WO2016089061A1 - Composition for forming coating layer having self-healing property, coating layer, and film - Google Patents

Abstract

The present invention relates to a composition for forming a coating layer having a self-healing property, a coating layer, and a film, the composition enabling the provision of a film exhibiting an excellent self-healing property and more improved mechanical properties by being applied to the exterior of various household electric appliances, a display and the like. The composition for forming a coating layer having a self-healing property comprises: a poly(C_2-4 alkylene glycol) modified multifunctional urethane (meth)acrylate-based binder; a di- or more functional (meth)acrylate-based compound; a UV initiator; and silica nanoparticles, wherein the binder has a tri- or more functional urethane bond, poly(C_2-4 alkylene glycol) modified (meth)acrylate-based compounds are respectively bound via the urethane bond, and at least two of the poly(C_2-4 alkylene glycol) modified (meth)acrylate-based compounds bound to each urethane bond comprise poly(C_2-4 alkylene glycol) repeating units having different repeating numbers.

Description

 [Explanation of invention]

[Title of Invention] ^"

 Composition, coating layer and film for forming a coating layer having self-healing properties

 [Cross Citation with Related Application (s)]

 This application is the Korean patent application No. 10-2014-0169892 dated December 1, 2014 and

Claims the benefit of priority based on Korean Patent Application No. 10-2015-0167372, filed Jan. 27, 2015, and all contents disclosed in the literature of such Korean patent applications are incorporated as part of this specification.

 Technical Field

The present invention relates to various molded articles of ^■ is applied to the exterior, for excellent magnetic coating layer having a self restoring property that enables the provision of a film having improved mechanical properties with the restored characteristic-forming composition, the coating layer and the film.

 Background Art

 In order to protect the product from damages caused by mechanical, physical and chemical effects from the outside, various coating layers or coating films may be used for electric and electronic devices such as mobile phones or various display devices, electronic material parts, home appliances, automotive interior and exterior, or various plastic products. It is applied to the surface of various molded articles. However, scratches on the surface of the product coating or cracks on the outer layer deteriorate the appearance characteristics, the main performance, and the life of the product. Therefore, various studies have been conducted to maintain the quality of the product for a long time by protecting the product surface.

In particular, research and interest in coating materials having self-healing properties (SELF-HEA and NG) have increased rapidly in recent years. The self-healing property is a property in which damage such as scratches is gradually healed or reduced itself when damage occurs such as scratches on the coating layer as an external physical force or stimulus is applied to the coating layer. Refers to. The coating material exhibiting such self-healing properties and the mechanism of self-healing properties are known in various ways, but the method of using a coating material exhibiting elasticity is most widely known. That is, when such a coating material is used, even if physical damage such as a scratch is applied on the coating layer, the damage part is gradually filled due to the elasticity of the coating material itself, thereby exhibiting the above-described self-healing properties. By the way, in the case of the existing coating layer exhibiting such self-healing properties, mainly because the elastic material is included, there was a disadvantage that the mechanical properties of the coating layer, such as hardness, wear resistance or coating film strength is not divided. In particular, when applying a coating layer exhibiting self-healing properties to the appearance of various home appliances, such as kitchen appliances and washing machines, the mechanical properties of the coating layer is required to a high level, the conventional coating layer having a self-healing property is such a high mechanical properties In most cases they could not be satisfied. For this reason, when a strong external stimulus is applied to the existing coating layer, there are many cases in which the coating layer itself is permanently damaged and even self-healing properties are lost.

 Due to the problems of the prior art, there is a continuous need for the development of a technology that enables the provision of a coating or film exhibiting improved mechanical properties with excellent self-healing properties.

 [Contents of the Invention]

 [Problem to solve]

 The present invention is applied to the exterior of a variety of molded articles, to provide a composition for forming a coating layer having a self-healing property that enables the provision of a film exhibiting improved mechanical properties with excellent self-healing properties.

 The present invention also provides a coating layer having a self-healing property formed by using the composition for forming a coating layer, and a film including the same.

 [Measures of problem]

 The present invention is a poly (alkylene glycol having 2 to 4 carbon atoms) modified polyfunctional urethane

(Meth) acrylate binders; Bifunctional or higher polyfunctional (meth) acrylate compounds; UV initiators; And silica nanoparticles,

 The binder has a trifunctional or more than a urethane bond, the poly (alkylene glycol having 2 to 4 carbon atoms) modified (meth) acrylate-based compound is bonded to each other through the urethane bond,

At least two of the poly (alkylene glycol having 2 to 4 carbon atoms) modified (meth) acrylate-based compounds bonded to each urethane bond are poly (alkylene glycol having 2 to 4 carbon atoms) repeating units having different repeating numbers. It provides a composition for forming a coating layer having a self-healing property comprising a. The present invention also relates to a poly (alkylene glycol having 2 to 4 carbon atoms) modified polyfunctional urethane (meth) acrylate-based binder, and a (meth) acrylate group of a bifunctional or higher polyfunctional (meth) acrylate-based compound is bonded to each other. A binder layer to form a crosslinked structure; And silica nanoparticles dispersed in the crosslinked structure of the binder layer, wherein the binder layer provides a coating layer having self-healing properties having a crosslinking density of about 5 mol / kg to 10 mol / kg.

 In addition, the present invention provides a film having a self-healing property including a coating layer having the self-healing property.

 Such a film may further include a substrate layer supporting the coating layer, and may further include a printing layer formed under the substrate layer, and an adhesive layer formed under the printing layer. Can be.

 The present invention also provides a molded article to which the film is attached. Hereinafter, a composition for forming a coating layer having a self-healing property, a coating layer, a film, and the like according to an embodiment of the present invention will be described in detail.

