KR20160056085A - UV curing coating composition - Google Patents

Abstract

The present invention relates to an ultraviolet (UV) curable paint composition which maintains adhesiveness to a surface and exhibits more improved functionality such as transparency, wear resistance, impact resistance, chemical resistance, moisture resistance, salinity tolerance, corrosion resistance, and weather resistance. To this end, the composition of the present invention includes metal-silicon-based nanocolloid, nanosilica colloid, amine-based silane, epoxy-based silane.

Description

UV curing coating composition < RTI ID = 0.0 >

The present invention relates to an ultraviolet curing coating composition having a function for surface protection of various resins.

Almost all materials that are used in various products, electronic devices, electronic components or various industries are exposed to frequent scratching environment, water or heat elements, and are subject to wear, impact, contamination and corrosion due to scratches There is a problem in that a great economic loss occurs due to the chemical change due to the chemical change. Therefore, studies on methods for minimizing the above problems by applying or treating a coating composition having functions such as abrasion resistance, impact resistance, chemical resistance, moisture resistance, salt resistance, corrosion resistance and weather resistance to a surface to be protected have reached a considerable level have.

However, most of these methods require a high-temperature process or a long-time process. Particularly, a material having a form including a resin susceptible to heat, including various low-molecular and high-molecular substances, There is a fear that this is denatured. Therefore, a coating method using ultraviolet curing, which is a process which can be terminated at a lower temperature in a short time, has been studied in recent years, and it has been gradually put to practical use.

However, such an ultraviolet-curable coating composition is difficult to uniformly coat on the surface, and as the thickness of the coating layer increases, ultraviolet rays do not sufficiently reach the inside of the coating layer and layer separation phenomenon may occur, .

In general, when the above-mentioned functionalities are improved, adhesion or adhesion between the surface and the coating layer tends to decrease. For example, when the content of the component having such a characteristic is increased in order to improve the functionality, the adhesion or adhesion between the surface and the coating layer is reduced. When the adhesion or adhesion between the surface and the coating layer is reduced, peeling or the like, in which the coating layer for protecting the surface is easily separated, may occur and the function can not be exhibited. On the other hand, when the content of the component having such a characteristic is increased in order to improve the adhesion or adhesion between the surface and the coating layer, the surface and the coating layer are firmly adhered to each other, so that the peeling phenomenon does not occur. Therefore, it is necessary to study the ultraviolet ray curing coating composition having the maximum improved functionality on the basis thereof while maintaining the adhesion or adhesion between the surface and the coating layer to a minimum as necessary.

Japanese Patent Laid-Open No. 1995-207190

An object of the present invention is to provide an ultraviolet curing coating composition which is improved in functionality such as abrasion resistance, impact resistance, chemical resistance, moisture resistance, salt resistance, corrosion resistance and weather resistance while maintaining the adhesion or adhesion strength between the surface and the coating layer.

Another object of the present invention is to provide an ultraviolet curing coating composition which is improved in functionality such as high hardness, abrasion resistance, salt resistance, stain resistance, corrosion resistance, oxidation resistance, chemical resistance and weather resistance while maintaining the improved impact resistance and high transparency.

Another object of the present invention is to provide an ultraviolet curing coating composition which can be applied more uniformly to a surface.

A metal-silicon-based nanocolloid, a nanosilica colloid, an amine-based silane, and an epoxy-based silane.

The metal-silicon-based nano-colloid may include one or more selected from aluminum, zinc, magnesium, tin, calcium, zirconium and antimony. However, the present invention is not limited thereto, and it is not limited so far as it is a metal that is not harmful to human body, does not significantly affect the environment, and can exhibit the effect of the present invention as a high hardness metal.

In one embodiment of the present invention, the metal-silicon-based nanocolloid may be an aluminum-silicon-based nanocolloid.

In one embodiment of the present invention, the UV coating composition may further include one or more additives selected from a photo initiator, an ultraviolet absorber, and a light absorber.

