Decorative film and method of manufacturing same

Abstract

The present specification relates to a decorative film and a method of manufacturing same, the decorative film comprising: a substrate; and a cured layer on the substrate, wherein the surface of the cured layer includes a dense wrinkle pattern, and the cured layer has an Rz of 5 μm or less, an Ra of 1 μm or less, and an Rz / Ra of 5 to 20.

Description

Decofilm and its manufacturing method

[0001] This application claims the benefit of Korean Patent Application No. 10-2023-0190979, filed with the Korean Intellectual Property Office on December 26, 2023, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to a decorative film and a method for manufacturing the same.

[0003] When purchasing furniture, the most readily accessible element for consumers is surface properties. Surface texture, in particular, is the most fundamental property customers can directly feel and verify, making it a crucial factor in enhancing customer satisfaction with a product.

[0004] However, because surface texture has traditionally depended on the composition of the treatment agent, developing a surface with the desired texture required the development of new treatment agents. Additionally, newly developed treatments often have different properties than existing products, making them difficult to replace.

[0005] To address these challenges of tactile change, we propose a method to vary the surface feel while maintaining the original properties.

[0006] Matte (or low-gloss) decorative sheets are widely used in the production of architectural interior materials and furniture films. For example, a technology is being used to produce matte decorative sheets by applying a coating treatment containing a matting agent (e.g., silica) to a substrate and then curing it.

[0007] In relation to the implementation of the matte properties of the deco sheet, general matting agents are porous and have a low apparent specific gravity, so they may deteriorate the contamination resistance of the deco sheet by increasing the surface adsorption of foreign substances (e.g., fine dust, moisture, grease, etc.) when positioned on the coating surface.

[0008] Recently, in line with the trend toward high-end decorative sheets, the demand for decorative sheets with a soft touch surface in addition to a matte finish is also increasing.

[0009] It is required to develop a decorative sheet that can provide superior tactile feel and matte properties while having stain resistance equivalent to or higher than that of conventional products.

[0010] The present invention aims to provide a decorative film capable of implementing excellent tactile feel and matte properties, and a method for manufacturing the same.

[0011] [1] One embodiment of the present specification provides a decorative film including a substrate and a cured layer having a surface structure including wrinkles on the substrate, wherein the cured layer has an Rz of 5 µm or less, an Ra of 1 µm or less, and an Rz / Ra of 5 to 20.

[0012] [2] In another embodiment of the present specification, the cured layer has a surface gloss of 15 or less under a gloss condition of 60°, and the cured layer has a surface gloss of 20 or more under a gloss condition of 85°.

[0013] [3] In another embodiment of the present specification, the cured layer may include 5 to 100 wrinkles per unit area (0.1 mm × 0.1 mm) of the surface.

[0014] [4] Another embodiment of the present specification comprises a first light irradiation step of curing the surface of an acrylic resin composition coated on a substrate by irradiating light with a wavelength of 200 nm to 400 nm under air conditions;

[0015] A second light irradiation step of inducing wrinkles on the surface of the surface-cured composition by irradiating light with a wavelength of 200 nm or less under inert gas conditions, and

[0016] A third light irradiation step is included, wherein the composition is irradiated with light having a wavelength of 200 nm to 400 nm to photo-cure the composition and form a cured layer.

[0017] A method for manufacturing a decorative film is provided, wherein the Rz of the above-mentioned cured layer is 5 ㎛ or less, Ra is 1 ㎛ or less, and Ra / Rz is 5 to 20.

[0018] [5] In another embodiment of the present specification, the acrylic resin composition,

[0019] 20 to 50 parts by weight of monofunctional acrylic monomer, and

[0020] Contains 40 parts by weight or more and less than 70 parts by weight of a multifunctional acrylic oligomer.

[0021] [6] In another embodiment of the present specification, the acrylic resin composition further includes at least one of 5 to 30 parts by weight of a multifunctional acrylic monomer and 2 to 10 parts by weight of a silicon-based acrylic oligomer.

[0022] The decorative film of one embodiment of the present specification can realize a smooth feel while maintaining a matte characteristic.

[0023] Another embodiment of the decorative film of this specification can control the wetness among the surface textures while maintaining the main physical properties.

[0024] Figure 1 is a structural diagram showing an example of a photocuring device used in manufacturing a cured layer according to the present invention.

[0025] Figure 2 is a scanning electron microscope (SEM) image of the surface of a sample manufactured in Example 3.

[0026] Figure 3 is a scanning electron microscope (SEM) image of the surface of a sample manufactured in Comparative Example 3.