 According to one embodiment of the invention, the invention is a poly (alkylene glycol having 2 to 4 carbon atoms) modified polyfunctional urethane (meth) acrylate-based binder; Bifunctional or higher polyfunctional (meth) acrylate compounds; UV initiators; And silica nanoparticles,

 The binder has a trifunctional or more than a urethane bond, a poly (alkylene glycol having 2 to 4 carbon atoms) modified (meth) acrylate-based compound is bonded to each other through the urethane bond,

 At least two of the poly (alkylene glycol having 2 to 4 carbon atoms) modified (meth) acrylate-based compounds bonded to each urethane bond are poly (alkylene glycol having 2 to 4 carbon atoms) repeating units having different repeating numbers. Provided is a composition for forming a coating layer having a self-healing property comprising a.

The composition for forming a coating layer of such an embodiment includes a poly (alkylene glycol having 2 to 4 carbon atoms) modified polyfunctional urethane (meth) acrylate-based binder, a bifunctional or higher polyfunctional (meth) acrylate-based compound, and silica nanoparticles. As containing, the poly (alkylene glycol having 2 to 4 carbon atoms) modified polyfunctional urethane The (meth) acrylate-based binder and the polyfunctional (meth) acrylate-based compound are cured by UV irradiation to form a binder layer, while silica nanoparticles are dispersed in the cured binder layer to provide a coating layer having self-healing properties. To form. In the composition of this embodiment, the poly (alkylene glycol having 2 to 4 carbon atoms) modified polyfunctional urethane (meth) acrylate-based binder has a good flexibility, the relatively long level of the manganese length of the cross-linked structure in the binder layer By maintaining it, a high level of elasticity can be expressed in the binder layer and the coating layer including the same. Due to such a high level of elasticity, even if damage such as scratches occurs due to an external physical stimulus on the coating layer, the damage portion is gradually filled by elasticity, so that the coating layer may exhibit excellent self-healing properties. Furthermore, the poly (alkylene glycol having 2 to 4 carbon atoms) modified polyfunctional urethane (meth) acrylate-based binder included in one embodiment and the composition may have a urethane bond of at least three functional groups, for example, 3 to 6 functional groups. Poly (alkylene glycols having 2 to 4 carbon atoms) modified (meth) acrylate-based compounds bonded to each other, and poly (alkylene glycols having 2 to 4 carbon atoms) modified (meth) acrylates bonded to each urethane bond based at least two of the compounds may be an attribute to each other polyester comprises a poly (alkylene glycol having 2 to 4 carbon atoms), the repeating unit having a different number of iterations (e. g., in the urethane bond of 3 to 6 functional ^" 2 to 4 kinds of poly (alkylene glycols having 2 to 4 carbon atoms) modified (meth) acrylate-based compounds containing different repeating poly (alkylene glycols having 2 to 4 carbon atoms) may be combined. has exist.) .

As will be described further below, by using a binder exhibiting such properties, for example, about 5 mol / kg to 10 mol / kg, black is about 5.5 mol / kg to 8.0 mol / kg using the composition of the embodiment. It was confirmed that a coating layer exhibiting a self-healing property exhibiting a crosslinking density of and a glass transition temperature (Tg) of, for example, about 10 to 30 ^° C., or about 12 to 25 ^° C. can be formed. This is expected because the degree of introduction of the crosslinked structure and the manganese length in the crosslinked structure can be optimized in the cured binder layer and the coating layer including the same by using the binder exhibiting the above-described characteristics. Furthermore, it has been confirmed that the coating layer which meets the above-mentioned crosslinking density and glass transition temperature not only exhibits excellent self-healing properties, but also exhibits excellent mechanical properties such as hardness, wear resistance or coating film strength. Therefore, a coating layer having a self-healing property formed using the composition of the embodiment, and a film including the same, the appearance of various home appliances such as a refrigerator or a washing machine, a screen protection of a display element, an exterior material (for example, a mobile phone bag) Cover, etc.) or the appearance molding of various products.

 The composition of the above embodiment is described in more detail for each component as follows.

 First, the composition of the embodiment includes the poly (alkylene glycol having 2 to 4 carbon atoms) modified polyfunctional urethane (meth) acrylate-based binder. As described above, such a binder has a structure in which a poly (alkylene glycol having 2 to 4 carbon atoms) modified (meth) acrylate-based compounds are bonded to each other through a trifunctional or trifunctional, for example, 3 to 6 functional urethane bond. At least two of the poly (alkylene glycol having 2 to 4 carbon atoms) modified (meth) acrylate-based compounds bonded to each urethane bond may have a poly (alkyl having 2 to 4 carbon atoms) having different repeating numbers. Lenglycol) repeating units.

 More specific examples of such binders include polyethylene glycol-modified polyfunctional urethane (meth) acrylate-based binders and polypropylene glycol-modified polyfunctional urethane (meth) acrylate-based binders. These binders may be used alone or in combination thereof. It is also possible to use a mixture. More suitably, in order to adjust the crosslinking density of the coating layer formed of the embodiment and the composition to an appropriate level, and to further improve the elongation and self-healing properties of the coating layer, the polyethylene glycol modified polyfunctional urethane (meth) acrylate Type binder and polypropylene glycol modified polyfunctional urethane (meth) acrylate type binder can be mixed and used.

Moreover, as said binder, you may use the other well-known component which shows suitable elasticity further. For example, a polycarbonate-modified bifunctional urethane (meth) acrylate-based binder having a bifunctional or more than two-functional urethane bond, to which a polycarbonate-modified (meth) acrylate-based compound is bound, is further added through the urethane bond. As used, the elongation and self-healing properties of the coating layer may be further improved.

 Such polycarbonate-modified bifunctional urethane (meth) acrylate-based binders may be prepared by using a diisocyanate compound and urethane reaction of a polycarbonate-modified (meth) acrylate-based compound described below according to a known method, or may be commercially obtained and used. have.

