KR20150021854A - Uv-curable composition for hard-coat paining - Google Patents

Abstract

The present invention relates to an ultraviolet ray-curable hard coating paint composition. A ultraviolet ray-curable hard coating paint composition in an embodiment is characterized by containing (A) 100 parts by weight of aliphatic urethane acrylate oligomer including six or more polymerizable functional groups; (B) 5-20 parts by weight of benzotriazole-modified urethane acrylate oligomer; (C) 5-15 parts by weight of polycarbonate-modified urethane acrylate oligomer; (D) 0.01-2 parts by weight of an oxidation stabilizer; and (E) 1-10 parts by weight of a photopolymerization initiator.

Description

UV-CURABLE COMPOSITION FOR HARD-COAT PAINING [0002]

The present invention relates to an ultraviolet curable hard coating composition. More specifically, it is applied to a surface of a plastic substrate such as polycarbonate, and is excellent in an effect of preventing yellowing even when left in an outdoor environment for a long time, and excellent in reliability, adhesion, hardness, abrasion resistance and impact resistance, And an ultraviolet curing type hard coating composition.

Automotive headlamps (headlamps) are lamps that illuminate the front for safe driving at night. In the conventional automotive headlamp market, glass with excellent transparency was used as a head lamp cover.

However, the headlamp cover of such a glass material has low durability, heavy weight, and high production cost. Therefore, in order to reduce the weight of the material for improving the fuel efficiency of the automobile and to reduce the production cost, Plastic, particularly polycarbonate, having excellent transparency and moldability is used.

However, in general, the polycarbonate material applied to an automobile headlamp lens is excellent in transparency and impact resistance, but has disadvantages such as scratch resistance, weather resistance, and chemical resistance. Therefore, in order to compensate for the scratch resistance and weatherability, which is a weak point of polycarbonate materials, a hard coating coating process is required which is coated with a coating composition excellent in weatherability 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, cracks and yellowing of the coating film occur when exposed to the outdoor environment for a long time due to the shrinkage stress between the molecules in the coating film, which causes problems such as appearance damage and adhesion deterioration of the coating film and discoloration. It is urgent to develop a hard coating material.

Also, the benzotriazole modified aliphatic urethane acrylate oligomer contained in the ultraviolet ray curable coating composition is produced by reaction of benzotriazole having a hydroxy group with isocyanate and an acrylate compound, and is preferably used for the weather resistance and oxidation resistance of the coating film. It is the ingredient used. However, the benzotriazole modified aliphatic urethane acrylate had a problem that the coating film disappeared and discolored when irradiated with energy of 3,500 kJ / m ² in the accelerated weatherability evaluation (SAE J1960). It is known that this is caused by the elimination of benzotriazole by ultraviolet irradiation.

In order to solve such coating film failure (coating film dropout), polycarbonate-modified urethane acrylate resin was used to improve the adhesion, but heat resistance and yellowing were further improved.

Accordingly, the present inventors have repeatedly conducted researches and found out that the present inventors have succeeded in producing a polyurethane resin composition having excellent adhesion, scratch resistance and impact resistance, including an aliphatic urethane acrylate oligomer, a benzotriazole modified urethane acrylate oligomer, a polycarbonate modified aliphatic urethane acrylate oligomer, The composition of the ultraviolet curing type hard coating composition used in a headlamp lens for automobiles excellent in yellowing prevention effect even under long outdoor conditions is derived and the present invention has been completed.

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

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

It is still another object of the present invention to provide an ultraviolet curable hard coating composition excellent in heat resistance, weather resistance and chemical resistance.

It is still another object of the present invention to provide a headlamp lens comprising the ultraviolet curable hard coating composition.

One aspect of the present invention relates to an ultraviolet curable hard coating composition. In one embodiment, the ultraviolet curable hard coating composition comprises (A) 100 parts by weight of an aliphatic urethane acrylate oligomer having 6 or more polymerizable functional groups, (B) 5 to 20 parts by weight of a 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, the aliphatic urethane acrylate oligomer (A) comprising at least six polymerizable functional groups is a reaction product of a bifunctional aliphatic isocyanate compound and a hydroxyacrylate monomer containing at least three polymerizable unsaturated groups .

