriazole-modified acrylate having a hydroxy group can be used.

In one embodiment, the aliphatic urethane acrylate oligomer may be obtained by reacting a bifunctional aliphatic isocyanate compound and a hydroxy acrylate monomer containing not more than two polymerizable unsaturated groups per molecule.

The bifunctional aliphatic isocyanate compound may include one or more of hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate.

Examples of the hydroxy acrylate monomer containing two or less unsaturated polymerizable polymer groups per molecule include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate and hydroxypentyl. One or more of acrylate and hydroxybutyl methacrylate.

As the benzotriazole-modified acrylate in the present invention can be used a conventional one. For example, those having a weight average molecular weight of 300 to 500 g / mol can be used. Transparency and usability in the above range can be excellent.

In one embodiment, the weight average molecular weight of the benzotriazole-modified urethane acrylate oligomer (B) may be 800 to 1500 g / mol. In the above range it may be excellent in weather resistance and chemical resistance of the present invention.

In one embodiment, the benzotriazole-modified urethane acrylate oligomer (B) may be included in an amount of 5 to 20 parts by weight based on 100 parts by weight of the aliphatic urethane acrylate oligomer (A) including the six or more polymerizable functional groups. Preferably the benzotriazole-modified urethane acrylate oligomer (B) may be included in 8 to 18 parts by weight, more preferably 10 to 15 parts by weight. When the benzotriazole-modified urethane acrylate oligomer (B) is included in less than 5 parts by weight, the weather resistance and chemical resistance of the present invention is lowered, and when it contains more than 20 parts by weight, curing of the present invention becomes difficult, and the yellowing prevention effect Can be degraded.

(C) polycarbonate modified urethane Acrylate  Oligomer

The polycarbonate modified urethane acrylate oligomer (C) may be included for the purpose of improving the elasticity, flexibility and adhesion of the present invention.

In one embodiment, the polycarbonate-modified urethane acrylate oligomer (C) is a product obtained by reacting a polycarbonate diol, a bifunctional aliphatic isocyanate compound and a hydroxy acrylate monomer containing up to 2 unsaturated groups per molecule. Can be.

As the compound of the bifunctional aliphatic isocyanate, one or more of hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate may be used.

As the hydroxy acrylate monomer, one or more of hydroxy ethyl acrylate, hydroxy propyl acrylate, hydroxy ethyl methacrylate, hydroxy butyl acrylate, hydroxy pentyl acrylate and hydroxy butyl methacrylate may be used. Can be.

In one embodiment, the weight average molecular weight of the polycarbonate-modified urethane acrylate oligomer (C) may be 1,000 ~ 2,000 g / mol. Preferably it may be 1,500 ~ 2,000 g / mol. In the above range may be excellent in adhesion, curability and workability to the substrate for the headlamp in the hard coating layer forming process of the UV-curable hard coating composition.

In one embodiment, the polycarbonate-modified urethane acrylate oligomer (C) may be included in an amount of 5 to 15 parts by weight based on 100 parts by weight of the aliphatic urethane acrylate oligomer (A) including the six or more polymerizable functional groups. Preferably 5 to 12 parts by weight may be included. More preferably 7 to 10 parts by weight may be included. When the polycarbonate-modified urethane acrylate oligomer (C) is included in less than 5 parts by weight, the adhesion of the coating layer formed in accordance with the present invention is reduced and dropping occurs, and when included in more than 15 parts by weight, the weather resistance of the present invention is lowered , Transparency may be reduced.

(D) Oxidation Stabilizer

The oxidation stabilizer (D) may be included for the purpose of improving the yellowing prevention effect by inhibiting the production of the quinone compound which is the main cause of the yellowing phenomenon. In the present invention, the oxidative stabilizer (D) may be used at least one of phenol-based and phosphorus oxidative stabilizer.

In one embodiment, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate may be used as the phenolic oxidative stabilizer. Tris (2,4-di-t-butyl phenyl) phosphite may be used as the phosphorus oxidation stabilizer. When using the above-described oxidation stabilizer (D) may be excellent in the yellowing prevention effect of the present invention.

In one embodiment the oxidative stabilizer comprises octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and tris (2,4-di-t-butyl phenyl) phosphite It can be mixed and used in a weight ratio of 1: 0.2 to 1: 0.8. When used in a mixture of the content ratio may be excellent in the thermal stability and weather resistance of the present invention.