 On the other hand, the poly (alkylene glycol having 2 to 4 carbon atoms) modified polyfunctional urethane (meth) acrylate-based binder having the above-described structure is, for example, a polyfunctional or higher polyhydric isocyanate compound and a poly (Alkylene glycol having 2 to 4 carbon atoms) .2 or more kinds of poly (alkylene glycol having 2 to 4 carbon atoms) modified (meth) acrylate-based compound containing a repeating unit may be formed by urethane reaction. As a result of the urethane reaction, a binder having the above-described structure and properties is formed by connecting each isocyanate group of the polyisocyanate compound and a hydroxyl group at the end of a poly (alkylene glycol having 2 to 4 carbon atoms) repeating units to form a urethane bond. Can be obtained.

Approach is used for the formation of the binder isocyanate compound is di hitting the isocyanate compound Well, the diisocyanate compound of the reamer, a diisocyanate cyclic oligomer, hex methylene compound diisocyanate isocyanurate ^zero leakage rate (Hexamethylene diisocyanate isocyanurate) , Isophorone diisocyanate isocyanurate, toluene 2,6-diisocyanate isocyanurate, triisocyanate compound and isomers thereof may be one or more selected from the group consisting of The above-mentioned binder can be formed using a trifunctional or more than trifunctional polyisocyanate compound.

In addition, in the specific examples of the polyvalent isocyanate compound, the oligomer, polymer cyclic multimer or isocyanurate of the diisocyanate compound may be formed from a conventional aliphatic or aromatic diisocyanate compound, A ligomer etc. (for example, Aekyung Chemical DN980S etc. which are HDI trimers) can also be obtained and used. More specific examples of such diisocyanate compounds include ethylene ^Diisocyanate , 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), ^1,12 -dodecane diisocyanate, cyclobutane-1,3-di: ^{icy ΰ} Τ " ^ne cyclohexane -1,3- diisocyanate, cyclonucleic acid -1,4- diisocyanate 1 _ isocyanate -3,3,5-trimethyl -5-isocyanatomethyl- cyclonucleic acid, 2,4- nucleohydro toluene _{diisocyanate,.} 2,6-dihydro-hex toluene diisocyanate, hexahydro-1,3-phenylene isocyanate diimide, hex dihydro-1,4-phenylene diisocyanate, -2,4'- di-hydrochloride buffer Phenylmethane diisocyanate, perhydro-4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-stilbene diisocyanate, 3,3 '-Dimethyl-4,4'-biphenylene diisocyanate (T IDI), toluene 2,4- Isocyanate, toluene 2,6-diisocyanate (TDI), diphenylmethane-2,4'-diisocyanate (MDI), 2,2'-diphenylmethane diisocyanate (MDI), diphenylmethane-4,4 '-Diisocyanate (MDI), isophorone diisocyanate (IP), and the like.

In addition, the two or more poly (alkylene glycols having 2 to 4 carbon atoms) modified (meth) acrylate-based compounds used for forming the binder may each have a number average molecular weight of about 200 to 1000, or about 250 to 800. And a poly (alkylene glycol having 2 to 4 carbon atoms) repeating units having a repeating number of 2 to 10 or 4 to 6, respectively. In addition, each poly (alkylene glycol having 2 to 4 carbon atoms) modified (meth) acrylate-based compound is in the above-described range. It may include a poly (alkylene glycol having 2 to 4 carbon atoms) repeating unit having a different repeating number within, and thus may have a different molecular weight. In a more specific example, the poly (alkylene glycol having 2 to 4 carbon atoms) modified (meth) acrylate-based compounds, having a number average molecular weight of about 200 to 500, or about 200 to 400, with a corresponding repeating number At least one first compound having a poly (alkylene glycol having 2 to 4 carbon atoms) repeating unit, and having a number average molecular weight of about 400 to 1000 or about 500 to 800, One or more second compounds each having from 4 to 4 alkylene glycol) repeating units may be used. In this case, the first and second compounds include poly (alkylene glycols having 2 to 4 carbon atoms) repeating units in different repeating numbers, and thus have different number average molecular weights as described above. As a result, the degree of introduction of the crosslinked structure in the cured binder layer and the coating layer and the manganese length in the crosslinked structure can be further optimized. Therefore, the magnetic composition exhibiting the above-described crosslink density and glass transition temperature using the composition of one embodiment can be optimized. It is possible to more effectively form a coating worm having recovery properties. As a result, it is possible to appropriately form a coating layer and the like having further improved self-healing properties and self-healing properties exhibiting mechanical properties.

 On the other hand, the reaction for forming the above-described binder can proceed according to the conventional urethane reaction conditions. For example, the urethane reaction may be performed by stirring for about 1 to 10 hours at about 20 to iocrc, and may be performed in the presence of a metal-containing catalyst such as tin such as DBTDL (Dibutyl tin dilaurate).

 The composition for forming a coating layer having a self-healing property of one embodiment also includes a multifunctional (meth) acrylate-based compound that is bifunctional or higher, more preferably trifunctional or higher. Such a compound may form a crosslinked structure together with the above-described binder to reach the binder layer, and may serve to further improve the mechanical properties of the cured binder layer and the coating layer including the same.

 As such a polyfunctional (meth) acrylate-based compound, any polyfunctional (meth) acrylate-based compound having bifunctional or higher, black or higher trifunctional or higher functionalities, for example, 3 to 6 functionalities can be used without any particular limitation. Specific examples of such a polyfunctional (meth) acrylate-based compound include polyfunctional urethane acrylate, 9-ethylene glycol diacrylate (9-EGDA), bisphenol A epoxy acrylate, polyether triacrylate, pentaerys Lithium tri / tetraacrylate (pentaerythritol tri / tetraacrylate; PETA), dipentaerythritol hexa-acrylate (DPHA), trimethylolpropane triacrylate (TMPTA) and nucleomethylene And at least one selected from the group consisting of hexamethylene diacrylate (HDDA).