In one embodiment of the present invention, the ultraviolet-curable coating composition comprises 30 to 60% by weight of metal-silicon-based nano-colloid, 30 to 60% by weight of nano-silica colloid, 0.1 to 5 0.1 to 5% by weight of an epoxy silane, and 0.1 to 10% by weight of an additive. In detail, the ultraviolet-curable coating composition comprises 35 to 55% by weight of a metal-silicon-based nano-colloid, 35 to 55% by weight of a nano-silica colloid, 0.2 to 4% by weight of an amine-based silane, 0.2 to 4% by weight, and 0.1 to 10% by weight of an additive. In particular, when the ultraviolet ray curing coating composition contains less than 30% by weight of the metal-silicon based nano-colloid relative to the total weight of the ultraviolet ray curing coating composition, the effect of high hardness or abrasion resistance may be remarkably deteriorated, The adhesion or adhesion to the surface can be significantly reduced. The additive may include one or more components selected from a photo initiator, an ultraviolet absorber, and a light absorber.

In one embodiment of the present invention, the metal-silicon-based nano-colloid may include a metal-silicon-based powder, an organosiloxane polymer, and a solvent. Specifically, the metal- And 50 to 150 parts by weight of the organosiloxane polymer.

The metal-silicon-based powder particle size may also be between 2 and 60 nm. If the particle size is less than 1 nm, the hardness of the coating layer may be lowered and the functionality such as abrasion resistance may be deteriorated. When the particle size exceeds 60 nm, the mixing property or dispersibility may be decreased to deteriorate the physical properties. The transparency of the applied layer may be lowered. Therefore, the particle size is preferably 2 to 60 nm, preferably 2 to 50 nm, more preferably 2 to 30 nm.

In one embodiment of the present invention, the organosiloxane polymer may comprise an organosiloxane polymer having a photosensitive group. In detail, when the ultraviolet ray curable coating composition is prepared using the photosensitive organosiloxane polymer having the photosensitive group, the problems of uncured or external curing of the ultraviolet rays which do not sufficiently reach the inside of the applied layer can be minimized , A more uniform coating layer can be formed on the surface. This can further improve the adhesion and adhesion between the surface and the coating layer. If the coating layer is not uniformly formed, the force applied to the surface can be varied even if the same force is applied. Therefore, the coating layer may not have the same physical properties, which increases the error range of the physical property measurement. For example, there may be differences in physical properties such as hardness, abrasion resistance, impact resistance, or chemical resistance depending on the surface position on which the coating layer is formed, which may result in errors in measurement, which may result in failure to properly protect the surface.

In one embodiment of the present invention, the organosiloxane polymer is selected from the group consisting of phenyltrimethoxysilane, phenyltriethoxysilane, diphenyltrimethoxysilane, diphenylethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, May be prepared by the polymerization of one or more selected compounds from compounds including tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane . As a compound for imparting a photosensitive function, glycidyloxypropyltrimethoxysilane or methacrylate propyltrimethoxysilane is more preferable, and it is preferable to react largely to the ultraviolet wavelength region. A compound having an acryl group, an ethylene group or a diazo group can be exemplified, but the present invention is not limited thereto, and compounds having the above functions are conventionally known to those skilled in the art, and thus are not limited to a great extent.

In one embodiment of the present invention, the organosiloxane polymer may comprise 70 to 130 parts by weight of a compound for imparting a photosensitive function to 100 parts by weight of the organosiloxane polymer.

In one embodiment of the present invention, the organosiloxane polymer may have a weight average molecular weight ranging from 500 to 30000, preferably from 600 to 25000, more preferably from 700 to 15000. When the weight average molecular weight is less than 500, the curing time may be increased or the crosslinking reaction may not be sufficiently performed, so that the functionality of the coating composition may be deteriorated. When the weight average molecular weight exceeds 30,000, it may not be easy to uniformly coat the surface of the ultraviolet curing coating composition containing the polymer.

In one embodiment of the present invention, the nanosilica colloid may include 80 to 185 parts by weight of Si powder per 100 parts by weight of the solvent.

The particle size of the Si powder may be 2 to 100 nm. In detail, when the particle size of the Si powder is less than 1 nm, the viscosity may increase due to gelation, resulting in deterioration of the mixing or dispersibility and deterioration of the physical properties. When the particle size exceeds 200 nm, the transparency of the coating layer have. Therefore, the particle size of the Si powder is preferably 2 to 100 nm, preferably 3 to 70 nm, more preferably 5 to 50 nm.