In one embodiment, the aliphatic urethane acrylate oligomer (A) containing at least 6 polymerizable functional groups has a weight average molecular weight of 1,000 to 2,000 g / mol.

In one embodiment, the oxidation stabilizer (D) is characterized by comprising a phenolic hydroxyl group-containing and phosphorus-based oxidative stabilizer in a weight ratio of 1: 0.2 to 1: 0.8.

In one embodiment, (A) 40 to 70 parts by weight of the polyfunctional acrylate monomer (F) is added to 100 parts by weight of the aliphatic urethane acrylate oligomer containing at least 6 polymerizable functional groups.

In one embodiment, the (F) multifunctional acrylate monomer is selected from the group consisting of butanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, Acrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane methacrylate, propoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, Is characterized by containing at least one of acrylate, acrylate, acrylate, acrylate, acrylate, acrylate, acrylate, acrylate, acrylate,

In one embodiment, 5 to 20 parts by weight of the ultraviolet absorbent (G) and 1 to 10 parts by weight of the (H) light stabilizer are further added to 100 parts by weight of the aliphatic urethane acrylate oligomer (A) containing at least 6 polymerizable functional groups .

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

In one embodiment, the hard coating layer has a thickness of 5 to 25 占 퐉.

In one embodiment, the plastic substrate is made of a material selected from the group consisting of polymethylmethacrylate (PMMA), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), triacetylcellulose (TAC), polycarbonate (PC), polyimide (PE), polypropylene (PP), polyethersulfone (PES), polyvinyl alcohol (PVA) and polyvinyl chloride (PVC).

The ultraviolet curing type hard coating composition according to the present invention is excellent in the effect of preventing yellowing even when it is left in an outdoor environment for a long period of time and is excellent in reliability, adhesion, hardness, abrasion resistance, impact resistance, heat resistance, weather resistance and chemical resistance It may be suitable for a headlamp lens for an automobile.

Fig. 1 (a) shows the results of the accelerated weathering test of the test piece of the comparative example according to the present invention, and Fig. 1 (b) is a photograph showing the results of the accelerated weathering test of the test piece prepared in the example of the present invention.

In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to be exemplary, self-explanatory, allowing for equivalent explanations of the present invention.

One aspect of the present invention relates to an ultraviolet curable hard coating composition. In one embodiment, the ultraviolet curable hard coating composition comprises (A) an aliphatic urethane acrylate oligomer having at least 6 polymerizable functional groups, (B) a benzotriazole modified urethane acrylate oligomer, (C) a polycarbonate modified urethane acrylate (D) an oxidation stabilizer, and (E) a photopolymerization initiator.

In one embodiment, the ultraviolet curable hard coating composition comprises (A) 100 parts by weight of an aliphatic urethane acrylate oligomer having 6 or more polymerizable functional groups, (B) 5 to 20 parts by weight of a 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. When it is included in the above range, it can be excellent in yellowing prevention effect, reliability, heat resistance, weather resistance and chemical resistance.

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

(A) More than 6 Polymerizable Functional group  Containing aliphatic urethane Acrylate Oligomer

The aliphatic urethane acrylate oligomer (A) containing at least 6 polymerizable functional groups may be included for the purpose of improving the hardness, crack resistance and scratch resistance at the time of forming the hard coat layer.

In one embodiment, the aliphatic urethane acrylate oligomer (A) containing the above-mentioned six or more polymerizable functional groups may be a conventional one. For example, it may be a reaction product of a bifunctional aliphatic isocyanate compound and a hydroxyacrylate monomer containing three or more polymerizable unsaturated groups.

In one embodiment, the bifunctional aliphatic isocyanate compound may include at least one of hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate, and examples of the hydroxyacrylate monomer include pentaerythritol tri Acrylate, dipentaerythritol triacrylate, and the like.