In addition, the composition of the embodiment may include a UV initiator, such a UV initiator can be used without any particular limitation to a compound known to be commonly used in the art. Specific examples of such UV initiators include benzophenone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, Oxime compounds or mixtures thereof, and more specific examples thereof include benzophenone, benzoyl methyl benzoate, acetophenone, 2,4-diethyl thioxanthone (2 , 4-diehtyl thioxanthone, 2-chloro thioxanthone, ethyl anthraquinone, 1-hydroxy cyclohexyl phenyl ketone (1-Hydroxy-cyclohexyl-phenyl-ketone, commercially available product) Examples thereof include Irgacure 184 manufactured by Ciba or 2-Hydroxy-2-methyl-1-phenyl-propanone (2-Hydroxy-2-methyl-1 -phenyl-propan-1 -one).

 On the other hand, the composition of one embodiment additionally comprises silica nanoparticles, these components are uniformly dispersed in the cured binder layer, it may serve to further improve the mechanical properties of the coating layer exhibiting self-healing properties. The silica nanoparticles may have a particle size of about 5 to 50 nm, or about 10 to 40 nm, from the viewpoint of appropriately improving the mechanical properties of the coating layer and not degrading the transparency of the coating layer.

 Compositions of one embodiment, in addition to each component described above, an organic solvent for dissolving or dispersing these components; Or one or more additives selected from the group consisting of surfactants, leveling agents and dispersion stabilizers.

 Such organic solvents may be used without any limitation as long as they are known in the art to be used in coating compositions. For example, ketone organic solvents, such as methyl isobutyl ketone, methyl ethyl ketone, and dimethyl ketone; Alcohol organic solvents such as isopropyl alcohol, isobutyl alcohol or normal butyl alcohol; Acetate organic solvents such as ethyl acetate or normal butyl acetate; Sealusolve organic solvents such as ethyl cellusolve or butyl cellusolve may be used, but the organic solvent is not limited to the examples described above. In addition, additives such as surfactants, leveling agents or dispersion stabilizers may be used without any limitation by preparing or commercially obtaining components previously known to be usable in the composition for forming the coating layer.

On the other hand, the composition for forming a coating layer having the above-described self-healing properties of the poly (alkylene glycol having 2 to 4 carbon atoms) modified polyfunctional urethane (meth) acrylate type Around the binder 50 to 90 weight _^0/0, or from about 60 to 88 weight _^0/0, and the second multi-functional or more functional (meth) acrylate-based hwahapmulwa about 5 to 45 parts by weight _^0/0, or from about 7 to 30 wt. _^0/0, and about 1 to 10 parts by weight _^0/0 of the silica nanoparticles, or from about 3 to 8, the composition for forming a binder comprising by weight ⁰ /; And about 0.1 to 5 parts by weight, or about 1 to 3 parts by weight of UV initiator based on 100 parts by weight of the binder-forming composition.

 In addition, the composition of the embodiment may further include about 0.5 to 10 parts by weight of the additive, and about 10 to 50 parts by weight of the organic solvent with respect to 100 parts by weight of the binder-forming composition.

 As the composition of the above-described embodiment includes each component in the above-described content range, it is possible to more effectively form a coating layer having the above-described crosslinking density and self-healing properties exhibiting glass transition silver. As a result, it is possible to appropriately form a coating layer or the like having further self-restoration properties and self-restoration properties exhibiting mechanical properties.

Meanwhile, according to another embodiment of the present invention, there is provided a coating layer having self-healing properties obtained by UV curing the composition of the above-described embodiment. The coating layer of another embodiment having such self-healing properties includes a poly (alkylene glycol having 2 to 4 carbon atoms) modified polyfunctional urethane (meth) acrylate-based binder and (meth) of a bifunctional or higher polyfunctional (meth) acrylate-based compound. A binder layer in which an acrylate group is bonded to each other to form a crosslinked structure; And silica nanoparticles dispersed in a crosslinked structure of the binder layer, wherein the binder layer may have a crosslinking density of about 5 m / kg to 10 mol / kg. In a more suitable example, the binder layer and the coating layer of another embodiment including the same may have a glass transition temperature (Tg) of about 10 to 30 ^° C.

 As already mentioned above, the compositions of one embodiment may have specific structural properties (ie,

Poly (alkylene glycols having 2 to 4 carbon atoms) modified (meth) acrylate-based compounds are bonded to each other through trifunctional or higher functional urethane bonds, and poly (alkylene glycols having 2 to 4 carbon atoms) are bonded to each urethane bond. At least two of the modified (meth) acrylate-based compounds include poly (alkylene glycols having 2 to 4 carbon atoms) satisfying poly (alkylene glycols having 2 to 4 carbon atoms) repeating units having different repeating numbers) denaturalization A polyfunctional urethane (meth) acrylate based binder is included with the other components. Coating layers of other embodiments formed from compositions of one embodiment comprising such binders have a crosslinking density of, for example, about 5 m / kg to 10 mol / kg, or about 5.5 mol / kg to 8.0 mol / kg, for example about 10 Glass transition temperature (Tg) of from about 30 ^° C., or about 12 to 25 ^° C., and by layering of these properties, together with excellent self-healing properties, mechanical properties such as improved hardness, wear resistance or coating strength Can be represented together.

 Therefore, the coating layer having the self-healing property and a film including the same may be used for the appearance of various home appliances such as a refrigerator or a washing machine, screen protection of a mobile phone or a display element, an exterior material (for example, a mobile phone back cover), It is very preferably applied to the appearance of various molded articles such as various automotive interior materials or various plastic products.

 On the other hand, the coating layer of the other embodiment may further be present in a small amount of residual UV initiator, residual organic solvent or additives dispersed in the binder layer. However, in the process of curing and forming the coating layer having the self-healing property, substantially all or almost all of these components may be removed.