In one embodiment of the invention the solvent is selected from the group consisting of methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, , 4-methyl-2-pentanol, cyclohexanol, methylcyclohexanol, n-hexanol, furfuryl alcohol, furfuryl methanol, tetrahydrofurfuryl alcohol and benzyl alcohol; But are not limited to, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, methyl t-butyl ketone, methyl n-pentyl ketone, methyl n-hexyl ketone, diethyl ketone, diisopropyl ketone, Ketones such as pentanone, cyclohexanone, methylcyclohexanone, cycloheptanone, cyclooctanone, 2,4-pentanedione, 2,5-hexadione and acetophenone; n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, octane, isooctane, 2,2,4-triethylpentane, cyclohexane, methylcyclohexane, benzene, toluene, Hydrocarbons such as benzene, ethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, pentylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene and diisopropylbenzene; Diisopropyl ether, di-n-butyl ether, di-isobutyl ether, di-n-hexyl ether, diisopropyl ether, diisopropyl ether, diisopropyl ether, , Phenetol, diphenyl ether, ethyl benzyl ether, bis (2-ethylhexyl) ether, ethylene oxide, 1,2-propylene oxide, 1,4- dioxane, 4-methyl dioxolane, Ethers such as dibenzyl ether and butyl phenyl ether; Methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec- pentyl acetate, methylpentyl acetate, - ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethyl propionate, n-butyl propionate, isoamyl propionate, Butyrolactate, n-pentyl lactate, methyl methoxy propionate, ethyl ethoxypropionate, ethyl lactate, ethyl lactate, ethyl lactate, diethyl oxalate, di- , Diethyl malonate, dimethyl phthalate, diethyl phthalate, diethyl carbonate and propylene carbonate And the like; Lactones such as gamma-butyrolactone, gamma-valerolactone and delta-valerolactone; Nitriles such as acetonitrile, propionitrile and acrylonitrile; Diethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 2,4-pentanediol, Glycols such as 5-hexanediol, 2,4-heptanediol, 2-ethylhexane-1,3-diol, diethylene glycol, dipropylene glycol, triethylene glycol and tripropylene glycol; Hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, and 4-hydroxy -4-methyl-2-pentanone, and the like; Examples of the glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono n-butyl ether, ethylene glycol mono n-pentyl ether, ethylene glycol mono n-hexyl ether, Ethyleneglycol monoethers such as glycol mono 2-ethylbutyl ether, ethylene glycol mono 2-ethylhexyl ether and ethylene glycol monophenyl ether; Ethylene glycol diethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether and ethylene glycol dibutyl ether; Ethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol mono n-butyl ether acetate and ethylene glycol diacetate; Propylene glycol monoethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether and propylene glycol mono t-butyl ether; Propylene glycol diethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether and propylene glycol methyl ethyl ether; Propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono n-propyl ether acetate, propylene glycol mono n-butyl ether acetate and propylene glycol diacetate; Methyl-3-methoxy-1-butanol, 3-methoxy-1-butanol, 3-methoxybutyl acetate, Diethylene glycol monomethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono-n-butyl ether, and diethylene glycol mono-n-hexyl ether, and the like, such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Glycol monoethers; Diethylene glycol diethyl ether such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Diethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate and diethylene glycol mono n-butyl ether acetate; Dipropylene glycol monoethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monopropyl ether; Dipropylene glycol diethers such as dipropylene glycol dimethyl ether; Glycol ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate and diethylene glycol monobutyl ether acetate; Or as a heterogeneous compound, at least one compound selected from the group consisting of N-methylpyrrolidinone, formamide, N-methylformamide, N-ethylformamide, N, N-dimethylformamide, N, Ndiethylformamide, May contain one or more of N, N-dimethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N, N-dimethylsulfoxide, sulfolane and 1,3- have. In addition to these, various solvents may be used, but it is more preferable to use ethyl acetate as a common solvent used in the coating composition.