[0027] Figure 4 is a scanning electron microscope (SEM) image of the surface of a sample manufactured in Example 5.

[0028] Figure 5 is a scanning electron microscope (SEM) image of the surface of a sample manufactured in Comparative Example 5.

[0029] <Explanation of symbols>

[0030] 100: Light curing device

[0031] 110: Light irradiation room

[0032] 111: First light irradiator (UV irradiator)

[0033] 112: Second light irradiator (UV irradiator)

[0034] 113: Third light irradiator (UV irradiator)

[0035] 120: Investigated light

[0036] 130: Conveyor belt

[0037] 140: Gas barrier

[0038] Psalm 150

[0039] The specification is described in detail below.

[0040] The present invention can have various modifications and various embodiments, and specific embodiments are illustrated in the drawings and described in detail in the detailed description.

[0041] However, this is not intended to limit the present invention to a specific embodiment, but should be understood to include all modifications, equivalents, or substitutes included in the spirit and technical scope of the present invention.

[0042] In the present invention, it should be understood that terms such as “include” or “have” are intended to specify the presence of a feature, number, step, operation, component, part or combination thereof described in the specification, but do not exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts or combinations thereof.

[0043] In addition, it should be understood that the drawings attached to the present invention are illustrated in an enlarged or reduced form for convenience of explanation.

[0044] Hereinafter, the present invention will be described in detail with reference to the drawings, and components that are the same or corresponding to each other regardless of the drawing reference numerals will be given the same reference numerals, and redundant descriptions thereof will be omitted.

[0045]

[0046] In the present invention, "molecular weight" refers to the "weight average molecular weight" of the polymer, and the weight average molecular weight may be a value measured through gel permeation chromatography (GPC). In this case, the unit of molecular weight is g / mol, which may be omitted.

[0047] In the present invention, "surface roughness (surface profile)" indicates the degree of fine irregularities existing on the surface, and can be expressed as "Ra" and "Rz". Here, "Ra" is an arithmetic mean roughness, and "Rz" is a cross-sectional curve of the surface, and is a deviation expressed by measuring the distance between the fifth peak from the high side and the fifth valley from the deep side of the curved structure by taking a reference length L, and is also called "ten point average roughness".

[0048]

[0049] The present invention relates to a decorative film capable of implementing excellent tactile feel and matte properties and a method for manufacturing the same.

[0050] The decorative film of the present invention comprises a substrate and a coating layer on the substrate, wherein the Rz of the coating layer is 5 µm or less, Ra is 1 µm or less, and Rz / Ra is 5 to 20.

[0051] Rz is greater than 0㎛, 0.5㎛ or more, or 1㎛ or more, and 5㎛ or less, 4㎛ or less, or 3㎛ or less.

[0052] Ra is greater than 0㎛, greater than 0.1㎛, or greater than 0.2㎛, and less than or equal to 1㎛, less than or equal to 0.9㎛, less than or equal to 0.8㎛, less than or equal to 0.7㎛, less than or equal to 0.6㎛, less than or equal to 0.5㎛, or less than or equal to 0.4㎛.

[0053] Rz / Ra is 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, 12 or less, 11 or less, 10 or less, 9 or less, or 8 or less, and 5 or more, 6 or more, or 7 or more.

[0054] In the present invention, Rz and Ra are used to express the properties of wrinkles that affect the feel, and indicate that a matte surface has dense wrinkles that are not unpleasantly rough and have a moist feel. The surface that realized this feel while maintaining the matte surface had to reduce the Rz and Ra values ​​overall, and among them, the Ra value decreased more, expressing that the Rz / Ra value is larger than before.

[0055] As another example, the deco film according to the present invention can realize significantly low gloss even if it includes a very small amount of a matting agent in the cured layer, or in some cases, does not include a matting agent, by inducing scattering of light incident on the surface through a radial curved structure formed on the surface of the cured layer. Specifically, the deco film may have a surface gloss of 15 or less when measured in terms of 60° gloss (gloss 60° condition) using a gloss meter, and more specifically, the upper limit may be 14 or less, 13 or less, 12 or less, 11 or less, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4.5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2.3 or less, and the lower limit may be 0.1 or more, 0.5 or more, 1 or more, 1.1 or more, or 2 or more.

[0056] The above decorative film may have a surface gloss of 20 or more when measured at 85° gloss (85° gloss condition) using a gloss meter, and more specifically, the lower limit may be 21 or more, 22 or more, 23 or more, 24 or more, 25 or more, 26 or more, 27 or more, 28 or more, 29 or more, 30 or more, 31 or more, 32 or more, 33 or more, 34 or more, or 35 or more, and the upper limit may be 60 or less, 55 or less, or 50 or less.