In one embodiment, the oxidative stabilizer (D) may be included in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the aliphatic urethane acrylate oligomer (A) including the six or more polymerizable functional groups. Preferably it may be included in 0.1 to 2 parts by weight. More preferably, it may be included in 0.1 to 1 part by weight. When the oxidizing stabilizer (D) is included in less than 0.01 parts by weight does not effectively suppress the generation of the quinone compound to cause a yellowing phenomenon, when included in more than 2 parts by weight of the oxidation stabilizer is lifted on the coating layer of the present invention May occur.

(E) Photopolymerization Initiator

In one embodiment of the invention may comprise a photopolymerization initiator (E). The photopolymerization initiator (E) may be included for the purpose of curing the composition according to the present invention to form a coating layer. In one embodiment, the photopolymerization initiator (E) is 2-hydroxy-2-methyl-1-phenylpropane-1-phenone, 1-hydroxycyclohexylphenylketone, benzophenone, 1- (4-isopropylphenyl) 2-hydroxy 2-methyl 1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl propane 1-one, α, α-diethoxyacetophenone, 2,2-diethoxy 1-phenyl ethanone and bis (2,4,6-trimethyl benzoyl) -phenylphosphine oxide and the like can be used. These may be used alone or in combination of two or more, but is not limited thereto.

In one embodiment, the photopolymerization initiator (E) may be included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the aliphatic urethane acrylate oligomer (A). Preferably 2 to 8 parts by weight may be included. More preferably 3 to 6 parts by weight may be included. When the photopolymerization initiator (E) is included in less than 1 part by weight, the curability of the composition of the present invention is lowered, and the adhesion and scratch resistance are lowered. Adhesion with the plastic substrate to be degraded, cloudiness may occur on the surface of the coating layer.

(F) Multifunctional Acrylate  Monomer

The multifunctional acrylate monomer (F) may be included for the purpose of improving the hardness, scratch resistance and adhesion of the present invention.

In one embodiment, the (F) polyfunctional acrylate monomer may include 1,6-hexanediol diacrylate and trimethylolpropane triacrylate.

In one embodiment, a mixture of 1,6-hexanediol diacrylate and trimethylolpropane triacrylate in a weight ratio of 1: 1.5 to 2 may be used. It may be excellent in hardness, scratch resistance and adhesion of the coating layer of the present invention in the above range.

In one embodiment, the multifunctional acrylate monomer (F) may be included in an amount of 40 to 70 parts by weight based on 100 parts by weight of the aliphatic urethane acrylate oligomer (A) including the six or more polymerizable functional groups. Preferably it may include 45 to 65 parts by weight. More preferably, it may include 55 to 65 parts by weight. When included in the above range may be excellent in the leveling and adhesion of the coating layer while preventing the haze phenomenon of the coating layer of the present invention.

(G) UV absorbers

In one embodiment of the invention may comprise a ultraviolet absorbent (G). The ultraviolet absorbent (G) may be included for the purpose of further improving the weather resistance of the coating layer of the present invention and the anti-yellowing effect of the substrate. The ultraviolet absorbent (G) may be a triazine ultraviolet absorber. In one embodiment, the ultraviolet absorbent (G) includes 6- [bis (2,4-dimethylphenyl) -1,3,5-triazine, 6- [bis (2,4-dimethylphenyl) -1,3, 5 triazine and tris [2,4,6- [2-4- (octyl-2-methylethanoate) oxy-2hydroxyphenyl] -1,3,5 triazine and the like can be used. These may be used alone or in combination of two or more, but is not limited thereto.

In one embodiment, the ultraviolet absorbent (G) may be included in an amount of 5 to 20 parts by weight based on 100 parts by weight of the aliphatic urethane acrylate oligomer (A). Preferably 10 to 20 parts by weight may be included. More preferably 10 to 15 parts by weight may be included. The weather resistance and anti-yellowing effect of the present invention in the above range has an advantage.

