Cured product and decorative film comprising same

Abstract

A cured product according to one exemplary embodiment of the present invention is a cured product of an acrylic resin composition, and has a peak at 9.00 minutes to 11.00 minutes when extracted at 133 m / z (mass / charge) and 203 m / z (mass / charge), respectively, in a map obtained by Pyro-GCMS (Thermal Cracking-Gas Chromatography / Mass Spectrometry) analysis of the cured product.

Description

Technical Field

[0001] This application claims the priority and benefit of Korean Patent Application No. 12-2022-0165687, filed with the Korean Intellectual Property Office on December 1, 2022, the entire content of which is incorporated herein by reference.

[0002] The present invention relates to a cured product and a decorative film including the cured product. Background Art

[0003] Decorative films having a matte property (or low gloss property) are widely used in the manufacture of films for interior building materials and furniture. More specifically, the matte property of the decorative film can be achieved by forming irregularities on the surface to cause diffuse reflection. For example, in the related art, a technique for manufacturing a decorative film having a matte property is generally employed in which a coating agent containing a matting agent (e.g., silica) is applied to a substrate and then the coating agent is cured.

[0004] However, when forming surface irregularities to achieve the matte property, there is a problem that contaminants penetrating between the peaks and valleys of the irregularities are not easily removed, resulting in deterioration of the stain resistance of the decorative film. In addition, since conventional matting agents are porous and have a low apparent specific gravity, they tend to remain in the surface layer of the coating, which leads to deterioration of the stain resistance, such as an increase in surface adsorption of foreign substances (e.g., fine dust, moisture, grease, etc.). Note that, in order to improve the stain resistance, it is advantageous to increase the curing density. For example, the use of a polyfunctional oligomer in the coating agent can be considered. However, when the amount of the polyfunctional oligomer increases, the glossiness of the cured product layer increases, which makes it unsuitable for a decorative film intended to exhibit a matte property. That is, since the matte property and the stain resistance are trade-off properties, it is necessary to study a decorative film capable of satisfying both properties simultaneously. Summary of the Invention

[0005] Technical Problem

[0006] The present invention is directed to providing a cured product and a decorative film including the cured product. More specifically, the present invention is directed to providing a cured product having excellent matte property and stain resistance and a decorative film including the cured product.

[0007] Technical Solution

[0008] An exemplary embodiment of the present invention provides a cured product, wherein the cured product is a cured product of an acrylic resin composition, and in the graph obtained by Pyro-GCMS (pyrolysis-gas chromatography / mass spectrometry) analysis of the cured product, when extracted at 133 m / z (mass / charge) and 203 m / z (mass / charge) respectively, it has peaks at 9.00 minutes to 11.00 minutes.

[0009] In addition, another exemplary embodiment of the present invention provides a decorative film, which includes a base material layer; and the above-mentioned cured product provided on the base material layer.

[0010] In addition, yet another exemplary embodiment of the present invention provides a method for manufacturing a decorative film, including:

[0011] Preparing a base material layer;

[0012] Applying an acrylic resin composition on the base material layer;

[0013] Irradiating the applied composition with light (L1) having a predetermined wavelength under an inert gas condition to form a first light irradiation with wrinkles on the surface of the applied composition; and

[0014] Irradiating the applied composition with light (L2) having a wavelength longer than that of the light (L1) under an air condition to form a second light irradiation of a cured product layer of the composition,

[0015] wherein, in the graph obtained by Pyro-GCMS (pyrolysis-gas chromatography / mass spectrometry) analysis of the cured product layer, when extracted at 133 m / z (mass / charge) and 203 m / z (mass / charge) respectively, the cured product layer has peaks at 9.00 minutes to 11.00 minutes.

[0016] Advantageous Effects

[0017] The cured product according to an exemplary embodiment of the present invention and the decorative film including the cured product exhibit matte properties and excellent stain resistance. Specifically, the cured product according to an exemplary embodiment of the present invention and the decorative film including the cured product can improve stain resistance to contaminants such as mustard that leave dark marks even on matte surfaces. Description of the Drawings

[0018] Figure 1 It is a schematic diagram showing a decorative film according to an exemplary embodiment of the present invention.

[0019] Figure 2It is a diagram showing the Pyro-GCMS (pyrolysis-gas chromatography / mass spectrometry) analysis results of the cured product according to Embodiment 1 of the present invention.

[0020] Figure 3 It is a diagram showing the Pyro-GCMS analysis results of the cured product according to Embodiment 2 of the present invention.

[0021] Figure 4 It is a diagram showing the Pyro-GCMS analysis results of the cured product according to Embodiment 3 of the present invention.