[0057] It is common for both 60° and 85° gloss levels to be low. In these cases, the surface feels rough to the touch and often appears uneven to the naked eye.

[0058] On the other hand, when the 60° gloss is less than 15 and the 85° gloss is increased, the surface remains matte when viewed with the naked eye, but the touch becomes smoother compared to a surface with an 85° gloss of less than 20.

[0059]

[0060] The tecofilm of the present invention can improve matte gloss and excellent touch by introducing a fine wrinkle structure into the surface structure of the cured layer.

[0061] Here, the term "wrinkled surface" means that the resin layer includes wrinkles on at least one surface thereof, and that the resin layer has a three-dimensional surface irregularity due to the wrinkles. For example, the surface has irregularities including large and small ridges, valleys, and wrinkles formed therefrom and recognizable as having a predetermined shape. Each of the ridges, valleys, and wrinkles may have a regular or irregular shape. Such a wrinkled surface may also be referred to as a surface having a micro-folding structure.

[0062] When observing the surface of the resin layer where wrinkles are formed in the normal direction of the resin layer, ridges, valleys, wrinkles, and unevenness formed from them are observed over the entire area of ​​the surface, for example, during the curing process described below.

[0063] The above wrinkles can be observed in a form including a line shape (e.g., a straight line, a curved line) having directionality. As an example, the wrinkles formed on the surface by repeating straight and curved shapes can impart a curvature like a mountain range shape to the surface of the resin layer. The surface irregularity structure formed by the wrinkles having a line shape as described above is clearly distinguished from the so-called point-wise irregularity shape formed by a method using particles in a composition for forming the resin layer or a method using an emulsion dispersion.

[0064] In addition, the cured layer may include wrinkles that can be recognized with a predetermined size and shape. For example, the wrinkles may have a width on the order of nm (less than about 1 ㎛) and a linear (straight or curved) shape that extends for several micrometers (㎛) or more. The width and / or height of the wrinkles and the length along which the wrinkles extend can be confirmed from an image (e.g., SEM) of the surface on which the wrinkles are formed, as shown in the attached drawings. In addition, the length in the extension direction may be greater than the width. Specifically, the ends of the wrinkles extending in a straight or curved shape may be incorporated into the resin layer with a slope that gradually decreases in height. In some cases, the ends of one wrinkle having the above size and shape may be the starting point of another wrinkle or a connection point with another wrinkle. In addition, when observing a cross-sectional curve near the wrinkles in a direction perpendicular to the extension direction of the wrinkles, the width of the wrinkles may be incorporated into the resin layer with a slope that gradually decreases in height in both directions starting from a point or portion (e.g., a ridge) that forms the height of the wrinkle. Meanwhile, when a ridge and its adjacent valley form a wrinkle or a portion thereof, the area of ​​the shape recognized, including the valley, can be considered the width of the wrinkle.

[0065] As an example, the width of the wrinkles may be 9 μm or less. Specifically, the width of the wrinkles may have an upper limit of 8 μm or less, 7 μm or less, 6 μm or less, 5 μm or less, 4 μm or less, or 3 μm or less, and a lower limit of 150 nm or more, 200 nm or more, 250 nm or more, or 300 nm or more. When the above ranges are satisfied, it may be advantageous to exhibit matte characteristics and excellent touch by the wrinkles.

[0066] In addition, the length of the wrinkles may have an upper limit of 100 ㎛ or less, 90 ㎛ or less, 80 ㎛ or less, 70 ㎛ or less, 60 ㎛ or less, 50 ㎛ or less, 40 ㎛ or less, or 30 ㎛ or less, and a lower limit of 1 ㎛ or more, 2 ㎛ or more, 3 ㎛ or more, 4 ㎛ or more, or 5 ㎛ or more. When the above range is satisfied, it may be advantageous to exhibit matte characteristics and excellent touch by the wrinkles.

[0067] The wrinkles may have a predetermined height for most of their extending length. For example, the wrinkles may have a height of 5 μm or less, 4 μm or less, 3 μm or less, 2 μm or less, 1.5 μm or less, 1.0 μm or less, or 0.1 to 0.9 μm, which may be equated to the "surface roughness" of the cured layer. Specifically, when the cross-sectional curve of the wrinkles is observed in a direction perpendicular to the extending direction of the wrinkles, a point or portion (e.g., a ridge) forming the height of the wrinkle and a point or portion (e.g., a valley) of the resin layer where the width of the wrinkles is mixed may have a "height difference" or "surface roughness" of 2 μm or less. The present invention can prevent contamination from remaining between the wrinkles due to thick wrinkles, thereby reducing contamination resistance, by controlling the height or surface roughness of the wrinkles within the above range.