In one embodiment, the weight average molecular weight of the aliphatic urethane acrylate oligomer (A) containing at least 6 polymerizable functional groups may be 1,000 to 2,000 g / mol. Preferably 1,500 to 2,000 g / mol. In the above range, the ultraviolet curing type hard coating composition may be excellent in adhesion to a substrate for a head lamp, ultraviolet curing property and workability in the process of forming a hard coating layer.

(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 a conventional one. For example, those obtained by reacting an aliphatic urethane acrylate oligomer and a benzotriazole-modified acrylate having a hydroxyl group can be used.

In one embodiment, the aliphatic urethane acrylate oligomer may be obtained by reacting a bifunctional aliphatic urethane acrylate oligomer and a hydroxyacrylate monomer containing up to two per molecule unsaturated groups capable of polymerization.

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

Examples of the hydroxyacrylate monomer containing two or less of the above-mentioned polymerizable unsaturated groups per molecule include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxypentyl Acrylate, and hydroxybutyl methacrylate.

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

In one embodiment, the weight average molecular weight of the benzotriazole modified urethane acrylate oligomer (B) may be 800 to 1,500 g / mol. Within the above range, the weather resistance and chemical resistance of the present invention can be excellent.

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) containing at least 6 polymerizable functional groups. The benzotriazole modified urethane acrylate oligomer (B) may be contained in an amount of 8 to 18 parts by weight, more preferably 10 to 15 parts by weight. When the amount of the benzotriazole modified urethane acrylate oligomer (B) is less than 5 parts by weight, the weather resistance and chemical resistance of the present invention are lowered. When the amount of the benzotriazole modified urethane acrylate oligomer is more than 20 parts by weight, hardening of the present invention becomes difficult, 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 adhesiveness of the present invention.

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

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

The hydroxyacrylate monomer may be at least one selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxypentyl acrylate and hydroxybutyl methacrylate .

In one embodiment, the polycarbonate modified urethane acrylate oligomer (C) may have a weight average molecular weight of 1,000 to 2,000 g / mol. Preferably 1,500 to 2,000 g / mol. In the range of the above range, the ultraviolet curing type hard coating composition may be excellent in adhesiveness, curability and workability to the substrate for headlamp during the formation of the hard coating layer.

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) containing at least 6 polymerizable functional groups. Preferably 5 to 12 parts by weight. More preferably 7 to 10 parts by weight. When the polycarbonate-modified urethane acrylate oligomer (C) is contained in an amount of less than 5 parts by weight, the adhesion of the coating layer formed according to the present invention is lowered to cause a dropout phenomenon. When the amount exceeds 15 parts by weight, , Transparency may be lowered.

(D) Oxidation stabilizer

The oxidation stabilizer (D) may be included for the purpose of inhibiting the production of quinone compounds which are the main cause of yellowing phenomenon and improving the yellowing prevention effect. In the present invention, the oxidation stabilizer (D) may be at least one selected from the group consisting of phenolic compounds and phosphorus-based oxidative stabilizers.

In one embodiment, the phenolic oxidative stabilizer is 2,6-di-tetra-butyl-4-methylphenol, octadecyl-3- (3,5-di-t-butyl- (3,3-bis (4'-hydroxy-3'-t-butylphenyl) butanoic acid) glycol ester and tetrabis Hydroxyphenyl) propionate) methane and the like can be used. These may be used singly or in combination of two or more, but are not limited thereto. Examples of the phosphorus-containing oxidizing stabilizer include triphenyl phosphite, triisodecyl phosphite, diphenyl-iso-octyl-phosphite, tris (2,4-di-t- butylphenyl) phosphite, tris (nonylphenyl) phosphite And distearyl-pentaerythritol-diphosphite. These may be used singly or in combination of two or more, but are not limited thereto. When the above-described oxidizing stabilizer (D) is used, the yellowing prevention effect of the present invention can be excellent.

In one embodiment, the phenolic and phosphorus-based oxidative stabilizers may be mixed in a weight ratio of 1: 0.2 to 1: 0.8. When they are mixed in the above-mentioned ratio, the thermal stability and weather resistance of the present invention can be excellent.