[0022] Figure 5 It is a diagram showing the Pyro-GCMS analysis results of the cured product according to Embodiment 4 of the present invention.

[0023] Figure 6 It is a diagram showing the Pyro-GCMS analysis results of the cured product according to Embodiment 5 of the present invention.

[0024] Figure 7 It is a diagram showing the Pyro-GCMS analysis results of the cured product according to Embodiment 6 of the present invention.

[0025] Figure 8 It is a diagram showing the Pyro-GCMS analysis results of the cured product according to Comparative Example 1 of the present invention.

[0026] Figure 9 It is a diagram showing the Pyro-GCMS analysis results of the cured product according to Comparative Example 2 of the present invention.

[0027] Figure 10 It is a diagram showing the Pyro-GCMS analysis results of the cured product according to Comparative Example 3 of the present invention.

[0028] <Description of reference numerals and symbols>

[0029] 10: Substrate layer

[0030] 20: Cured product Detailed description of the invention

[0031] Hereinafter, the present invention will be described in more detail.

[0032] Throughout the present invention, when a member is referred to as being "on" another member, the member may be in direct contact with the other member, or there may also be an intermediate member between the two members.

[0033] In the present invention, when a component is referred to as "comprising" a certain component, this means that the component may further comprise another component, rather than excluding another component, unless explicitly stated to the contrary.

[0034] When purchasing furniture, consumers regard surface properties, especially stain resistance, as one of the most important characteristics, and it is also one of the factors that are easily encountered. In particular, when the surface is matte-finished, contaminants are often trapped in the minute surface irregularities formed to reduce glossiness, which adversely affects stain resistance. Even in the case where dark-colored contaminants such as soy sauce, ketchup, pickled vegetable juice, and mustard are left on the surface, they significantly change the appearance, so a technique for preventing discoloration is necessary. However, due to the nature of the matte coating, it is difficult to achieve such prevention.

[0035] Accordingly, the present invention is directed to providing a cured product and a decorative film including the cured product, which can improve stain resistance against contaminants such as mustard that leave dark colors even on a matte surface.

[0036] The cured product according to an exemplary embodiment of the present invention is a cured product of an acrylic resin composition, and in a graph obtained by Pyro-GCMS (pyrolysis-gas chromatography / mass spectrometry) analysis of the cured product, when extracted at 133 m / z (mass / charge) and 203 m / z (mass / charge) respectively, it has peaks at 9.00 minutes to 11.00 minutes.

[0037] Pyro-GCMS refers to a system in which a pyrolysis device (pyrolyzer), a gas chromatograph (GC), and a mass spectrometer (MS) are connected in series, and the pyrolysis products generated by pyrolysis are separated using GC and then detected using MS. In other words, Pyro-GCMS is a system that pyrolyzes a sample using a pyrolysis device, separates the resulting pyrolysis products into individual components using GC, and then analyzes them using MS to identify each separated substance by its mass spectrum and determine its quantity. Since each peak appearing in the graph obtained by Pyro-GCMS analysis has an inherent mass spectrum therein, the pyrolysis products can be identified by interpreting the corresponding mass spectrum, and its content can be determined from the area of each peak.

[0038] In particular, the inventors of the present invention have found that when the cured product has peaks at 9.00 minutes to 11.00 minutes when extracted at 133 m / z and 203 m / z respectively in a graph obtained by Pyro-GCMS analysis, the surface of the cured product exhibits excellent stain resistance. In particular, in a graph obtained by Pyro-GCMS analysis of the cured product, if no peaks are observed at 9.00 minutes to 11.00 minutes when extracted at 133 m / z and 203 m / z respectively, the desired effect of improving stain resistance against contaminants such as mustard that leave dark colors even on a matte surface of the present invention cannot be achieved.

[0039] In an exemplary embodiment of the present invention, in the graph obtained by Pyro-GCMS analysis of the cured product, when extracted at 133 m / z and 203 m / z respectively, the cured product may have peaks at 9.00 minutes to 11.00 minutes, 9.50 minutes to 10.90 minutes, or 10.00 minutes to 10.80 minutes.

[0040] In an exemplary embodiment of the present invention, the cured product may have a surface glossiness value of 10 or less, 6 or less, 1 to 5, or 1.5 to 4 under 60° glossiness conditions. When the surface glossiness value of the cured product under 60° glossiness conditions falls within a specific range, the matte performance required for the decorative film can be ensured. In the present invention, the glossiness value under 60° glossiness conditions can be measured using a glossmeter according to ASTM D2457 and is a numerical value representing the surface glossiness. A lower glossiness value may indicate a more matte surface.