[0068] Meanwhile, the above "most of the length over which the height is observed" means a length that is 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, or 95% or more of the length over which the wrinkles continuously extend along their shape. When the height difference in the direction of extension of the wrinkles gradually decreases and the height is significantly lowered, a shape in which the end of the wrinkle is mixed into the resin layer may be observed, or a shape in which a contact point with another wrinkle having a different size or shape from the wrinkle may be observed. In the latter case, a more complex wrinkle structure may form unevenness on the surface.

[0069] The wrinkles may be observed over the entire area of ​​the surface, and may form surface wrinkles or unevenness while showing a regular or irregular distribution. For example, the wrinkles on the surface may form surface unevenness by having a shape in which multiple wrinkles branch in different directions from one specific point. Specifically, the wrinkles on the surface may have a shape similar to "Y" or "〈". In this case, wrinkles having a shape similar to "Y" or "〈" may be densely arranged to form surface unevenness.

[0070] The present invention can increase the frequency of finer wrinkles by forming wrinkles having the above-described shape and / or size in a cured layer, thereby reducing gloss even without using a matting agent or using a small amount of matting agent in the cured layer, preventing contaminants from remaining between the wrinkles and contaminating the surface, and improving wax affinity of the surface.

[0071] As an example, the above-described tecofilm may contain 5 to 200 wrinkles per unit area (0.1 mm × 0.1 mm) of the cured layer surface (equivalent to 500 to 20,000 wrinkles per 1 mm × 1 mm). Specifically, the surface of the cured layer of the above-mentioned tectofilm may have 5 to 180, 5 to 150, 5 to 120, 5 to 100, 5 to 80, 5 to 70, 5 to 60, 5 to 50, 7 to 200, 10 to 200, 12 to 200, 15 to 200, 18 to 200, 8 to 100, 10 to 80, 12 to 70, or 14 to 60 wrinkles per unit area (0.1 mm X 0.1 mm).

[0072]

[0073] In a specific example of the present application, a cured layer having the above-described characteristics can be obtained through a curing treatment of a composition having a predetermined composition. Specifically, the cured layer can include a cured product of a curable composition.

[0074] In one example, the treatment agent used in the present application, i.e., the coating composition, may be a photocurable solvent-free composition. That is, the composition may not contain a solvent, such as an organic solvent or an aqueous solvent. When a solvent-free composition is used, the drying process for the solvent may be omitted, thereby increasing process efficiency. In addition, the use of a solvent-free composition can prevent deterioration of the surface properties required for the film of the present application due to bubbles, etc. generated when the solvent volatilizes during the solvent drying process. Specifically, the composition may be a UV-curable solvent-free composition and may include a reactive component (photocurable component) having a curable reactive group.

[0075] In one example, the cured layer may include a cured product of a composition comprising an oligomer component (A) and a monomer component (B). That is, after the photocuring treatment described below is performed on a resin composition having a predetermined configuration, a cured layer having a surface formed with wrinkles as described above can be produced.

[0076] The above oligomer component (A) may include a multifunctional acrylic oligomer, and the monomer component (B) may include a monofunctional acrylic monomer. At this time, the number of functional groups refers to the number of substituents that can participate in the initiation reaction, and monofunctional groups have one functional group, and polyfunctional groups may be difunctional, trifunctional, tetrafunctional, pentafunctional, or six or more functional groups.

[0077] The above acrylic resin composition may include 20 to 50 parts by weight of a monofunctional acrylic monomer and 40 to 70 parts by weight of a polyfunctional acrylic oligomer.

[0078] The above oligomer component (A) may further include a silicon-based acrylic oligomer. When the silicon-based acrylic oligomer is included, it may be included in an amount of 5 to 30 parts by weight, or 2 parts by weight or more and 10 parts by weight or less.

[0079] The above monomer component (B) may further include a multifunctional acrylic monomer. When the above multifunctional acrylic monomer is included, it may be included in an amount of 5 to 30 parts by weight or 10 to 30 parts by weight.

[0080] The above composition may further include an initiator (C). The type of initiator is not particularly limited, as long as it is an initiator that can be used in the curing process described below, and known commercially available products may also be used.