In one embodiment of the present invention, the amine-based silane is not limited as long as it is a silane compound having at least one amino group, and both a water-soluble component or an oil-soluble component having a molecular weight of 20 to 2000 can be used. Such as 3-aminopropyltrialkoxysilane. Therefore, the present invention is not limited thereto, and is well known to those skilled in the art, so that detailed description thereof will be omitted.

In an embodiment of the present invention, the epoxy silane is not limited as long as it is a silane compound having at least one epoxy group, but since the epoxy group has a property of binding with the amino group and bridging with the amino group, So that the adhesion or adhesion between the surface and the coating layer can be improved. The epoxy silane is not limited as long as it has a weight average molecular weight of 50 to 5,000, but there are various kinds such as 2- (3,4-epoxycyclohexyl) ethyl trimethylsilane and 3-glycidylpropylmethyldimethoxysilane. The above description is omitted.

In one embodiment of the present invention, the photoinitiator is 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'- methoxystyryl) (2,4-trichloromethyl- (3 ', 4'-dimethoxyphenyl) -6-triazine, 2,4-trichloromethyl- Triazine compounds; Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) , 5'-tetraphenylbiimidazole; 2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- Benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin butyl ether, 2,2-dimethoxy-benzoin methyl ether, (4-methylthiophenyl) -2-morpholino-1-propan-1-one, 2-benzyl-2-dimethylamino- -1-butanone and the like; Benzophenone compounds; Fluorenone-based compounds; Thioxanthone compounds; Xanthone compounds; Anthraquinone compounds; Acridine-based compounds; Dicarbonyl compounds; Phosphine oxide-based compounds; Amine based synergists; Coumarin-based compounds; Chalcone compounds; Or a mixture thereof, but it is not limited thereto, and those skilled in the art can easily use it as is known in the art.

In one embodiment of the present invention, the ultraviolet absorber is selected from the group consisting of a benzotriazole ultraviolet absorber, a benzophenone ultraviolet absorber, a salicylic acid ultraviolet absorber, a cyanoacrylate ultraviolet absorber, a hindered phenol ultraviolet absorber, Or a mixture of two or more of them may be used. Preferably, 2- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol as the benzotriazole-based ultraviolet absorber; Or 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol]; This is good. Those skilled in the art can use commonly known materials, so a detailed description thereof will be omitted. An ultraviolet absorber doped with an Al-based nanoparticle in a compound such as the ultraviolet absorber can be exemplified.

In one embodiment of the present invention, the light absorber is tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate; Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate; 1,2,3-tris (1,2,2,6,6-pentamethyl-4-piperidyl) -4-tridecylbutane-1,2,3,4-tetracarboxylate; And 1,2,3-tris (2,2,6,6-tetramethyl-4-piperidyl) -4-tridecylbutane-1,2,3,4-tetracarboxylate; , ≪ / RTI >

In one embodiment of the present invention, the UV curable coating composition may further include 0.1 to 10 parts by weight of a polyaminoamide compound per 100 parts by weight of the metal-silicon-based nano-colloid. The polyaminoamide compound has an effect of improving functionality such as impact resistance, bending resistance and processability. In particular, an ultraviolet curing coating composition using an organosiloxane polymer having a photosensitive group for high hardness and high abrasion resistance may have a problem of deteriorating processability and ductility. The polyaminoamide compound plays a role in complementing these problems.

In one embodiment of the present invention, a method for producing a polyaminoamide compound is such that polyethylene polyamine is placed in a reaction vessel and 100 parts by weight of fatty acid is added to 100 parts by weight of polyethylene polyamine at a temperature of 70 to 100 캜. A method of producing a polyaminoamide compound by heating at a temperature of 260 ° C and removing water in the formed reaction by distillation. The molecular weight of the polyaminoamide compound is not particularly limited, but may be 1,000 to 10,000 weight average molecular weight. The polyethylene polyamine is an amine containing three or more nitrogen atoms in the molecule and may be exemplified by a mixture of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethylheptamine, and polyethyleneamine , Preferably triethylene tetramine, tetraethylene pentamine or pentaethylene hexamine. The fatty acid may contain hydrocarbon radicals having 2 to 22 carbon atoms. Preferably fatty acids having 8 or more carbon atoms, more preferably unsaturated fatty acids having 14 or more carbon atoms, such as oleic acid, tall oil fatty acid, linoleic acid and linolenic acid. Since the method for producing the polyaminoamide compound is well known to those skilled in the art, the detailed description thereof will be omitted and other reactants or other manufacturing methods may be used as the same or similar components. It is not limited.