[0041] In an exemplary embodiment of the present invention, the surface of the cured product may have a wrinkled surface, and the surface roughness (Rz) of the cured product may be 3 μm to 10 μm, 3.5 μm to 9 μm, or 4 μm to 8 μm. When the surface roughness (Rz) of the cured product falls within a specific range, the matte performance required for the decorative film can be ensured, and the surface of the cured product can also exhibit a smooth touch.

[0042] The surface roughness (Rz) of the cured product can be measured according to ISO 4281 and can also be referred to as the ten-point mean roughness. More specifically, the surface roughness of the cured product is a numerical value representing the degree of irregularity, and is generated by taking the reference length L as the cross-sectional curve of the surface of the cured product, and measuring the deviation of the interval between the fifth ridge on the higher side of the undulating structure and the fifth valley on the deeper side with a straight line that does not cross the cross-sectional curve parallel to the average line of this part. In this case, the reference length (L) may be on the order of several mm, for example, in the range of about 0.1 mm to 1 mm, specifically, about 0.8 mm.

[0043] The wrinkled surface enables the surface roughness (Rz), glossiness value, etc. of the cured product to be satisfied.

[0044] The wrinkled surface means that the cured product includes wrinkles on at least one of its surfaces and has three-dimensional surface irregularities due to the wrinkles. For example, the surface has irregularities that include large and small ridges, valleys, and wrinkles formed by them that can be visually recognized in a predetermined shape. Each ridge, valley, and wrinkle can have a regular or irregular shape. Such a wrinkled surface can also be referred to as a surface having a micro-folded structure.

[0045] When observing the wrinkled surface of the cured product in the normal direction of the cured product, for example, through the curing process described below, ridges, valleys, wrinkles, and irregularities formed thereby are observed over the entire area of the surface.

[0046] The wrinkles can be observed in the form of line shapes including directional shapes (e.g., straight lines and curves). For example, the wrinkles on the surface formed by repeating straight shapes and curved shapes can provide a mountain-like undulation to the surface of the coating. In this way, the surface irregular structure formed by the wrinkles having a line shape can be clearly distinguished from the so-called dot-like irregular shapes formed by using particles in the composition for forming the cured product layer or by adopting an emulsion dispersion method.

[0047] The surface of the cured product can include visually recognizable wrinkles having a predetermined size and shape. More specifically, the wrinkles can have a width ranging from several hundred nm to several tens of μm, and a line (straight or curved) shape extending with a length ranging from several μm to several hundred μm. The width and the extended length of the wrinkles can be confirmed from an image (e.g., SEM) obtained by capturing the wrinkled surface.

[0048] While forming an inclined surface with a gradually decreasing height, the end portions of the wrinkles extending in a straight shape or a curved shape can be incorporated into the cured product. In some cases, the end portion of one wrinkle having the above-described size and shape can become the starting point of another wrinkle or the connection point with another wrinkle. Further, when observing the cross-sectional curve in the vicinity of the wrinkle in a direction perpendicular to the extending direction of the wrinkle, the width of the wrinkle can be incorporated into the coating while forming an inclined surface with a height gradually decreasing in two directions based on the point or portion (e.g., ridge) forming the height of the wrinkle. Note that when a ridge and a valley adjacent to the ridge form a wrinkle or a part of a wrinkle, the visually recognizable shape region including the valley can be regarded as the width of the wrinkle.

[0049] In an exemplary embodiment of the present invention, the surface of the cured product can have a dendrite shape, which is a radially undulating structure extending from a point as a center to the periphery.

[0050] In an exemplary embodiment of the present invention, the cured product can be manufactured by curing a composition having a predetermined configuration. The composition can be a photocurable solvent-free composition. That is, the composition can not contain organic solvents, aqueous solvents, etc. When using a solvent-free composition, the drying process of the solvent can be omitted, and thus the process efficiency can be improved. Additionally, when using a solvent-free composition, deterioration of the surface properties caused by bubbles or the like generated during the evaporation of the solvent during the solvent drying process can be prevented.

[0051] In an exemplary embodiment of the present invention, the cured product is a cured product of an acrylic resin composition.

[0052] More specifically, the acrylic resin composition may include 1 to 60 parts by weight of an acrylic oligomer, 1 to 40 parts by weight of a siloxane oligomer, and 30 to 100 parts by weight of a monomer, and may include 5 parts by weight or less of an initiator based on 100 parts by weight of the acrylic oligomer, siloxane oligomer, and monomer.

[0053] The acrylic oligomer refers to an oligomer obtained by using a monomer containing an acrylic group. The acrylic oligomer may include one or more of a methyl acrylate oligomer, a (meth)acrylate oligomer, a (meth)methyl acrylate oligomer, an ethyl acrylate oligomer, a urethane (meth)acrylate oligomer, etc.