(H) Light stabilizer

The light stabilizer (H) may be included for the purpose of preventing surface defects of the present invention and increasing weather resistance. As the light stabilizer (H), a hindered amine light stabilizer (HALS) may be used. In one embodiment, the hindered amine UV stabilizer is 2,2,6,6-tetramethyl-4-biperidylstearate, 1,2,2,6,6-pentamethyl-4-piperidyl Benzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1-[(3,5-di-t-butyl-4-hydroxyphenyl) propy Onyloxyethyl] -2,2,6,6-tetramethyl-4-piperidyl- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, bis (2,2,6 , 6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6 -Pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-t-butyl-4-hydroxybenzyl) malonate, N, N'-bis (2,2,6, 6-tetramethyl-4-piperidyl) hexamethylenediamine, tetra (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetra (1,2,2,6, 6-pentamethyl-4-piperidyl) butanetetracarboxylate and bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) butanete Tracarboxylates and the like can be used. These may be used alone or in combination of two or more, but is not limited thereto.

In one embodiment, the light stabilizer (H) may be included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the aliphatic urethane acrylate oligomer (A). Preferably 2 to 8 parts by weight may be included. More preferably 3 to 6 parts by weight may be included. While preventing the surface defects of the present invention in the above range has the advantage of excellent weather resistance and anti-yellowing effect.

In addition, one embodiment of the present invention may further include a solvent that can be dissolved in the above-described components to easily adjust the viscosity, improve the smoothness of the coating layer and improve the workability during coating. As said solvent, a conventional thing can be used. For example, alcohol, ketone and acetate solvents can be used.

In one embodiment, the alcohol solvent may be methanol, ethanol, isopropyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, or the like. These may be used alone or in combination of two or more, but is not limited thereto.

In one embodiment, the ketone solvent may be methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, or the like. These may be used alone or in combination of two or more, but is not limited thereto.

In one embodiment, the acetate solvent may be ethyl acetate, butyl acetate and the like.

In one embodiment, the solvent may include 180 to 240 parts by weight based on 100 parts by weight of the aliphatic urethane acrylate oligomer (A). Preferably 190 to 220 parts by weight may be included. More preferably 190 to 210 parts by weight may be included. It can be excellent in viscosity control and workability without inhibiting the physical properties of the composition of the present invention in the above range.

In another embodiment of the present invention, the UV curable hard coat coating composition may further include a wetting agent, a leveling agent, an antifoaming agent, and the like, which are conventionally added to the coating composition in addition to the above components. These components may be included for the purpose of enhancing the workability of the paint and the smoothness of the coating film.

Another aspect of the present invention relates to a headlamp lens including the ultraviolet curable hard coat coating composition. In one embodiment the headlamp lens is a plastic substrate; And a hard coating layer formed on one surface of the plastic substrate, wherein the hard coating layer may be formed by including the above-mentioned UV-curable hard coating composition.

The plastic substrate may be polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), triacetyl cellulose (TAC), polycarbonate (PC), polyimide (PI), polyethylene (PE) ), Polypropylene (PP), polyether sulfone (PES), polyvinyl alcohol (PVA) and polyvinyl chloride (PVC) can be selected and used. Preferably polycarbonate can be used. When using the plastic substrate of the above kind it may be excellent in adhesion with the UV-curable hard coating composition of the present invention.

In one embodiment, the hard coating layer may be formed by applying an ultraviolet cured to one surface of the plastic substrate to a thickness of 5 ~ 25㎛. Preferably it may be formed to a thickness of 5 ~ 20㎛. More preferably, it may be formed to a thickness of 7 ~ 15㎛. In the above range, the surface of the plastic substrate is excellent in adhesion and excellent in physical properties, and can prevent appearance defects.

In addition, the manufacturing method of the ultraviolet curable hard coat coating composition of this invention can use a conventional thing. For example, an aliphatic urethane acrylate oligomer (A), a benzotriazole-modified urethane acrylate oligomer (B), a polycarbonate-modified urethane acrylate oligomer (C), and an oxidative stabilizer containing at least six polymerizable functional groups described above ( D), photopolymerization initiator (E), polyfunctional acrylate monomer (F), UV absorber (G) and light stabilizer (H), solvent and surface control additives, etc. It can manufacture according to the conventional method of mixing in the temperature range of normal temperature.