In one embodiment of the present invention, the UV curable coating composition may further comprise 0.1 to 10 parts by weight of a styrene-butadiene block copolymer based on 100 parts by weight of the metal-silicon-based nano-colloid. Specifically, the styrene-butadiene block copolymer has a high restoring force, excellent impact resistance, and processing stability while maintaining functionality such as improved abrasion resistance and high transparency, and can further improve adhesion or adhesion with the surface. The method and specific properties of the styrene-butadiene block copolymer are well known to those skilled in the art and are not particularly limited, and examples thereof include Styrolux 3G46, 3G55, 656C, 684D, 693D, BATCHES, S, T and Styroflex 2G66 of STYROLUTION . However, if the styrene-butadiene block copolymer has a styrene-butadiene blend ratio, a molecular weight, or the like, or if other components are added, the styrene-butadiene block copolymer will fall within the scope of the present invention.

In one embodiment of the present invention, a method of producing an ultraviolet-curable coating composition is a method of producing an ultraviolet-curable coating composition, comprising the steps of: preparing an ultraviolet-curable coating composition comprising an Al-Si nanocolloid, a nanosilica colloid, an amine silane, an epoxy silane, a photoinitiator, Styrene-butadiene block copolymer and the like may be stirred and dispersed to prepare an ultraviolet curing coating composition. In detail, the stirring and dispersion can be carried out for 60 to 120 minutes. If the stirring time is less than 60 minutes, the mixing or reaction is not properly performed and the surface protecting effect may be deteriorated. If the stirring time exceeds 120 minutes, It may not be a desirable mode in terms of process efficiency.

In one embodiment of the present invention, the method of applying the ultraviolet curing coating composition to the resin surface includes:

S1) applying the ultraviolet curing coating composition to the resin surface; And

S2) irradiating ultraviolet rays onto the surface of the resin which has been subjected to the step S1) and curing the resin;

. ≪ / RTI >

In an embodiment of the present invention, step S1) may be performed by knife coating, reverse roll coating, roll coating, calender coating, curtain coating, Such as extrusion coating, cast coating, dip coating, spray coating, air-knife coating and foaming coating, And applying the ultraviolet curing coating composition to the surface. However, since these methods are well known to those skilled in the art, further detailed description will be omitted.

In one embodiment of the present invention, the ultraviolet ray irradiation process in step S2) is well known to those skilled in the art within a general range, and can be suitably adjusted according to the purpose. For example, the amount of ultraviolet light may be 50 to 300 mJ / cm 2, preferably 100 to 200 mJ / cm 2.

In one embodiment of the present invention, step S2) may include irradiating ultraviolet rays for 10 to 600 seconds. If the ultraviolet rays are irradiated for less than 10 seconds, the crosslinking may not occur sufficiently and the peeling phenomenon due to uncured or the surface protecting function may not be exhibited properly. If the ultraviolet ray is irradiated for more than 600 seconds, The heat generated can cause thermal deformation on the surface, such as the surface of the synthetic resin itself, on the synthetic resin itself. Therefore, it is preferable to irradiate the ultraviolet ray at the minimum time that the ultraviolet ray hardening coating composition can sufficiently cross-link the reaction. The ultraviolet ray irradiation time can be controlled according to various factors such as the content of each component of the ultraviolet ray coating composition, the amount of ultraviolet ray, the thickness of the applied layer or the application method, but preferably 30 to 480 seconds, more preferably 45 to 420 seconds have.

In the present invention, as a main use of the ultraviolet ray curing coating composition, a resin including a synthetic resin such as plastic weak in heat can be exemplified. However, the ultraviolet ray curing coating composition of the present invention is not limited to this, If possible, fall within the scope of the present invention.

The UV curable coating composition of the present invention has an advantage that functionalities such as abrasion resistance, impact resistance, chemical resistance, moisture resistance, salt resistance, corrosion resistance and weather resistance can be further improved while maintaining adhesion or adhesion with the surface.