In one embodiment, the oxidation 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) containing at least 6 polymerizable functional groups. And preferably 0.1 to 2 parts by weight. More preferably 0.1 to 1 part by weight. When the oxidizing stabilizer (D) is contained in an amount of less than 0.01 part by weight, the formation of the quinone compound is not effectively inhibited and yellowing phenomenon occurs. When the oxidizing stabilizer (D) is contained in an amount exceeding 2 parts by weight, Lt; / RTI >

(E) Light curing Initiator

In one embodiment of the present invention, it may include a photopolymerization initiator (E). The photopolymerization initiator (E) may be included for the purpose of forming a coating layer by curing the composition according to the present invention. In one embodiment, the photopolymerization initiator (E) is at least one selected from the group consisting of 2-hydroxy-2-methyl-1-phenylpropane-1-phenone, 1- hydroxycyclohexyl phenyl ketone, benzophenone, 1- (4- Methyl-1-on, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy- 2,2-diethoxy 1-phenylethanone, and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. These may be used singly or in combination of two or more, but are 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. More preferably 3 to 6 parts by weight. When the amount of the photopolymerization initiator (E) is less than 1 part by weight, the curability of the composition of the present invention is deteriorated to decrease the adhesiveness and scratch resistance. When the amount is more than 10 parts by weight, The adhesion to the plastic substrate to be treated is lowered, and the surface of the coating layer may be cloudy.

(F) Multifunctional Acrylate Monomer

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

In the present invention, as the polyfunctional acrylate monomer (F), one or more of monomers having bifunctional, trifunctional and hexafunctional acrylate functional groups may be used. In one embodiment, the polyfunctional acrylate monomer (F) includes butanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, tetraglycol di Acrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane methacrylate, propoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, Acrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, glyceryl propoxy triacrylate, and trisisocyanurate triacrylate. These may be used singly or in combination of two or more, but are not limited thereto.

In one embodiment, the bifunctional and trifunctional acrylate monomers may be mixed in a weight ratio of 1: 1.5 to 2. Within the above range, the coating layer of the present invention can be excellent in hardness, scratch resistance and adhesion.

In one embodiment, the polyfunctional acrylate monomer (F) may be contained in an amount of 40 to 70 parts by weight based on 100 parts by weight of the aliphatic urethane acrylate oligomer (A) containing at least 6 polymerizable functional groups. Preferably 45 to 65 parts by weight. More preferably 55 to 65 parts by weight. When it is included in the above range, the coating layer of the present invention can be leveled and adhered while preventing the haze phenomenon of the coating layer.

(G) Ultraviolet absorber

In one embodiment of the present invention, an ultraviolet absorber (G) may be included. The ultraviolet absorber (G) may be included for the purpose of further improving the weather resistance of the coating layer of the present invention and the yellowing prevention effect of the substrate. The ultraviolet absorber (G) may be a triazine-based ultraviolet absorber. In one embodiment, the ultraviolet absorber (G) may include 6- [bis (2,4-dimethylphenyl) -1,3,5-triazine, 6- [bis (2,4- 5 triazine and tris [2,4,6- [2- {4- (octyl-2-methylethanoate) oxy-2 hydroxyphenyl}] - 1,3,5 triazine. These may be used singly or in combination of two or more, but are not limited thereto.

In one embodiment, the ultraviolet absorber (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. More preferably 10 to 15 parts by weight. Within the above range, there is an advantage that the weather resistance and yellowing prevention effect of the present invention is excellent.

(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-based ultraviolet stabilizer includes 2,2,6,6-tetramethyl-4-biperiodyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinic acid imide, 1 - [(3,5-di- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, bis (2,2,6,6-tetramethyl- , 6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (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) butane tetracarboxylate and bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) butane Tricarboxylate and the like can be used. These may be used singly or in combination of two or more, but are 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. More preferably 3 to 6 parts by weight. There is an advantage in that the surface defects of the present invention are prevented in the above-mentioned range and the weather resistance and yellowing prevention effect are excellent.