[0081] The content of the initiator is not particularly limited. For example, the composition may contain 10 parts by weight or less of the initiator relative to 100 parts by weight of the combined oligomer component (A) and monomer component (B). Specifically, the content of the initiator may be 5 parts by weight or less, 4 parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, or 1 part by weight or less. And, the lower limit of the content may be, for example, 0.1 parts by weight or more or 0.5 parts by weight or more. As described below, in the present application, since stepwise curing is performed when curing the cured layer, the curing efficiency is excellent even when a small amount of the initiator is used.

[0082] The above composition may further include a light stabilizer (D). As long as the light stabilizer can be used in the curing process described below, the type thereof is not particularly limited, and known commercially available products may also be used.

[0083] The content of the light stabilizer is not particularly limited. For example, the composition may contain 10 parts by weight or less of the light stabilizer relative to 100 parts by weight of the combined oligomer component (A) and monomer component (B). Specifically, the content of the light stabilizer may be 5 parts by weight or less, 4 parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, or 1 part by weight or less. In addition, the lower limit of the content may be, for example, 0.1 parts by weight or 0.5 parts by weight. The light stabilizer can prevent damage to the laminated film due to ultraviolet rays.

[0084] The above acrylic resin composition may further include a silicon-based additive or a matting agent. When the sum of the oligomer component (A) and the monomer component (B) is 100 parts by weight, the content of the silicon-based additive may be 0 phr or more and 5 phr or less. Since the weight ratio is expressed as parts by weight in general, phr can be replaced with parts by weight.

[0085] The above acrylic resin composition can be used without or with a small amount of a matting agent component.

[0086] Specifically, the matting agent has a particle shape and can impart a matte effect to the film by increasing the light scattering rate at the film surface. However, the use of the matting agent brings about the problem of increased stain resistance, as previously described. However, since the cured layer of the present application has the surface properties described above, it can effectively implement the matte properties. Therefore, the film of the present application can implement sufficient matte properties without using the matting agent used to implement the matte effect in the prior art.

[0087] In addition, even if a matting agent is used, the amount of matting agent used to achieve matte properties in the prior art may not be used. That is, according to the present application, the amount of matting agent used can be significantly reduced. For example, the composition may contain a matting agent component in an amount of 5 parts by weight or less, specifically 4 parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, or 1 part by weight, relative to 100 parts by weight of the combined oligomer component (A) and monomer component (B). Accordingly, the film of the present application has the advantage of being able to prevent problems such as reduced contamination resistance due to the use of a matting agent.

[0088] The thickness of the hardened layer is not particularly limited as long as the surface characteristics described above are satisfied. For example, the thickness of the hardened layer may be 3 ㎛ or more, 5 ㎛ or more, 10 ㎛ or more, or 15 ㎛ or more, provided that the surface characteristics described above are satisfied. In addition, for example, the thickness of the hardened layer may be 100 ㎛ or less, 90 ㎛ or less, 80 ㎛ or less, 70 ㎛ or less, 60 ㎛ or less, 50 ㎛ or less, 40 ㎛ or less, 30 ㎛ or less, 20 ㎛ or less, or 15 ㎛ or less.

[0089] The type of substrate layer to which the composition described above is directly applied is not particularly limited. For example, the substrate layer may include polyvinyl chloride (PVC) or polyethylene terephthalate (PET). Although not particularly limited, considering suppression of whitening, mechanical properties such as impact resistance, ease of processing, and chemical resistance, it may be preferable to use glycol-modified polyethylene terephthalate (PETG) among polyethylene terephthalate (PET).

[0090] The thickness of the substrate layer is also not particularly limited. For example, the thickness of the substrate layer may be 50 ㎛ or more, 100 ㎛ or more, 150 ㎛ or more, 200 ㎛ or more, 250 ㎛ or more, 300 ㎛ or more, 350 ㎛ or more, 400 ㎛ or more, 450 ㎛ or more, or 500 ㎛ or more. And, for example, the thickness of the substrate layer may be 3,000 ㎛ or less, 2,000 ㎛ or less, 1,000 ㎛ or less, 900 ㎛ or less, 800 ㎛ or less, 700 ㎛ or less, 600 ㎛ or less, 500 ㎛ or less, 400 ㎛ or less, or 300 ㎛ or less.

[0091] In addition, the method of applying the composition on the substrate can be performed by a method known in the art, and can be performed using, for example, Mayer, D-bar, rubber roll, G / V roll, air knife, slot die, microgravure, etc.