The ultraviolet ray curing coating composition of the present invention has an advantage that the functional properties such as high hardness, abrasion resistance, salt resistance, stain resistance, corrosion resistance, oxidation resistance, chemical resistance and weather resistance can be further improved while maintaining the improved impact resistance and high transparency have.

The ultraviolet curing coating composition of the present invention has an advantage that it can be more uniformly applied to the surface.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the ultraviolet curing coating composition of the present invention will be described in detail with reference to the accompanying drawings. The following drawings are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. Therefore, the present invention is not limited to the following drawings, but may be embodied in other forms, and the drawings presented below may be exaggerated in order to clarify the spirit of the present invention. Hereinafter, the technical and scientific terms used herein will be understood by those skilled in the art without departing from the scope of the present invention. Descriptions of known functions and configurations that may be unnecessarily blurred are omitted.

Hereinafter, examples and experimental results will be described in detail.

(Example 1)

0.7 kg of diphenylethoxysilane having a weight average molecular weight of 7000, 0.7 kg of methyltrimethoxysilane having a weight average molecular weight of 8000 and 0.9 kg of vinyltriethoxysilane having a weight average molecular weight of 9000 were mixed in a reactor and stirred , 0.1 kg of nitric acid in one normal concentration and 0.6 kg of water was slowly added to the reaction solution. After cooling to room temperature and below 50 < 0 > C, an organosiloxane polymer was prepared.

4 kg of an Al-Si-based powder having an average particle size of 20 nm, 3 kg of the organosiloxane polymer and 3 kg of ethyl acetate were mixed in a reactor, and the mixture was stirred at a temperature of 27 ± 2 ° C for 40 minutes at a rotation speed of 40 times / To prepare an Al-Si-based nano-colloid.

4 kg of an Si powder having an average particle size of 20 nm and 3 kg of ethyl acetate were stirred at a temperature of 27 ± 2 ° C for 30 minutes at a rotation speed of 30 times / minute to prepare a nanosilica colloid.

4.5 kg of the Al-Si-based nano-colloid, 4.5 kg of the nano-silica colloid, 3 kg of the organosiloxane polymer, 0.2 kg of 3-aminopropyltrialkoxysilane as an amine-based silane, 3-glycidylpropylmethyldimethine (2H-benzotriazole-2-yl) - (2,2,2-trifluoroethyl) -2,3,5,5-tetramethylpentane doped with Al- 0.2 kg of 4- (1,1,3,3-tetramethylbutyl) phenol and 0.2 kg of tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) And 0.3 kg of butanetetracarboxylate were mixed to prepare a mixed solution. Subsequently, the mixed solution was stirred and dispersed at a temperature of 27 ± 2 ° C for 1 hour to prepare an ultraviolet curable coating composition.

The UV curable coating composition was coated on the surface of a 1 mm thick polyethylene resin using an immersion coating method and the surface of the coated polyethylene resin was irradiated with ultraviolet rays for 4 minutes using an ultraviolet curing machine (OUL-A431, ONUV) Respectively.

(Example 2)

Except that 2.5 kg of Al-Si-based nano-colloid was substituted for 4.5 kg.

(Example 3)

Except that 7 kg of Al-Si-based nano-colloid was used instead of 4.5 kg.

(Example 4)

The procedure of Example 1 was repeated except that 2.5 kg of silica nanocolloid was used instead of 4.5 kg of silica nanocolloid.

(Example 5)

The procedure of Example 1 was repeated except that 7 kg of silica nanocolloid was used instead of 4.5 kg of silica nanocolloid.

(Example 6)

A mixture of 0.2 kg of glycidyloxypropyltrimethoxysilane and 1 kg of methacrylate propyltrimethoxysilane was slowly added to 3 kg of the organosiloxane polymer prepared according to Example 1. Then, the mixture was heated and refluxed for 2 hours to prepare an organosiloxane polymer having a photosensitive group. The weight average molecular weight of the polymer can be controlled by controlling the heating temperature and the reaction time. The weight average molecular weight of the organosiloxane polymer having the photosensitive group was measured to be about 2000.