 In addition, the coating layer may be in the form of a film alone, or may be in the form of a layer formed by coating on a predetermined substrate layer to be described later, or in the form of a laminated film laminated / formed on a substrate layer.

 Meanwhile, the coating layer of another embodiment described above may be formed through a method of mixing each component to form a composition of one embodiment, applying and drying such a composition on a base layer, and UV curing the dried composition. In this case, when the coating layer alone becomes a film form, using a release film or the like as the base layer, by separating the coating layer after the UV curing can be obtained in the form of a film.

 In the method of forming the coating layer, in the mixing step of each of the components can be uniformly mixed and the composition of one embodiment using a stirring apparatus or a mixing method known to be commonly used for organic compound mixing.

In addition, in the step of applying the composition of one embodiment on the substrate layer, for example, a conventional coating method such as Meyer bar coating method, applicator coating method, rail coating method Without limitation, all of them can be used to apply the composition on the substrate layer. Then, ^at a temperature of about 20 to 80 ^° C, it may be dried for about 1 to 30 minutes to remove substantially all of the organic solvent included in the composition.

In the subsequent UV curing step, UV (for example, ultraviolet rays having a wavelength of about 200 to 400 nm) may be irradiated with an amount of light of about 50 to 2,000 mJ / cm ² to cure the composition on the substrate layer. As a result, it is possible to form a coating layer having a self-healing property according to another embodiment.

 On the other hand, according to another embodiment of the invention, there is provided a film having a self-healing .characteristics including the coating layer of another embodiment described above. As already described above, such a film may be in the form of a single layer film including only the above-described coating layer, but may also be in the form of a laminated film further including a base layer supporting the coating layer.

 In such a film, the base layer may be made of glass, metal or resin, or a variety of materials, more preferably in the form of a resin base layer or a resin base film. Such a resin base layer or a resin base film may be a polycarbonate resin, a polyester resin such as polyethylene terephthalate resin (PET water), a polyolefin resin such as PE or PP, a poly (meth) acrylate resin such as PMMA, High molecular resins such as salose-based resins such as TAC, polyimide-based resins, or cyclic olefinic resins such as COC or COP.

 By forming a coating layer of another embodiment having self-healing properties on the substrate, the layer described above (or separating from the substrate layer after forming the coating layer), a film according to the another embodiment can be obtained. Such films include a coating layer that exhibits excellent mechanical and self-healing properties, such as the appearance of various household appliances or decorative molded products, such as a washing machine or a washing machine, screen protection of a mobile phone or a display device, an exterior material, various automobiles, and the like. It can be applied very favorably to the appearance of various molded articles such as interior materials for interior use or various plastic products.

In a more specific example of such a film, the substrate worm has a thickness of about 50 to 400 μΓ, or about 70 to 400 μΐ, black is about 100 to 300 μΓΠ, and the coating layer is about 10 to 100 μηη, Or about 15 to 50 μηη. As a result, the film exhibits suitable mechanical properties, so that the film can be preferably attached and applied to the appearance of home appliances.

 On the other hand, the film of another embodiment described above may further include a protective film layer formed on the coating layer, and an adhesive layer between the coating layer and the protective film layer. Such a protective film layer may be laminated using any PET film or the like, which is conventionally known as a release film, without any particular limitation, and in order to adhere the protective film layer on a coating layer having the self-healing property, an appropriate adhesive layer. This can be applied. This adhesive layer may have a thickness of about 5 to 50 u m, or about 10 to 30 μΓΓ.

The film of another embodiment may be supplied in the form such that the protective film layer is adhered on the coating layer, for example, a home appliance manufacturer, when applying the film to the appearance of home appliances, the ^' protective film layer And the adhesive layer can be removed. In addition, the film may further include a printing layer formed on the lower portion of the base layer and an adhesive layer formed on the lower portion of the printing layer, and may be attached to an exterior of a molded article such as various home appliances in this form. In this case, various patterns may be printed on the printed layer to enhance the appearance of the home appliance.

 The film described above may be applied to the exterior of various household appliances, decorative molded articles or automobile interior materials such as a garage or a washing machine, or may be applied to the exterior of a mobile phone or a display element. In a more specific example, it can be preferably applied to the exterior of various molded articles such as exterior materials (for example, a back cover) or various plastic products for screen protection of a mobile phone or a display element, thereby causing damage such as scratches by external stimuli Even if this occurs, it exhibits excellent self-healing properties to restore itself, while exhibiting excellent mechanical properties, thereby appropriately protecting the exterior of various molded articles such as various home appliances, display elements, automotive interior materials, and mobile phones.

 【Effects of the Invention】

According to the present invention, a coating layer having a self-healing property exhibiting both mechanical properties such as improved hardness, abrasion resistance or coating strength, together with excellent self-healing properties, a film and the like may be provided. Therefore, the coating layer and the film containing the coating layer can be applied to the exterior of various home appliances such as refrigerators and washing machines or decorative molded articles, or the appearance of various molded articles such as screen protection of mobile phones or display elements or interior materials for automobiles. have.

 [Brief Description of Drawings]

 1 is a polyethylene glycol modified polyfunctional urethane in Preparation Example 1

It is shown by comparing the FNR spectrum before and after the urethane reaction for the production of the (meth) acrylate-based binder.

 [Specific contents to carry out invention]

 The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples. Preparation Example 1 Preparation of Polyethylene Glycol Modified Polyfunctional Urethane (meth) acrylate Binder

HDI-based trimers of Aekyung used as DN980S 3 polyvalent isocyanate Ney functional or more ^"teugye compound of the polyethylene glycol-modified (meth) acrylate as an acrylate-based compound, a different number of repeats of the polyethylene glycol repeating units to different including Polyethyleneglycol monoacrylate (Mn = 300) and polyethyleneglycol monoacrylate (Mn = 500) each having a number average molecular weight were used.