[0092] The three-step curing method for curing the above-mentioned curing layer is:

[0093] A first light irradiation step of curing the surface of an acrylic resin composition coated on a substrate by irradiating light with a wavelength of 200 nm to 400 nm under air conditions;

[0094] A second light irradiation step of inducing wrinkles on the surface of the surface-cured composition by irradiating light with a wavelength of 200 nm or less under inert gas conditions, and

[0095] A third light irradiation step may be included in which the composition having wrinkles induced on the surface is irradiated with light having a wavelength of 200 nm to 400 nm to photocure the composition and form a cured layer.

[0096] The method for manufacturing a decorative film according to the present invention has a step of curing an acrylic resin composition by irradiating it with short wavelength light of a specific range under different conditions in three stages. Here, the short wavelength is an expression that is distinct from the long wavelength, and means a wavelength with strong energy and a short wavelength length, and refers to UV, X-ray, etc., which have a wavelength shorter than blue light among visible light, and refers to light with a wavelength of 400 nm or less, and further, 100 nm to 450 nm. This is a different expression from the narrow wavelength and broad wavelength, which are expressions that are distinguished by the range of the emission spectrum emitted by a light source to be described later.

[0097] Specifically, the first light irradiation step is the first step of irradiating light to an acrylic resin composition applied to a substrate, applying ultraviolet (UV) energy to harden the surface of the acrylic resin composition. At this time, the surface hardening provides a level of fixing strength that prevents the applied composition from flowing away without hardening the entire application, which would allow wrinkles to form in a step described below.

[0098] In the present specification, the first light irradiation step may be performed in an oxygen atmosphere, an air atmosphere, or a nitrogen atmosphere. Here, the air atmosphere refers to a natural air state without artificial treatment, such as an air atmosphere with an oxygen concentration of approximately 21%, the oxygen atmosphere refers to an artificial air state with a higher oxygen concentration than the air atmosphere, and the nitrogen atmosphere refers to an artificial air state with a higher nitrogen concentration than the air atmosphere with a nitrogen concentration of 78%.

[0099] To this end, the first light irradiation step may be performed in an air atmosphere using light having a wavelength of 200 nm to 400 nm with high energy. Specifically, it may be performed by irradiating light having a wavelength of 250 to 380 nm, 280 to 380 nm, 250 to 350 nm, or 280 to 320 nm under air conditions. At this time, the surface temperature of the cured composition and / or the cured layer may be 20 to 90°C, specifically 20 to 80°C or 30 to 70°C.

[0100] The light source used in the first light irradiation step is selected to emit light with a broad wavelength, emitting all or part of the light within the range of 100 to 450 nm. Using a light source with such a broad wavelength facilitates surface curing control. For example, a metal halide lamp with a broad emission spectrum within the range of 100 to 450 nm can be used.

[0101] On the other hand, when the first light irradiation step is performed using a light source with a narrow wavelength in the long wavelength (365 nm to 405 nm) range of UV, such as an LED, the shape of the wrinkles may be sharp, so that contaminants are better fixed to the surface treatment layer, which may reduce contamination resistance.

[0102] In addition, in the first light irradiation step, the distance between the acrylic resin composition and the light source may be 5 to 150 mm, and specifically, 5 to 140 mm, 5 to 130 mm, 5 to 120 mm, 5 to 110 mm, 5 to 100 mm, 5 to 80 mm, 5 to 60 mm, 5 to 40 mm, 10 to 70 mm, 10 to 50 mm, 10 to 30 mm, 20 to 80 mm, 20 to 60 mm, 20 to 50 mm, 20 to 30 mm, 25 to 75 mm, 50 to 80 mm, 40 to 60 mm, or 45 to 55 mm. If the distance between the surface treatment layer and the light source is satisfied, the surface may be properly cured without over-curing, thereby reducing the gloss of the surface, and if it is not satisfied, the surface may be over-cured, thereby increasing the gloss.

[0103] In addition, in the first light irradiation step, the light irradiation amount may be 25 mJ / cm2 to 150 mJ / cm2, specifically 25 mJ / cm2 to 120 mJ / cm2, 25 mJ / cm2 to 100 mJ / cm2, 25 mJ / cm2 to 90 mJ / cm2, 25 mJ / cm2 to 75 mJ / cm2, 25 mJ / cm2 to 70 mJ / cm2¸ 25 mJ / cm2 to 50 mJ / cm2, 50 mJ / cm2 to 75 mJ / cm2, 40 mJ / cm2 to 60 mJ / cm2, 25 mJ / cm2 to 45 mJ / cm2, 35 mJ / cm2 to 45 mJ / cm2 or 38 It can be from 43 mJ / cm2 to 43 mJ / cm2.