Except that 3 kg of the organosiloxane polymer was replaced with the organosiloxane polymer having the photosensitive group described above.

(Example 7)

0.5 kg of triethylenetetramine was placed in a reaction vessel, and 0.5 kg of oleic acid was added at a temperature of 70 to 100 캜. After heating to a temperature of 260 캜, water in the reaction was removed by distillation to prepare a polyaminoamide compound.

The procedure of Example 6 was repeated except that 0.3 kg of the polyaminoamide compound was further added and mixed.

(Example 8)

Except that 0.2 kg of Styrolux T manufactured by STYROLUTION was further added and mixed.

(Example 9)

The procedure of Example 9 was repeated, except that the organosiloxane polymer having a photosensitive group having a weight average molecular weight of 300 was mixed.

(Comparative Example 1)

Except that the Al-Si-based nano-colloid was not mixed.

(Comparative Example 2)

The procedure of Example 1 was repeated except that the nanosilica colloid was not mixed.

≪ Evaluation of physical properties &

1. Hardness

Measured using a manual pencil hardness tester (CT-PC1, manufactured by CORETECH) according to the method and conditions specified in KS D 6711: 2012, and the pencil was measured by applying a force of 7.5 N at an angle of 45 degrees Respectively.

2. Adhesion and Adhesion

Cross-cuts were made 10 times in 2 mm increments horizontally and vertically on specimens with coating layers formed according to the ASTM D3359 Adhesion Test Method and conditions, and then the surface was wiped off and tightly adhered with tape. One side was pulled at a 90 ° angle with a constant force, and the degree of the peeled portion was observed.

3. Abrasion resistance

(MTC-015, MMS) according to the method and conditions set forth in ASTM D 1242. [ The length of 5 cm was measured with a test load of 0.3 kg for 8 hours at a reciprocating speed of 40 times / minute. 5, good 4, moderate 3, degenerative or altered 2, and degenerative or altered 1 were assessed as being equal to those before enucleation.

4. Impact resistance

According to the method and conditions specified in KS D 3520: 2008, the specimens with a radius of 6.33 mm at a height of 50 cm and a load of 0.6 kg were measured 100 times. In the case where the state of the coating layer is the same as that before the execution, 5, good case is 4, normal case is 3, crack is formed in the coating layer or 2 when the defect occurs, and the coating layer is broken or peeled off to exert its function And when it was not possible, it was evaluated as 1.

5. Flexibility

The degree of cracking occurred when the specimen was folded at 90 degrees according to the method and conditions specified in KS M 5000: 2009.

6. Moisture resistance

The specimens were allowed to stand for 7 days in a reactor with a temperature of 40 ± 2 ° C and a relative humidity of 90 ± 3% RH, and then taken out to observe the surface state of the coating layer.

7. Salt resistance (corrosion resistance)

A 5% NaCl aqueous solution was sprayed onto the X-cut specimen at 35 ° C using a salt spray tester (SST-9MS, TERCHY) according to the method and conditions specified in KS D 9520: 2009, Salt spray test).

8. Stain resistance

The contamination was formed by drawing a line 5 cm long in the direction of 45 ° to the coating layer with red and aquatic magic magic, and after 24 hours, contamination source was removed with a remover (ethyl alcohol) to measure the presence or absence of contamination.

9. Chemical resistance

A 20 mm × 20 mm cotton cloth impregnated with ethyl alcohol was reciprocated 10 times with a force of about 5 N to the coating layer, and then the surface state of the coating layer was observed.

10. Weight average molecular weight

The weight average molecular weights of the respective polymers in the above examples were determined by calculating the polystyrene reduced weight average molecular weight and the values calculated therefrom by Gel-permeation chromatography (GPC) using a dispersed polystyrene as a reference material. (HLC-8120GPC; Tosoh Corporation) using tetrahydrofuran as a mobile phase, and a column of SuperH2000 and SuperH5000 manufactured by Tosoh Corporation was used. The flow rate was measured at a flow rate of 0.5 ml / min based on the difference in refractive index .

An evaluation of the above adhesion, bending resistance, abrasion resistance, impact resistance, moisture resistance, salt resistance, stain resistance and chemical resistance can be achieved by integrating and recalculating each of the measured values to obtain a relative rating of 1, 2, 3, Respectively.