[0054] The weight average molecular weight of the acrylic oligomer may be 100 g / mol to 50,000 g / mol, 500 g / mol to 30,000 g / mol, or 1,000 g / mol to 10,000 g / mol. When the weight average molecular weight of the above acrylic oligomer falls within a specific range, the durability of the cured product can be further improved.

[0055] According to an exemplary embodiment of the present invention, by including a siloxane oligomer, the effect of reducing gloss can be achieved, and surface wrinkles can be controlled to improve fingerprint resistance. The weight average molecular weight of the siloxane oligomer may be 1,000 g / mol to 50,000 g / mol, or 5,000 g / mol to 10,000 g / mol. The siloxane oligomer may be a urethane acrylate oligomer having an inserted siloxane group, but is not limited thereto.

[0056] The monomer may be an acrylic monomer, specifically, an acrylate monomer containing a hydrophilic group, but is not limited thereto. The monomer may include one or more of (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 2-hydroxyethylene glycol (meth)acrylate, 2-hydroxypropylene glycol (meth)acrylate, acrylic acid, methacrylic acid, 2-(meth)acryloyloxyacetic acid, 3-(meth)acryloyloxypropyl acid, 4-(meth)acryloyloxybutyric acid, 1,6-hexanediol diacrylate, acrylic acid dimer, itaconic acid, maleic acid, caprolactone-modified hydroxyacrylate (CHA), tetraethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane ethoxytriacrylate, etc.

[0057] The composition may contain 1 to 60 parts by weight of an acrylic oligomer, 1 to 40 parts by weight of a siloxane oligomer, and 30 to 100 parts by weight of a monomer, and may contain 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less of an initiator relative to 100 parts by weight of the acrylic oligomer, siloxane oligomer, and monomer. By sequentially applying short-wavelength light within a specific range under different conditions during the curing of the composition, the present invention can exhibit a high curing rate even when the initiator is contained in a small amount within a specific range.

[0058] The composition may further contain a high-hardness filler to enhance the durability of the cured product. For example, the filler may be a filler that can enhance the surface hardness without affecting the gloss of the cured product after the composition is cured. More specifically, as the filler, silica, alumina, glass beads, organic beads (such as polymer particles), etc. may be used. The filler may be contained in an amount of 3 parts by weight or less relative to 100 parts by weight of the composition so as not to impair the gloss and stain resistance of the cured product.

[0059] In an exemplary embodiment of the present invention, the thickness of the cured product may be 0.1 μm to 25 μm, 1 μm to 20 μm, or 5 μm to 18 μm. If the thickness of the cured product is less than 0.1 μm, the cured product may be difficult to have a wrinkled surface, and if the thickness exceeds 25 μm, the total thickness of the decorative film may become thick, which may limit its application.

[0060] In addition, another exemplary embodiment of the present invention provides a decorative film including a base material layer; and the above-mentioned cured product provided on the base material layer.

[0061] In the decorative film according to an exemplary embodiment of the present invention, the description of the cured product is the same as above.

[0062] There is no particular limitation on the type of the base material layer. For example, the base material layer may include ethylene glycol-modified polyethylene terephthalate (PETG), polyvinyl chloride (PVC), or polyethylene terephthalate (PET). There is also no particular limitation on the thickness of the base material layer. For example, the thickness of the base material layer may be 30 μm or more, 50 μm or more, 100 μm or more, 150 μm or more, 200 μm or more, 250 μm or more, 300 μm or more, 350 μm or more, 400 μm or more, 450 μm or more, or 500 μm or more. Additionally, the thickness of the base material layer may be 3,000 μm or less, 2,000 μm or less, 1,000 μm or less, 900 μm or less, 800 μm or less, 700 μm or less, 600 μm or less, 500 μm or less, 400 μm or less, or 300 μm or less.

[0063] Figure 1 Schematically shows a decorative film according to an exemplary embodiment of the present invention. As Figure 1 shown, the decorative film according to an exemplary embodiment of the present invention includes a base material layer 10 and a cured product 20 provided on the base material layer 10. In this case, in the graph obtained by Pyro-GCMS analysis of the cured product 20, when extracted at 133 m / z and 203 m / z respectively, the cured product 20 has a peak at 9.00 minutes to 11.00 minutes.