There is no particular limitation on the method of applying and curing the UV-curable hard coating composition of the present invention prepared as described above. The coating composition may be applied to, for example, brushing, spray coating, dip coating, or spin coating, which is widely used in the art, but is not limited thereto.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, the following examples are provided to help the understanding of the present invention, and the scope of the present invention is not limited to the following examples. Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

Example  And Comparative example

Example 4 and Comparative Examples 1-4

To prepare a UV-curable hard coating composition comprising the components and contents shown in Table 1 below.

(A) DM 87A of Double bond chemical was used as a 6 functional aliphatic urethane acrylate oligomer having a molecular weight of about 1,600 g / mol and reacted with isophorone diisocyanate and pentaerythritol triacrylate.

(B) Otsuka Corporation's RUVA-93 was used as the benzotriazole-modified aliphatic urethane acrylate oligomer.

(C) As the polycarbonate-modified aliphatic urethane acrylate, UA5095 was used.

(D) A phenolic oxidation stabilizer (SONGNOX 1076 from Songwon) and a phosphorus oxidation stabilizer (SONGNOX 1680 from Songwon) were used in a weight ratio of 1: 0.4.

(E) CP-4 was used as a photoinitiator.

1,6-hexanediol diacrylate was used as the (F-1) bifunctional acrylate monomer.

Trimethylolpropane triacrylate was used as the (F-2) trifunctional acrylate monomer.

(F-3) Dipentaerythritol hexaacrylate (DIPENTAERYTHRITOL HEXAACRYLATE, DPHA) was used as the 6 functional acrylate monomer.

(G) (Hydrazine phenyl triazine, HPT) was used as a ultraviolet absorber.

(H) UV HALS (Tinuvin 152, CIBA) was used as a light stabilizer.

(I) Isopropyl alcohol was used as a solvent.

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Test Example

UV-curable hard coating coating compositions of Examples 4 and Comparative Examples 1 to 4 prepared above were air spray coated on a transparent polycarbonate specimen (trade name: Samyang Corporation 3022 L3) at about 12 μm (based on the dry coating thickness), and then 80 ° C. After drying the solvent by hot air drying for about 300 seconds at a temperature condition of 300 mW / ㎠ and irradiated with energy of 3500 mJ / ㎠ at a position of about 20 cm in air with a high pressure mercury lamp of 300 mW / ㎠ to evaluate the following items It carried out, and the results are shown in Table 2 below, described as excellent: ○, normal: △, poor: ×.

(1) Adhesiveness test: It evaluated by carrying out the cross cut tape test based on ASTMD3359.

(2) Pencil hardness test: According to ISO 15184 and JIS K 5600-5-4, the hardness at the time of HB abnormality is evaluated as being excellent.

(3) Scratch resistance test: Steelwool ＃ 0000 grade was used to confirm coating damage after rubbing 10 times with 500g of force.

(4) Moisture resistance test: After 240 hours at 50 ± 2 ℃, 98 ± 2% of the test temperature and relative humidity, taken out and left for 1 hour, significant discoloration, fading, swelling, cracking, glossiness in the coating It evaluated whether there existed no fall etc. and there was no abnormality in adhesiveness.

(5) Water resistance test: The specimen is immersed in tap water (TAP WATER, test temperature 40 ℃) for 240 hours, taken out, the surface moisture is removed by AIR BLOW, and then left for 1 hour at room temperature. It was evaluated whether there was no swelling, cracking, gloss reduction, or the like, and no abnormality in adhesion.

(6) Heat resistance test: After leaving for 300 hours at the test temperature (80 ± 2 ℃) condition, taken out and left for 1 hour at room temperature, there is no noticeable discoloration, discoloration, swelling, cracking, gloss reduction, etc. Was evaluated.

(7) Chemical resistance test: After using the glass cleaner and engine oil separately, reciprocating 20 times with a force of 3 N, rubbing the surface of the coating film to visually inspect the appearance, and leaving it at room temperature for 24 hours to observe a significant discoloration of the coating film, It evaluated whether there was no discoloration, swelling, cracking, gloss reduction, etc., and there was no abnormality in adhesiveness.

(8) Cold-resistance cycle test: test the specimen (3 h at 80 ± 2 ° C for 1 h at room temperature → 3 h at -40 ° C → 1 h at room temperature → 7 ± 15 h at 50 ± 2 ° C, 95% RH) After repeated 5 times, it was left to stand at room temperature for 1 hour to evaluate whether there was no noticeable discoloration, discoloration, swelling, cracking, gloss reduction, etc. of the coating film, and no abnormality in adhesion.