The following Table 1 shows the hardness, adhesive property, flexural resistance, abrasion resistance, impact resistance, moisture resistance, salt resistance and weather resistance of the surface of the polyethylene coated with the ultraviolet curable coating composition according to Examples 1 to 9 and Comparative Examples 1 and 2 Stain resistance and chemical resistance.

In the ultraviolet curing coating composition of the present invention, when the content of Al-Si-based nano-colloid or silica nano-colloid is increased, the hardness and abrasion resistance tend to be improved, but the properties such as flexural resistance and impact resistance, Respectively.

In addition, it was found that addition of a styrene-butadiene block copolymer in the ultraviolet curing coating composition of the present invention has an effect of improving ductility and adhesion such as flex resistance.

In addition, when the organosiloxane polymer having a photosensitive group is used in the ultraviolet curing coating composition of the present invention, the adhesiveness is improved, and the curing time is further shortened.

In the ultraviolet curing coating composition of the present invention, when the weight average molecular weight of the organic siloxane polymer having a photosensitive group is 500 or less, the curing time is increased and the curing is not sufficiently performed. Further, the polymerization time was increased to increase the weight average molecular weight, and as a result, the organosiloxane polymer having a photosensitive group in the above-mentioned state was measured to have a weight average molecular weight of about 30,000. Accordingly, the weight average molecular weight of the organosiloxane polymer having a photosensitive group is preferably 500 to 30,000, more preferably 600 to 25,000, and still more preferably 700 to 15,000.

In addition, in the ultraviolet curing coating composition of the present invention, the addition of the polyaminoamide compound further improved most of the functionality, and in particular, the adhesive property was improved even though the hardness was improved.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Those skilled in the art will recognize that many modifications and variations are possible in light of the above teachings.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed.

Claims (12)

A metal-silicon-based nanocolloid, a nanosilica colloid, an amine-based silane, and an epoxy-based silane. The method according to claim 1,
Wherein the metal-silicon-based nano-colloid comprises one or more selected from aluminum, zinc, magnesium, tin, calcium, zirconium and antimony. 3. The method of claim 2,
Wherein the metal-silicon-based nano-colloid is an aluminum-silicon-based nano-colloid. The method according to claim 1,
Wherein the ultraviolet ray coating composition further comprises at least one additive selected from a photoinitiator, an ultraviolet ray absorber and a light absorber. 5. The method of claim 4,
The ultraviolet-curable coating composition comprises 30 to 60 wt% of a metal-silicon-based nano-colloid, 30 to 60 wt% of a nano-silica colloid, 0.1 to 5 wt% of an amine-based silane, 0.1 to 5 wt% And 0.1 to 10% by weight of an additive. The method according to claim 1,
Wherein the metal-silicon-based nano-colloid comprises a metal-silicon-based powder, an organosiloxane polymer and a solvent. The method according to claim 6,
Wherein the metal-silicon-based nano-colloid comprises 80 to 185 parts by weight of the metal-silicon-based powder and 50 to 150 parts by weight of the organosiloxane polymer with respect to 100 parts by weight of the solvent. 8. The method of claim 7,
Wherein the organosiloxane polymer is an organosiloxane polymer having a photosensitive group. The method according to claim 1,
Wherein the nanosilica colloid comprises 80 to 185 parts by weight of Si powder per 100 parts by weight of the solvent. The method according to claim 1,
Wherein the ultraviolet-curing coating composition further comprises 0.1 to 10 parts by weight of a polyaminoamide compound per 100 parts by weight of the metal-silicon-based nano-colloid. The method according to claim 1,
Wherein the UV curable coating composition further comprises 0.1 to 10 parts by weight of a styrene-butadiene block copolymer based on 100 parts by weight of the metal-silicon-based nano-colloid. A method of applying an ultraviolet curing coating composition prepared according to any one of claims 1 to 10 to a resin surface,
S1) applying the ultraviolet curing coating composition to the resin surface; And
S2) irradiating ultraviolet rays onto the surface of the resin which has been subjected to the step S1) and curing the resin;
Is applied to the surface of the resin.