[0064] Furthermore, a method for manufacturing a decorative film according to an embodiment of the present invention includes the following steps: preparing a base material layer; applying an acrylic resin composition on the base material layer; performing a first light irradiation with light (L1) having a predetermined wavelength under an inert gas condition to form wrinkles on the surface of the applied composition; and performing a second light irradiation with light (L2) having a wavelength longer than that of light (L1) under an air condition to form a cured product layer of the composition, wherein, in the graph obtained by Pyro-GCMS analysis of the cured product layer, when extracted at 133 m / z and 203 m / z respectively, the cured product layer has a peak at 9.00 minutes to 11.00 minutes.

[0065] In the method for manufacturing a decorative film according to an exemplary embodiment of the present invention, the descriptions of the base material layer and the cured product are the same as those above.

[0066] There is no particular limitation on the method for applying the composition onto the base material layer. For example, known methods such as a Meyer rod, a D-rod, a rubber roll, a G / V roll, an air knife, or a slot die may be used to apply the composition onto the base material layer.

[0067] There is no particular limitation on the device used for irradiating light in each step. For example, when irradiating light with a wavelength of 300 nm or less in the first light irradiation step and irradiating light with a wavelength of 400 nm or less in the second light irradiation step, a known mercury or metal halide lamp or the like can be used.

[0068] The first light irradiation step is a step of irradiating light onto the composition applied to the substrate material layer and causing the surface of the applied composition (or the composition cured by light irradiation) to shrink due to the excimer generated by the irradiated light to form wrinkles. The wrinkled surface induces diffuse reflection of the light incident on the surface, thereby imparting a matte property.

[0069] The wrinkled surface can have the surface roughness and gloss characteristics as described above. Therefore, a matting agent may not be used in the present invention.

[0070] In the first light irradiation step, light having a wavelength of 300 nm or less and high energy can be irradiated. For example, light having a wavelength of 200 nm or less can be irradiated. Specifically, in the first light irradiation step, light having a wavelength of 130 nm or more, 140 nm or more, 150 nm or more, 160 nm or more, or 170 nm or more can be irradiated. The upper limit of the wavelength of the light irradiated in the first light irradiation step can be, for example, 200 nm or less, 190 nm or less, or 180 nm or less.

[0071] The first light irradiation step can be carried out in an inert atmosphere. The gas used to generate the inert atmosphere can be, for example, He, Ne, Ar, and / or N2.

[0072] The inert atmosphere for carrying out the first light irradiation step can be an atmosphere with an oxygen (O2) concentration of about 4,000 ppm or less. Specifically, the upper limit of the oxygen concentration in the inert atmosphere can be 3,000 ppm or less, 2,500 ppm or less, 2,000 ppm or less, 1,500 ppm or less, or 1,000 ppm or less, and more specifically 900 ppm or less, 800 ppm or less, 700 ppm or less, 600 ppm or less, 500 ppm or less, 400 ppm or less, or 300 ppm or less. In addition, the lower limit of the oxygen concentration in the inert atmosphere can be, for example, 50 ppm or more, 100 ppm or more, 200 ppm or more, 300 ppm or more, 400 ppm or more, 500 ppm or more, 600 ppm or more, 700 ppm or more, 800 ppm or more, 900 ppm or more, or 1,000 ppm or more.

[0073] An inert atmosphere can be formed such that the oxygen concentration in nitrogen (N2) falls within a specific range.

[0074] When the first light irradiation is carried out under the inert atmosphere conditions as described above, it is beneficial to ensure the above-mentioned wrinkles and surface characteristics. For example, if the first light irradiation is carried out in an inert atmosphere with an oxygen concentration exceeding a specific range, it becomes difficult to form the above-mentioned wrinkles, and the above-mentioned surface characteristics cannot be provided.

[0075] When the first light irradiation step is carried out, the distance between the composition and the light source, that is, the distance from the surface of the composition applied on the substrate material layer to the light source, can be 5 mm or more. Specifically, the lower limit of the distance can be 10 mm or more, 15 mm or more, 20 mm or more, 25 mm or more, 30 mm or more, 35 mm or more, 40 mm or more, 45 mm or more, or 50 mm or more, and the upper limit thereof can be 90 mm or less, 85 mm or less, 80 mm or less, 75 mm or less, 70 mm or less, 65 mm or less, 60 mm or less, 55 mm or less, or 50 mm or less. In the first light irradiation step, when the distance between the composition and the light source is adjusted to a specific range, an appropriate amount of light can reach the composition at an appropriate intensity. Therefore, it is beneficial to form a wrinkled surface having the above shape and size and ensure the above surface characteristics (for example, surface roughness and glossiness value).