In addition, one embodiment of the present invention may further comprise a solvent capable of dissolving the above-mentioned components to easily control the viscosity, improving the smoothness of the coating layer and improving the workability at the time of coating. As the above-mentioned solvent, a conventional one can be used. For example, alcohol-based, ketone-based, and acetate-based solvents can be used.

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

In one embodiment, examples of the ketone-based solvent include methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, and dipropyl ketone. These may be used singly or in combination of two or more, but are not limited thereto.

In one embodiment, the acetate-based solvent may be ethyl acetate, butyl acetate, or the like.

In one embodiment, the solvent may be contained in an amount of 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. More preferably 190 to 210 parts by weight. Within the above range, viscosity control and workability can be excellent without impairing the physical properties of the composition of the present invention.

In another embodiment of the present invention, the ultraviolet curable hard coating composition may further include a wetting agent, a leveling agent, a defoaming 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 paint film.

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

Examples of the plastic substrate include polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), triacetylcellulose (TAC), polycarbonate (PC), polyimide (PI) ), Polypropylene (PP), polyethersulfone (PES), polyvinyl alcohol (PVA), and polyvinyl chloride (PVC). Preferably, polycarbonate can be used. When the above-described plastic substrate is used, adhesion with the ultraviolet curable hard coating composition of the present invention can be excellent.

In one embodiment, the hard coating layer may be applied on one side of the plastic substrate to a thickness of 5 to 25 탆 and cured by ultraviolet rays. Preferably 5 to 20 占 퐉. More preferably 7 to 15 占 퐉. In the above range, it is excellent in adhesion with the surface of the plastic substrate, and the physical properties are excellent, and the appearance defects can be prevented.

In addition, a conventional method for producing the ultraviolet curable hard coating composition of the present invention can be used. (A), a benzotriazole modified urethane acrylate oligomer (B), a polycarbonate-modified urethane acrylate oligomer (C), an oxidation stabilizer (C), and a polymerizable urethane acrylate oligomer (D), a photopolymerization initiator (E), a multifunctional acrylate monomer (F), an ultraviolet absorber (G) and a light stabilizer (H), a solvent and an additive for controlling the surface are added to a mixing apparatus such as a dissolver and a stirrer And the mixture is stirred at room temperature.

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

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. However, the following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited to the following examples. The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

Example  And Comparative Example

Example  1 to 4 and Comparative Example  1-4

An ultraviolet curing type hard coating composition containing the components and contents shown in the following Table 1 was prepared.

(A) DM 87A of double bond chemical, which is a hexahydrophthalic urethane acrylate oligomer and has a molecular weight of about 1,600 g / mol and isophorone diisocyanate and pentaerythritol triacrylate, was used.

(B) Benzotriazole-modified aliphatic urethane acrylate oligomer RUVA-93 from Otsuka was used.

(C) UA5095 of polycarbonate modified aliphatic urethane acrylate was used.

(D) a phenol-based oxidative stabilizer (Songwon SONGNOX 1076) and a phosphorus-based oxidative stabilizer (Songwon SONGNOX 1680) at a weight ratio of 1: 0.4.

(E) CP-4 as a photopolymerization initiator was used.

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

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

(F-3) Dipentaerythritol hexaacrylate (DPHA) was used as the hexafunctional acrylate monomer.

(G) Ultraviolet absorber (hydrazine phenyltriazine, HPT) was used.

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

(I) Isopropyl alcohol was used as a solvent.

unit
(Parts by weight) Example Comparative Example One 2 3 4 One 2 3 4 A 100 100 100 100 100 100 100 100 B 12 12 12 12 12 25 12 12 C 8 8 8 8 25 - 8 - D 0.12 0.12 0.12 0.12 0.12 0.12 - 0.12 E 4 4 4 4 4 4 4 4 F F-1 60 - - 20 60 - - 20 F-2 - 60 - 40 - 60 - 40 F-3 - - 60 - - - 60 - G 12 12 12 12 12 12 12 12 H 4 4 4 4 4 4 4 4 I 200 200 200 200 200 200 200 200