[0104] When using the same light source, the farther the distance of the light source from the composition and / or surface treatment layer, the less light there is, and the closer the distance of the light source from the composition and / or surface treatment layer, the more light there is. Therefore, in order to control the amount of light irradiated to the composition and / or surface treatment layer, it is necessary to consider not only the light amount of the light source itself, but also the change in light amount depending on the distance.

[0105] In addition, the second light irradiation step is a step of increasing the scattering rate of light incident on the surface by shrinking the surface of the acrylic resin composition and / or its cured product to which the excimer generated by the irradiated light is applied, thereby forming wrinkles. The present invention can increase the scattering rate of light by shrinking the surface of the acrylic resin composition and / or its cured product into the above-described radial curved structure using the excimer, thereby reducing the glossiness of the cured layer even without using a very small amount of a matting agent or, in some cases, without using one. The method can be performed by irradiating light having a wavelength of 200 nm or less, specifically 190 nm or less, 180 nm or less, 170 nm or less, 160 nm or less, 150 nm or less, 140 nm or less, 130 nm or less, 120 nm or less, 110 nm or less, or 100 nm or less, and a wavelength of 130 nm or more, 140 nm or more, 150 nm or more, 160 nm or more, or 170 nm or more in an inert atmosphere. The gas used to create the inert atmosphere can be, for example, He, Ne, Ar, and / or N2.

[0106] The inert atmosphere in which the second light irradiation step is performed may be an atmosphere having an oxygen (O2) concentration of about 4,000 ppm or less. Specifically, the upper limit of the oxygen concentration in the inert atmosphere may be 3,000 ppm or less, 2,500 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. And the lower limit 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.

[0107] In one example, the inert atmosphere can be formed such that the concentration of oxygen in nitrogen gas (N2) satisfies the above range.

[0108] When the second light irradiation is performed under the inert atmosphere conditions described above, it is advantageous for securing the wrinkles and surface characteristics described above. For example, when the second light irradiation is performed in an inert atmosphere with an oxygen concentration exceeding the above range, it is difficult to form the wrinkles described above, and the surface characteristics described above cannot be provided. For example, wrinkles may not be formed evenly across the entire surface area to satisfy the characteristics described above, but may be observed rarely on the surface.

[0109] In one example, when performing the second light irradiation step, the distance between the composition and the light source, i.e., the distance from the surface of the composition applied on the substrate layer to the light source, may be 5 mm or more. Specifically, the lower limit of the distance may be, for example, 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 may be, for example, 150 mm or less, 130 mm or less, 110 mm or less, 100 mm or less, 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 second light irradiation step, when the distance between the composition and the light source is adjusted to the above range, an appropriate amount of light can reach the composition with an appropriate intensity, and as a result, a surface having wrinkles of the shape and size described above is formed, and it is advantageous to secure surface properties (e.g., surface roughness, gloss) of the above-described degree.

[0110] In one example, the amount of light irradiated in the second light irradiation step may be 1 mJ / cm2 or more or 5 mJ / cm2 or more. Specifically, the lower limit of the light irradiation amount in the second light irradiation step may be, for example, 10 mJ / cm2 or more, 15 mJ / cm2 or more, 20 mJ / cm2 or more, 25 mJ / cm2 or more, or 30 mJ / cm2 or more, and the upper limit may be, for example, 150 mJ / cm2 or less, 120 mJ / cm2 or less, 110 mJ / cm2 or less, 100 mJ / cm2 or less, 90 mJ / cm2 or less, 80 mJ / cm2 or less, 70 mJ / cm2 or less, 60 mJ / cm2 or less, 50 mJ / cm2 or less, 40 mJ / cm2 or less, 30 mJ / cm2 or less, or 25 mJ / cm2 or less. In the second light irradiation step, when the light irradiation amount is adjusted to the above range, it is advantageous to form a surface with the wrinkles described above and to secure surface properties (e.g., surface roughness, gloss) of the above-described degree.

[0111] In the present specification, the third light irradiation step may be performed in an oxygen atmosphere, an air atmosphere, or a nitrogen atmosphere. In this case, the air atmosphere refers to a natural air state without artificial treatment, such as an atmospheric air atmosphere with an oxygen concentration of approximately 21%, the oxygen atmosphere refers to an artificial air state with a higher oxygen concentration than the air atmosphere, and the nitrogen atmosphere refers to an artificial air state with a higher nitrogen concentration than the air atmosphere with a nitrogen concentration of 78%. When the third light irradiation step is performed in a nitrogen atmosphere, it may be performed in a nitrogen (N2) atmosphere containing a small amount of oxygen (O2).