[0076] The irradiation amount of the light irradiated in the first light irradiation step can be 1 mJ / cm 2 or 5 mJ / cm 2 or more. Specifically, the lower limit of the irradiation amount of the light in the first light irradiation step can be 10 mJ / cm 2 or more, 15 mJ / cm 2 or more, 20 mJ / cm 2 or more, 25 mJ / cm 2 or more, or 30 mJ / cm 2 or more, and the upper limit thereof can be 100 mJ / cm 2 or less, 90 mJ / cm 2 or less, 80 mJ / cm 2 or less, 70 mJ / cm 2 or less, 60 mJ / cm 2 or less, 50 mJ / cm 2 or less, 40 mJ / cm 2 or less, 30 mJ / cm 2 or less, or 25 mJ / cm 2 or less. In the first light irradiation step, when the irradiation amount of the light is adjusted to a specific range, it is beneficial to form the above-mentioned wrinkled surface and ensure the above surface characteristics (for example, surface roughness and glossiness value).

[0077] The second light irradiation step is a step of applying light energy having a wavelength different from that of the light in the first light irradiation step to the composition coated on the base material layer and having wrinkles formed on the surface by the first light irradiation step, so that the composition is cured to form a cured product layer.

[0078] In the second light irradiation step, light having a wavelength in the range of 200 nm to 400 nm may be irradiated. Specifically, the second light irradiation step may be a step of irradiating light having a wavelength of 210 nm or more, 220 nm or more, 230 nm or more, 240 nm or more, 250 nm or more, 260 nm or more, 270 nm or more, 280 nm or more, 290 nm or more, or 300 nm or more. The upper limit of the wavelength of the light irradiated in the second light irradiation step may be 350 nm or less, 340 nm or less, 330 nm or less, 320 nm or less, 310 nm or less, or 300 nm or less. By performing the second light irradiation step in which relatively long-wavelength light is irradiated, the composition that is only cured to a certain level by the first light irradiation step and has wrinkles formed on its surface can be cured in the thickness direction.

[0079] The second light irradiation step may be a step of irradiating light having a longer wavelength than that in the first light irradiation step within the above wavelength range.

[0080] The second light irradiation step is performed in an air atmosphere. During irradiation, the air atmosphere can increase the curing rate of the composition and provide a cleaning effect on the surface of the coating as oxygen molecules (O2) are converted to ozone (O3).

[0081] When performing the second light irradiation step, the distance between the composition and the light source, that is, the distance from the surface of the composition applied on the base material layer to the light source, may be 50 mm or less, 40 mm or less, 30 mm or less, or 20 mm or less. Specifically, the upper limit of the distance may be 19 mm or less, 18 mm or less, 17 mm or less, 16 mm or less, 15 mm or less, 14 mm or less, 13 mm or less, 12 mm or less, 11 mm or less, or 10 mm or less, and the lower limit may be 0.5 mm or more, 1 mm or more, 2 mm or more, 3 mm or more, 4 mm or more, or 5 mm or more. When performing the second light irradiation step, the distance between the composition and the light source may be less than the distance in the first light irradiation step. In the second light irradiation step, when the distance between the composition and the light source is adjusted within a specific range, it is beneficial to increase the curing degree of the entire cured product layer.

[0082] The irradiation amount of the light irradiated in the second light irradiation step may be greater than the irradiation amount of the light irradiated in the first light irradiation step. For example, the irradiation amount of the light irradiated in the second light irradiation step may be 150 mJ / cm 2Above, especially 160 mJ / cm 2 Above, 170 mJ / cm 2 Above, 180 mJ / cm 2 Above, 190 mJ / cm 2 Above, 200 mJ / cm 2 Above, 210 mJ / cm 2 Above, 220 mJ / cm 2 Above, 230 mJ / cm 2 Above, 240 mJ / cm 2 Above, 250 mJ / cm 2 Above, or 300 mJ / cm 2 Above. Additionally, the upper limit can be 500 mJ / cm 2 Below, or 400 mJ / cm 2 Below, specifically 350 mJ / cm 2 Below, 340 mJ / cm 2 Below, 320 mJ / cm 2 Below, 310 mJ / cm 2 Below, or 300 mJ / cm 2 Below. When adjusting the irradiation amount of light within a specific range during the second light irradiation period, it is beneficial to increase the curing degree of the entire coating.

[0083] As described above, when performing the first light irradiation step and the second light irradiation step, the surface of the coating can have a relatively dense curing density.

[0084] Next, examples will be described in detail to specifically describe the present invention. However, the examples of the present invention can be modified in other forms, and the scope of the present invention is not to be construed as limited to the following examples. The examples of the present invention are provided to more fully explain the present invention to those skilled in the art.