40 g of such polyvalent isocyanate compounds, 30 g of polyethylene glycol monoacrylate (Mn = 300), and polyethylene glycol monoacrylate (Mn = 500). 30 g was mixed with 0.1 g of DBTDL (dibutyl tin dilaurate) and 200 g of methyl ethyl ketone, and stirred at 60 ^° C. for about 5 hours to proceed urethane reaction.

By the end of this urethane reaction, the polyethyleneglycol modified polyfunctional urethane (meth) acrylate type binder of manufacture example 1 was manufactured. The progress of the urethane reaction and the production of the binder was confirmed through the FNR. For reference, FT-IR spectra before and after the urethane reaction are shown in FIG. 1. Referring to Figure 1, about By confirming that the peak derived from the isocyanate group (-NCO) appearing at the position of 2268.5 cm ^{" 1} disappears, it can be confirmed whether the urethane reaction proceeds and the production of the binder. Preparation Example 2: Polypropylene glycol-modified polyfunctional urethane ( Preparation of meth) acrylate binder

 Multifunctionality of DN980S of Aekyung Chemical, HDI-based trimer

Used as the ^"isocyanate compound, and polypropylene glycol-modified (meth) an acrylate-based compound, a different number of repeats of the polypropylene glycol repeat units, different numbers of polypropylene glycol monoacrylate (Mn = having a number average molecular weight including 400) and polypropylene glycol monoacrylate (Mn = 600) were used, respectively.

40 g of such a polyisocyanate compound, 40 g of polypropylene glycol monoacrylate (Mn = 400), 40 g of polypropylene glycol mono acrylate (Mn = 600), 0.15 g of DBTDL (Dibutyl tin dilaurate) and methyl ethyl ketone (methyl ethyl ketone) was combined with 300 g and stirred at 60 ^° C. for about 5 hours to proceed urethane reaction.

By the completion of such urethane reaction, the polypropylene glycol-modified polyfunctional utetan (meth) acrylate-based binder of Production Example 2 was prepared. The progress of the urethane reaction and the production of the binder was confirmed through whether the peak derived from isocyanate group (-NCO) appearing at a position of about 2268.5 cm ᅳ ¹ through FT-IR in the same manner as in Preparation Example 1. Comparative Production Example 1: Preparation of Polyethylene Glycol Modified Polyfunctional Urethane (meth) acrylate-Based Binder

Polyethylene glycol-modified polyfunctional in Preparation Example 1 in the same manner as in Preparation Example 1, except that only 60 g of polyethylene glycol monoacrylate (Mn = 500) was used without using polyethylene glycol monoacrylate (Mn = 300). A urethane (meth) acrylate binder was prepared. The progress of the urethane reaction and the production of the binder was confirmed through FT-IR. Comparative Production Example 2 Preparation of Polyethylene Glycol Modified Polyfunctional Urethane (meth) acrylate-Based Binder

 In Preparation Example 1, polyethylene glycol-modified polyfunctional urethane (meth) acrylates were prepared in the same manner as in Preparation Example 1, except that HDI (diisocyanate compound) having a bifunction was used instead of DN980S of Aekyung Chemical which was an HDI-based trimer. A binder was prepared. The progress of the urethane reaction and the production of the binder was confirmed through FT-IR. Examples 1 and 2: Preparation of Coating Layer Forming Composition Having Self-Resisting Properties Polyethyleneglycol-modified polyfunctional urethane (meth) acrylate binder obtained in Production Example 1, penta as a bifunctional or higher polyfunctional (meth) acrylate compound Erysri was mixed with pentaerythritol triacrylate (PETA) and silica nanoparticles having a particle diameter of 30 nm in the amounts shown in Table 1 to form a composition for forming a binder.

 To 100 parts by weight of the binder-forming composition, 2 parts by weight of UV initiator (Irgacure 184), 1 part by weight of leveling agent and 35 parts by weight of methyl ethyl ketone were mixed to prepare the compositions of Examples 1 and 2. Example 3 Preparation of a Coating Layer Formation Composition Having Self-Healing Properties

 Polypropylene glycol-modified polyfunctional urethane (meth) acrylate-based binder obtained in Production Example 2, pentaerythritol triacrylate (pentaerythritol triacrylate; PETA) as a bifunctional or higher polyfunctional (meth) acrylate-based compound, and a particle size of 30 nm Silica nanoparticles having a mixture was mixed to the content shown in Table 1 to form a composition for forming a binder.

To 100 parts by weight of the binder-forming composition, 2 parts by weight of the UV initiator (Irgacure 184), 1 part by weight of leveling agent and 35 parts by weight of methyl ethyl ketone were mixed to prepare the composition of Example 3. Example 4 Preparation of a Coating Layer Formation Composition Having Self-healing Properties As the polyethyleneglycol modified polyfunctional urethane (meth) acrylate-based binders and polypropylene glycol-modified polyfunctional urethane (meth) acrylate-based binders obtained in Production Examples 1 and 2, respectively, as bifunctional or more than polyfunctional (meth) acrylate-based compounds Pentaerythri triacrylate (pentaerythrit triacrylate (PETA)) and silica nanoparticles having a particle size of 30nm were mixed to the content shown in Table 1 to form a composition for forming a binder.

 To 100 parts by weight of the binder-forming composition, 2 parts by weight of UV initiator (Irgacure 184), 1 part by weight of leveling crab and 35 parts by weight of methyl ethyl ketone were mixed to prepare the composition of Example 4. Example 5 Preparation of a Coating Layer Formation Composition Having Self-Healing Properties

 Polyethyleneglycol-modified polyfunctional urethane (meth) acrylate-based binder obtained in Production Example 1, dipentaerythritol hexa-acrylate (DPHA) and 30 nm as a difunctional or higher polyfunctional (meth) acrylate-based compound Silica nanoparticles having a particle size of were mixed in the amounts shown in Table 1 to form a composition for forming a binder.