(9) Accelerated weathering test: Five test specimens were simultaneously examined under the conditions of the following xenon arc furnace defined in SAE J 2527, followed by significant discoloration of the coating film (color difference (ΔE *): 3.0 or less), fading, swelling, cracking, It evaluated whether there was no gloss fall, etc., and there was no abnormality in adhesiveness.

(* Xenon arc furnace setting conditions: 4000kJ / ㎡ [340nm], BLACK PNL Temperature-(LIGHT) 38 ± 2 ℃ (DARK) 40 minutes irradiation (50 ± 5% RH), cycle-60 minutes irradiation (50 ± 5% RH ) 60 minutes unirradiated (95 ± 5% RH, table / backside SPRAY), irradiance -0.55 ± 0.02W / (m ² ㆍ nm) [340nm])

(10) Chipping resistance test: After the test piece was subjected to the Chipping resistance test under the following conditions by a test stone machine (GRAVELO METER: SAE J 400 standard product), there were no significant cracks, scratches, etc. of the coating film, and abnormality in adhesion. Evaluate.

(* Chipping resistance test condition: 1) Shooting Distance: 150mm; 2) Shooting Angle: 45 °; 3) Shooting Pressure: 3.0 kgf / cm 2; 4) Test Temperature: -40 ° C; 5) Zeolite: 50g (JIS Crushed gravel No 7 stone, 2.5 ~ 5mm, 350 ~ 400 pieces))

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Figure 1 (a) is a result of the accelerated weather resistance evaluation of the specimen of the comparative example for the present invention, Figure 1 (b) is a photograph showing the result of the accelerated weather resistance of the specimen prepared in the embodiment of the present invention. Comparing the results of FIG. 1 and the test example, Comparative Examples 1 to 4, which do not include the component of Example 4 of the present invention or deviate from the component ratio, have hardness, adhesion, chemical resistance, weather resistance, etc. It was found that the property of the deterioration.

Simple modifications and variations of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (6)

(A) 100 parts by weight of an aliphatic urethane acrylate oligomer comprising 6 or more polymerizable functional groups, (B) 12 parts by weight of benzotriazole-modified urethane acrylate oligomer, (C) 8 parts by weight of polycarbonate-modified urethane acrylate oligomer, (D) 0.12 parts by weight of the oxidation stabilizer and (E) 4 parts by weight of the photopolymerization initiator, (F) 60 parts by weight of the polyfunctional acrylate monomer, (G) 12 parts by weight of the ultraviolet absorber and (H) 4 parts by weight of the light stabilizer,
The (D) oxidative stabilizer comprises octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and tris (2,4-di-t-butyl phenyl) phosphite. Includes 0.4 weight ratio
Said (F) polyfunctional acrylate monomer is a 1,6-hexanediol diacrylate and trimethylolpropane triacrylate which mix | blend the weight ratio of 1: 2.
The aliphatic urethane acrylate oligomer according to claim 1, wherein the aliphatic urethane acrylate oligomer comprising at least six polymerizable functional groups is a reaction product of a bifunctional aliphatic isocyanate compound and a hydroxy acrylate monomer containing at least three polymerizable unsaturated groups. UV curable hard coating composition, characterized in that.
The ultraviolet curable hard coating composition of claim 1, wherein the (A) aliphatic urethane acrylate oligomer including at least six polymerizable functional groups has a weight average molecular weight of 1,000 to 2,000 g / mol.
Plastic substrates; And
It includes; a hard coating layer formed on one surface of the plastic substrate,
The hard coating layer is a headlamp lens comprising the UV-curable hard coating composition of any one of claims 1 to 3.
The headlamp lens of claim 4, wherein the hard coating layer has a thickness of 5 to 25 μm.
The method of claim 4, wherein the plastic substrate is polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), triacetyl cellulose (TAC), polycarbonate (PC), polyimide (PI) ), Polyethylene (PE), polypropylene (PP), polyether sulfone (PES), polyvinyl alcohol (PVA) and polyvinyl chloride (PVC) is selected from the headlamp lens.

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