[0085] <Examples>

[0086] <Examples 1 to 6 and Comparative Examples 1 to 3>

[0087] The composition was prepared by mixing the components shown in Tables 1 and 2 below.

[0088] A poly(ethylene terephthalate glycol) (PETG) film (20 cm wide × 30 cm long) containing ethylene glycol was prepared as the base material layer, and the prepared composition was applied to the surface of the prepared film to a thickness of 3 μm to 6 μm using a bar coating method. Thereafter, first, in an inert atmosphere, at 1 mJ / cm 2 to 100 mJ / cm 2Under a light quantity, a film applied with the composition is irradiated with light having a wavelength of 300 nm or less, and then, in an air atmosphere, irradiated with light having a wavelength in the range of 200 nm to 400 nm under a light quantity of 150 mJ / cm 2 to 500 mJ / cm 2 so that the applied film is cured to prepare a decorative film.

[0089] [Table 1]

[0090]

[0091] [Table 2]

[0092]

[0093] Monomer 1: Cyclic monofunctional monomer (IBOA, isobornyl acrylate)

[0094] Monomer 2: Linear bifunctional monomer (HDDA, 1,6 - hexanediol diacrylate)

[0095] Monomer 3: Cyclic bifunctional monomer (TCDDA, tricyclodecane dimethanol diacrylate) Oligomer 1: Linear hexa - functional acrylic oligomer (Mw 5,000 g / mol or less)

[0096] Oligomer 2: Linear nona - functional acrylic oligomer (Mw 10,000 g / mol or less)

[0097] Oligomer 3: Siloxane - based oligomer (Mw 10,000 g / mol or less)

[0098] Additive 1: First light stabilizer

[0099] Additive 2: Second light stabilizer

[0100] Additive 3: Levelling agent

[0101] [Experimental Example 1]

[0102] The results of the evaluation of the surface properties of the decorative films of the examples and comparative examples and the Pyro - GCMS analysis are shown in Table 3 below.

[0103] [Table 3]

[0104]

[0105] The methods for the evaluation characteristics in Table 3 are as follows.

[0106] [Gloss value]

[0107] According to ASTM D2457, using a gloss meter, the gloss is measured under 60° gloss conditions.

[0108] <Roughness (Rz, μm)>

[0109] According to ISO 4281, the roughness is measured as the ten-point mean roughness. The deviation is represented by taking the reference length L (0.8 mm) as the cross-sectional curve of the surface of the first coating or the second coating, and measuring the interval between the fifth ridge from the higher side and the fifth valley from the deeper side of the undulating structure with a straight line that does not cross the cross-sectional curve parallel to the average line of this part.

[0110] <Stain resistance>

[0111] The stain resistance is evaluated according to DIN 68861:2011, part 1. After exposure to mustard as a pollutant, the degree of staining of the surface is visually inspected and graded from grade 1 (severe staining) to grade 5 (no visible change).

[0112] <Presence or absence of peaks>

[0113] In the graph obtained by Pyro-GCMS analysis, indicate the positions of the peaks that appear when extracted at 133 m / z and 203 m / z, and mark X when no peaks appear.

[0114] Pyro-GCMS analysis method

[0115] - Equipment specifications: Frontier Lab PY-3030D / Agilent 7890B / 5977B

[0116] - Pyrolysis temperature: 600 °C, 10 min

[0117] - UA-5 column, 30 m X 250 μm X 0.25 μm

[0118] - 40 °C for 2 min, 20 °C / min to 310 °C for 14 min

[0119] - Scanning mode, EIC 133, 203 m / z

[0120] - Data processing: Confirm that the detection positions are the same based on the EIC data.

[0121] Figure 2 is a graph showing the Pyro-GCMS analysis results of the cured product according to Example 1 of the present invention.

[0122] Figure 3 is a graph showing the Pyro-GCMS analysis results of the cured product according to Example 2 of the present invention.

[0123] Figure 4It is a diagram showing the Pyro-GCMS analysis results of the cured product according to Embodiment 3 of the present invention.

[0124] Figure 5 It is a diagram showing the Pyro-GCMS analysis results of the cured product according to Embodiment 4 of the present invention.

[0125] Figure 6 It is a diagram showing the Pyro-GCMS analysis results of the cured product according to Embodiment 5 of the present invention.

[0126] Figure 7 It is a diagram showing the Pyro-GCMS analysis results of the cured product according to Embodiment 6 of the present invention.

[0127] Figure 8 It is a diagram showing the Pyro-GCMS analysis results of the cured product according to Comparative Example 1 of the present invention.

[0128] Figure 9 It is a diagram showing the Pyro-GCMS analysis results of the cured product according to Comparative Example 2 of the present invention.