Test Example

The prepared ultraviolet curable hard coating composition of Examples 1 to 4 and Comparative Examples 1 to 4 was air-spray-coated on a transparent polycarbonate specimen (trade name: Samyang 3022 L3) at about 12 탆 (based on dry film thickness) Dried at a temperature of 80 ° C for about 300 seconds to remove the solvent and irradiated at an energy of 3500 mJ / cm 2 at a position of about 20 cm in air with a high pressure mercury lamp of 300 mW / cm 2 to hard coat the hard coated specimen The results are shown as excellent:?, Medium:?, Poor: X, and the results are shown in Table 2 below.

(1) Adhesion test: A cross cut tape test was performed according to ASTM D3359.

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

(3) Scratch resistance test: Using Steelwool # 0000 grade, 500 g of force was applied, and the damage of the coating film was confirmed after rubbing 10 times.

(4) Moisture resistance test: The sample was allowed to stand for 240 hours at a test temperature and relative humidity of 50 ± 2 ° C. and 98 ± 2%, and then allowed to stand for 1 hour to observe significant discoloration, discoloration, swelling, There was no deterioration or deterioration of adhesion, and the like.

(5) Water resistance test: The specimens were immersed in tap water (TAP WATER, test temperature: 40 ° C) for 240 hours, and then taken out to remove moisture from the surface by an air blast. After standing for 1 hour at room temperature, , Swelling, cracking, gloss reduction, and adhesion were evaluated.

(6) Heat resistance test: The sample was allowed to stand for 300 hours under the test temperature (80 ± 2 ° C), then taken out and allowed to stand at room temperature for 1 hour. Thereafter, there was no discoloration, discoloration, swelling, .

(7) Chemical resistance test: Glass washing agent and engine oil were individually used and then reciprocated 20 times with a force of 3 N. Then, the surface of the coating was rubbed and the appearance was visually observed. After standing for 24 hours at room temperature, Fading, swelling, cracking, gloss reduction, and adhesion were evaluated.

(8) Heat and Cycle Test: The specimen is allowed to stand for 3 hours at 80 ± 2 ° C, left for 1 hour at room temperature, left for 3 hours at -40 ° C, left for 1 hour at room temperature, 50 ± 2 ° C and 7 to 15 hours at 95% After repeating 5 times, it was allowed to stand at room temperature for 1 hour, and it was evaluated whether there was no discoloration, discoloration, swelling, cracking, gloss drop, or the like in the coating film.

(9) Accelerated weathering test: Five test specimens were simultaneously exposed to the following xenon arc conditions specified in SAE J 2527, and then observed at the time of observing the discoloration (color difference (ΔE *): 3.0 or less), fading, swelling, Gloss was not deteriorated, and adhesion was evaluated as abnormal.

(50 ± 5% RH), Cycle - 60 minutes (50 ± 5% RH), 40 minutes irradiation (40 ± 60% RH) ) 60 nm non-irradiation (95 ± 5% RH, surface / backside SPRAY), irradiation intensity - 0.55 ± 0.02 W / (㎡ · nm) [340 nm]

(10) Chipping resistance test: The chipping resistance test was carried out on a test specimen with a GRAVELO METER (SAE J 400 standard product) under the following conditions, and there was no remarkable cracking or scratch on the coating film, Respectively.

(* Chipping resistance test conditions: 1) Shooting Distance: 150mm; 2) Shooting Angle: 45 °; 3) Shooting Pressure: 3.0 kgf / ㎠; 4) Test Temperature: -40 ℃; 5) Grain: 50g (JIS Crushed gravel No 7 stone, 2.5 to 5 mm, 350 to 400 pieces))