 To 100 parts by weight of the binder-forming composition, 2 parts by weight of the UV initiator (Irgacure 184), 1 part by weight of leveling agent and 35 parts by weight of methyl ethyl ketone were mixed to prepare the composition of Example 5.

 .

 Comparative Examples 1 and 2: Preparation of Coating Layer Forming Composition Having Self-Resisting Properties In Example 1, a comparison was made in the same manner as in Example 1 except that the binders of Comparative Preparation Examples 1 and 2 were used instead of the binder of Preparation Example 1 The binders of Examples 1 and 2 were prepared, respectively.

TABLE 1 Specific compositions of Examples 1 to 5 and Comparative Examples 1 and 2

 Binder Type Binder PETA DPHA Silica Nano Content (wt%; Content (wt%; Content (wt%); Particles

Binder Content For Binder Formation Binder Content (wt%; For Forming Binder For Formation In Compositions In Compositions) Content) content) content in the composition in the composition) content) Example 1 Preparation Example 1 85 10 5

Example 2 Preparation 1 75 20 5

Example 3 Preparation 2 75 20 5

Example 4 Preparation 1 + 35 + 35 25 5

 Preparation Example 2

Example 5 Preparation 1 75 20 5

Comparative Example 1 Comparative Preparation Example 85 10 5

 One

Comparative Example 2 Comparative Preparation Example 85 10 5

 2 Test Example: Formation of coating layer and film, evaluation of physical properties

Examples 1 to 5, and the compositions obtained in Comparative Examples 1 and 2, respectively, coated on PET film with meyer bar 40, dried for 2 minutes in an oven at 60 ^° C and irradiated with ultraviolet light of 100mJ / ciif to improve the self-healing properties The coating layer which has, and the film was formed, respectively.

 The physical properties of this coating layer were measured and evaluated by the following method.

1. Crosslink density: The coating layer was swelled and measured and evaluated by the Flory-Rehner equation. More specifically, after measuring the initial mass (Mi) of the coating layer sample (sample size: 2cm in width, 7cm in length, thickness 100), the sample was immersed in 50 mL of fluorine solvent for 168 hours, and then taken out to obtain the final swelled sample. Mass (Mf) was measured. From these initial and final masses, the mass change was calculated from the equation of ΔΜ = Mf-Mi. From this mass change (ΔΜ), the percent swelling volume change of the coating layer sample was calculated, and the crosslink density was finally calculated by introducing the value calculated in the Flory-Rehner equation.

2. Tg: The glass transition temperature of the coating layer was measured using DSC. 3. Self-healing property: The surface of the coating layer was rubbed by reciprocating 30 times with a copper brush having a load of 750g, and then the time for scratch recovery at room temperature was visually confirmed and measured.

 4. Pencil hardness: The pencil hardness of the coating layer was measured in accordance with JIS K5400 with a 500g load.

 5. Scratch resistance measurement: After a certain load was rubbed in steel wool (# 0000) 10 times reciprocating, it was visually observed whether the scratch on the surface of the coating layer. By repeatedly measuring the load, the scratch resistance was evaluated at the maximum load just before the scratch occurred. Physical properties evaluation results measured above are summarized in Table 2 below.

TABLE 2 Property evaluation results of Examples 1 to 3 and Comparative Examples 1 and 2

상기 표 1을 참고하면, 소정의 가교 말도 및 Tg 범위를 층족하는 실시예

Referring to Table 1 above, an embodiment of striking a predetermined cross-linking degree and Tg range

It was confirmed that the coating layers 1 to 5 exhibited excellent self-healing properties, but also excellent mechanical properties such as hardness and scratch resistance. On the other hand, the coating layers of Comparative Examples 1 and 2 not only exhibit self-healing properties, but also have poor mechanical properties such as hardness and scratch resistance.