[0129] Figure 10 It is a diagram showing the Pyro-GCMS analysis results of the cured product according to Comparative Example 3 of the present invention.

[0130] As Figures 2 to 10 As shown by the results, in the diagrams obtained through the Pyro-GCMS analysis of the cured products according to Embodiments 1 to 6, it can be confirmed that the cured products have peaks at 9.00 minutes to 11.00 minutes when extracted at 133 m / z and 203 m / z, respectively. In addition, in the diagrams obtained through the Pyro-GCMS analysis of the cured products according to Comparative Examples 1 to 3, it can be confirmed that the cured products do not have peaks at 9.00 minutes to 11.00 when extracted at 203 m / z.

[0131] Therefore, according to an exemplary embodiment of the present invention, it can be confirmed that when the cured product has peaks at 9.00 minutes to 11.00 minutes when extracted at 133 m / z and 203 m / z, respectively, in the diagram obtained through Pyro-GCMS analysis, the surface of the cured product exhibits excellent stain resistance.

Claims

1. A cured product, wherein, the cured product is a cured product of an acrylic resin composition, and in the graph obtained by Pyro-GCMS (pyrolysis-gas chromatography / mass spectrometry) analysis of the cured product, when extracted at 133 m / z (mass / charge) and 203 m / z (mass / charge) respectively, the cured product has a peak at 9.00 minutes to 11.00 minutes.

2. The cured product according to claim 1, wherein, The cured product has a surface glossiness value of 10 or less under 60° glossiness conditions.

3. The cured product according to claim 1, wherein, the surface of the cured product has a wrinkled surface, and the surface roughness (Rz) of the cured product is 3 μm to 10 μm.

4. The cured product according to claim 1, wherein, the acrylic resin composition comprises 1 to 60 parts by weight of an acrylic oligomer, 1 to 40 parts by weight of a siloxane oligomer, and 30 to 100 parts by weight of a monomer, and relative to 100 parts by weight of the acrylic oligomer, siloxane oligomer, and monomer, comprises 5 parts by weight or less of an initiator.

5. The cured product according to claim 4, wherein The weight average molecular weight (Mw) of the acrylic oligomer is 100 g / mol to 50,000 g / mol.

6. The cured product according to claim 4, wherein, The weight average molecular weight (Mw) of the siloxane oligomer is 1,000 g / mol to 50,000 g / mol.

7. The cured product according to claim 4, wherein, The monomer includes one or more selected from (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 2-hydroxyethyleneglycol (meth)acrylate, 2-hydroxypropyleneglycol (meth)acrylate, acrylic acid, methacrylic acid, 2-(meth)acryloyloxyacetic acid, 3-(meth)acryloyloxypropionic acid, 4-(meth)acryloyloxybutyric acid, 1,6-hexanediol diacrylate, acrylic acid dimer, itaconic acid, maleic acid, caprolactone-modified hydroxyacrylate (CHA), tetraethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate, and trimethylolpropane ethoxytriacrylate.

8. The cured product according to claim 4, wherein, The acrylic resin composition further comprises one or more fillers selected from silica, alumina, glass beads, and organic beads.

9. A decorative film, comprising: a base material layer; and the cured product according to any one of claims 1 to 8 provided on the base material layer.

10. A method for manufacturing a decorative film, the method comprising: preparing a base material layer; applying an acrylic resin composition on the base material layer; irradiating the applied composition with light L1 having a predetermined wavelength under inert gas conditions to form a first light irradiation with wrinkles on the surface of the applied composition; and irradiating the applied composition with light L2 having a wavelength longer than that of the light L1 under air conditions to form a second light irradiation of a cured product layer of the composition, Among them, in the graph obtained by Pyro-GCMS (pyrolysis-gas chromatography / mass spectrometry) analysis of the cured product layer, when extracted at 133 m / z (mass / charge) and 203 m / z (mass / charge), respectively, the cured product layer has peaks at 9.00 minutes to 11.00 minutes.

11. The method according to claim 10, wherein the acrylic resin composition contains 1 to 60 parts by weight of an acrylic oligomer, 1 to 40 parts by weight of a siloxane oligomer, and 30 to 100 parts by weight of a monomer, and contains 5 parts by weight or less of an initiator relative to 100 parts by weight of the acrylic oligomer, siloxane oligomer, and monomer.

12. The method according to claim 11, wherein, The weight-average molecular weight (Mw) of the acrylic oligomer is 100 g / mol to 50,000 g / mol.

13. The method according to claim 11, wherein The weight-average molecular weight (Mw) of the siloxane oligomer is 1,000 g / mol to 50,000 g / mol.

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