Evaluation items Example Comparative Example One 2 3 4 One 2 3 4 Attachment 100 /
100 100 /
100 100 /
100 100 /
100 93 /
100 82 /
100 83 /
100 90 /
100 Pencil hardness 2H 2H 3H 3H H HB HB HB Scratch resistance ○ ○ ○ ○ ○ × △ △ Moisture resistance ○ ○ ○ ○ △ △ ○ △ Water resistance ○ ○ ○ ○ ○ ○ ○ △ Heat resistance ○ ○ ○ ○ △ △ △ ○ Chemical resistance ○ ○ ○ ○ △ ○ △ ○ Cold and heat cycle resistance ○ ○ ○ ○ × △ △ △ Accelerated weathering resistance (ΔE *)
Spec: ΔE * <3.0 2,500 kJ / ㎡ 1.4 1.5 1.5 1.4 2.1 2.3 2.6 2.5 4,500 kJ / ㎡ 1.9 1.8 1.6 1.9 3.5 5.2 5.7 5.7 My Chipping Castle ○ ○ ○ ○ × × × ×

Fig. 1 (a) shows the results of the accelerated weathering test of the test piece of the comparative example according to the present invention, and Fig. 1 (b) is a photograph showing the results of the accelerated weathering test of the test piece prepared in the example of the present invention. When the results of FIG. 1 and the test examples are summarized, Comparative Examples 1 to 4, which do not include the components of Examples 1 to 4 of the present invention or out of the composition ratios, exhibit hardness, Chemical properties, weather resistance, and the like were deteriorated.

Claims (10)

(A) 100 parts by weight of an aliphatic urethane acrylate oligomer having 6 or more polymerizable functional groups, (B) 5 to 20 parts by weight of a benzotriazole modified urethane acrylate oligomer, (C) 5 to 20 parts by weight of a polycarbonate- (D) 0.01 to 2 parts by weight of an oxidation stabilizer, and (E) 1 to 10 parts by weight of a photopolymerization initiator.
The method of claim 1, wherein the aliphatic urethane acrylate oligomer (A) containing at least six polymerizable functional groups is a reaction product of a bifunctional aliphatic isocyanate compound and a hydroxyacrylate monomer having three or more polymerizable unsaturated groups Based coating composition.
The ultraviolet curable hard coating composition according to claim 1, wherein the aliphatic urethane acrylate oligomer (A) containing at least 6 polymerizable functional groups has a weight average molecular weight of 1,000 to 2,000 g / mol.
The ultraviolet curable hard coating composition according to claim 1, wherein the oxidizing stabilizer (D) comprises a phenolic antioxidant and a phosphorus antioxidant in a weight ratio of 1: 0.2 to 1: 0.8.
The ultraviolet curable resin composition according to claim 1, which comprises (A) 40 to 70 parts by weight of (F) a polyfunctional acrylate monomer based on 100 parts by weight of an aliphatic urethane acrylate oligomer having 6 or more polymerizable functional groups. Hard coating composition.
[7] The method of claim 5, wherein the polyfunctional acrylate monomer (F) is selected from the group consisting of butanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, tetra Glycidyl acrylate, glycol diacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane methacrylate, propoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, trimethylol propane An ultraviolet curing type hard coating which comprises at least one of trimethylolpropane triacrylate, trimethacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, glyceryl propoxy triacrylate and tris isocyanurate triacrylate. Coating composition.
(A) 5 to 20 parts by weight of an ultraviolet absorber (G) and 1 to 10 parts by weight of a (H) light stabilizer, based on 100 parts by weight of an aliphatic urethane acrylate oligomer containing at least 6 polymerizable functional groups Wherein the ultraviolet curing type hard coating composition further comprises an ultraviolet curing type hard coating composition.
Plastic substrates; And
And a hard coating layer formed on one surface of the plastic substrate,
Wherein the hard coating layer comprises the ultraviolet curable hard coating composition according to any one of claims 1 to 7.
The headlamp lens of claim 8, wherein the hard coating layer has a thickness of 5 to 25 占 퐉.
The method of claim 8, wherein the plastic substrate is selected from the group consisting of polymethylmethacrylate (PMMA), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), triacetylcellulose (TAC), polycarbonate (PC) ), Polyethylene (PE), polypropylene (PP), polyethersulfone (PES), polyvinyl alcohol (PVA) and polyvinyl chloride (PVC).

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