Claims

 [Claim]  [Claim 1]  Poly (alkylene glycols having 2 to 4 carbon atoms) modified polyfunctional urethane (meth) acrylate-based binders;  Bifunctional or higher polyfunctional (meth) acrylate compounds;  UV initiators; And  Including silica nanoparticles ，  The binder has a trifunctional or more than a urethane bond, a poly (alkylene glycol having 2 to 4 carbon atoms) modified (meth) acrylate-based compound is bonded to each other through the urethane bond,  At least two of the poly (alkylene glycol having 2 to 4 carbon atoms) modified (meth) acrylate-based compounds bonded to each urethane bond are poly (alkylene glycol having 2 to 4 carbon atoms) repeating units having different repeating numbers. Composition for forming a coating layer having a self-healing property comprising a. Γclaim 2  The method of claim 1, wherein the poly (alkylene glycol having 2 to 4 carbon atoms) modified polyfunctional urethane (meth) acrylate-based binder is polyethylene glycol modified. A composition for forming a coating layer having a self-healing property comprising at least one member selected from the group consisting of a polyfunctional urethane (meth) acrylate-based binder and a polypropylene glycol-modified polyfunctional urethane (meth) acrylate-based binder. [Claim 3]  The method of claim 1, further comprising a polycarbonate-modified bifunctional urethane (meth) acrylate-based binder having a bi- or higher-functional urethane linkage, each of which a polycarbonate-modified (meth) acrylate-based compound is bonded through the urethane bond. A composition for forming a coating layer having a self-healing property. [Claim 4] According to claim 1, wherein the poly (alkylene glycol having 2 to 4 carbon atoms) modified polyfunctional urethane (meth) acrylate-based binder  Trifunctional or higher functional polyisocyanate compound,  Formed by the reaction of two or more poly (alkylene glycols having 2 to 4 carbon atoms) modified (meth) acrylate-based compounds containing poly (alkylene glycols having 2 to 4 carbon atoms) repeating units at different repeating numbers; A composition for forming a coating layer having self-healing properties. [Claim 5]  The polyisocyanate compound of claim 4, wherein the polyisocyanate compound is an oligomer of a diisocyanate compound, a polymer of a diisocyanate compound, a cyclic multimer of a diisocyanate compound, a hexamethylene diisocyanate isocyanurate, an isophorone di Isophorone diisocyanate isocyanurate, toluene 2,6-diisocyanate isocyanurate, triisocyanate compound and composition for forming a coating layer having a self-healing property selected from the group consisting of these isomers. [Claim 6]  The composition for forming a coating layer according to claim 4, wherein the two or more poly (alkylene glycols having 2 to 4 carbon atoms) modified (meth) acrylate-based compounds each have a self-healing property having a number average molecular weight of 200 to 1000. [Claim 7] The method according to claim 6, wherein the two or more poly (alkylene glycol having 2 to 4 carbon atoms) modified (meth) acrylate-based compound is at least one first compound having a number average molecular weight of 200 to 500, 400 to 1000 At least one second compound having a number average molecular weight of The first and second compounds include poly (alkylene glycol having 2 to 4 carbon atoms) repeating units in different repeating numbers, and have a self-healing property having a different number average molecular weight. [Claim 8]  The method of claim 1, wherein the polyfunctional (meth) acrylate-based compound is a polyfunctional urethane acrylate, 9-ethylene glycol diacrylate (9-EGDA), bisphenol A epoxy acrylate, polyether triacrylate, pentaerys Leela tri / tetraacrylate (PETA), dipentaerythritol hexa-acrylate (DPHA), trimethyl propane triacrylate (TMPTA) and hexamethylene Composition for forming a coating layer having a self-healing property of at least one selected from the group consisting of diacrylate (hexamethylene diacrylate; HDDA). [Claim 9]  The method of claim 1, wherein the UV initiator is benzophenone (Benzophenone), benzoyl methyl benzoate (Benzoyl methyl benzoate), acetophenone (acetophenone), 2,4-diethyl thioxanthone (2,4-diehtyl thioxanthone), 2-chloro thioxanthone, ethyl anthraquinone, 1-hydroxy cyclohexyl-phenyl-ketone and 2-hydroxy-2-methyl A composition for forming a coating layer having one or more types of self-healing properties selected from the group consisting of -1-phenyl-propanone (2-Hydroxy-2-methyl-1-phenyl-propan-1-one). [Claim 10]  The composition for forming a coating layer according to claim 1, wherein the silica nano mips have a self-healing property having a particle diameter of 5 to 50 nm. [Claim 11] The method of claim 1, further comprising: an organic solvent; Or at least one additive selected from the group consisting of a surfactant, a leveling agent, and a dispersion stabilizer. [Claim 12]  The method of claim 1, 50 to 90 weight ⁰ /. Of the poly (alkylene glycol having 2 to 4 carbon atoms) modified polyfunctional urethane (meth) acrylate-based binder, And 5 to 45 parts by weight _^0/0 of the second multi-functional or more functional (meth) acrylate compound, A binder-forming composition comprising 1 to 10 weight ⁰ /. Of the silica nanoparticles; And  A composition for forming a coating layer having a self-healing property comprising 0.1 to 5 parts by weight of a UV initiator with respect to 100 parts by weight of the binder-forming composition. [Claim 13]  The composition for forming a coating layer according to claim 12, further comprising 0.5 to 10 parts by weight of an additive and 10 to 50 parts by weight of an organic solvent based on 100 parts by weight of the binder forming composition. [Claim 14] A poly (alkylene glycol having 2 to 4 carbon atoms) modified polyfunctional urethane (meth) acrylate-based binder and a (meth) acrylate group of a bifunctional or higher polyfunctional (meth) acrylate-based compound ⁷ ^ A binder layer forming a; And.  It includes silica nanoparticles dispersed in the crosslinked structure of the binder layer, The binder layer is a coating layer having a self-healing property having a crosslinking density of 5 mol / kg to 10 mol / kg. [Claim 15] The coating layer according to claim 14, having self-healing properties with a glass transition silver (Tg) of 10 to 30 ^° C. [Claim 16]  15. The method of claim 14, wherein the binder has a trifunctional or more than three functional urethane bonds, the poly (alkylene glycol having 2 to 4 carbon atoms) modified (meth) acrylate-based compound is bonded to each other through the urethane bond, each urethane At least two of the poly (alkylene glycol having 2 to 4 carbon atoms) modified (meth) acrylate-based compounds bonded to the bond include poly (alkylene glycol having 2 to 4 carbon atoms) repeating units having different repeating numbers. Coating layer having a self-healing property. [Claim 17]  A film having self-healing properties comprising a coating layer having a self-healing property of claim 14. [Claim 18]  18. The film having self-healing properties according to claim 17, further comprising a base worm supporting the coating layer.  .  [Claim 19]  The method of claim 18, wherein the base layer is a polyolefin resin, poly (meth) acrylate resin, cellulose resin, polyimide resin, cyclic olefin resin, polycarbonate resin and polyester resin A film having self-healing properties, which is a resin base film comprising a resin selected from the group consisting of: [Claim 20] The film of claim 18, wherein the base layer has a thickness of 50 to 400 μ ΓΠ and the coating layer has a self-healing property having a thickness of 10 to 100 μπη. [Claim 21]  The film of claim 17, further comprising a protective film layer formed on the coating layer, and an adhesive layer between the coating layer and the protective film layer. [Claim 22]  The film of claim 18, further comprising a printing layer formed under the substrate layer and an adhesive layer formed under the printing layer. [Claim 23]  The molded article to which the film of Claim 17 is affixed. [Claim 24] The method of claim 23, wherein the ^"home appliances, mobile phones or automobile interior molded article for a display device.