[0112] In addition, the third light irradiation step is a step of performing true curing by additionally irradiating ultraviolet (UV) rays to the composition and / or cured layer in which wrinkles are formed, and can be performed in an air atmosphere using light having a wavelength of 400 nm or less, specifically, a wavelength of 100 to 400 nm, 200 to 400 nm, 200 to 300 nm, 300 to 400 nm, 150 to 300 nm, 200 to 250 nm, or 270 to 320 nm.

[0113] In addition, in the third light irradiation step, the light irradiation amount may be 25 mJ / cm2 to 400 mJ / cm2, specifically 25 mJ / cm2 to 3500 mJ / cm2, 25 mJ / cm2 to 300 mJ / cm2, 25 mJ / cm2 to 250 mJ / cm2, 25 mJ / cm2 to 200 mJ / cm2, 25 mJ / cm2 to 150 mJ / cm2, 25 mJ / cm2 to 120 mJ / cm2, 25 mJ / cm2 to 100 mJ / cm2, 25 mJ / cm2 to 90 mJ / cm2, 25 mJ / cm2 to 75 mJ / cm2, 25 mJ / cm2 to 70 mJ / cm2¸ 25 mJ / cm2 to 50 mJ / cm2, 50 mJ / cm2 to 75 mJ / cm2, 40 mJ / cm2 to 60 mJ / cm2, 25 mJ / cm2 to 45 mJ / cm2, 35 mJ / cm2 to 45 mJ / cm2 or 38 mJ / cm2 to 43 mJ / cm2.

[0114] As an example, the third light irradiation step may be performed by irradiating the composition and / or the cured layer with light having a broad wavelength of 200 to 400 nm at a light dose of 60 to 90 mJ / ㎠. At this time, the distance between the composition and / or the cured layer and the light source may be 50±10 mm or 100±10 mm.

[0115] The light irradiated in the present invention can be irradiated according to a known method capable of irradiating light of a required wavelength at each stage. For example, light having a wide wavelength range in the UV region of 400 nm or less can be irradiated using a mercury, gallium, or metal halide lamp, etc. In this case, mercury is a light source with a maximum emission wavelength (λmax) of the late 200 nm, gallium is a light source with a maximum emission wavelength (λmax) of 350 nm to 450 nm, and metal halide is a light source with a maximum emission wavelength (λmax) of 300 nm to 399 nm.

[0116] In addition, in the present invention, the time for which light is irradiated can be a very short time of 1 to 2 seconds, and this light irradiation time can be controlled by the speed at which the composition moves during the light irradiation, for example, the moving speed of the composition coated on the substrate. For example, the moving speed of the composition and / or the substrate coated with the composition can be 1 to 50 m / min, and specifically, 5 to 40 m / min, 10 to 40 m / min, 20 to 40 m / min, 30 to 40 m / min, 15 to 25 m / min, 5 to 15 m / min, 15 to 20 m / min, 35 to 40 m / min, or 18 to 22 m / min.

[0117] The present invention can exhibit a high curing rate even if an initiator is included in a small amount within the above range by using short wavelength light of a specific range in stages under different conditions during curing of the composition.

[0118]

[0119] Meanwhile, the acrylic resin composition formed in the above-described curing layer may include a monofunctional acrylic monomer and a polyfunctional acrylic oligomer. Here, the monofunctional acrylic monomer can lower the viscosity of the composition, thereby improving the processability of the composition, such as movement, handling, and application (coating). The acrylic resin composition formed in the above-described curing layer must maintain a viscosity suitable for the process, and preferably, the viscosity of the acrylic resin composition may be 100 cP to 1000 cP, 100 cP to 950 cP, 100 cP to 900 cP, 100 cP to 850 cP, or 150 cP to 850 cP at room temperature. At this time, the room temperature is the natural temperature without heating or cooling, and is, for example, 20±5°C.

[0120]

[0121] Additionally, the acrylic resin composition may further include at least one of a multifunctional acrylic monomer, a silicon-based acrylic oligomer, a matting agent, and a flexible treatment agent.

[0122]

[0123] In another example of the present application, the present application relates to a decorative film or decorative sheet comprising the laminated film. The decorative film can be used for decorative materials, furniture, etc. The furniture or decorative materials may have curves, edges, and / or flat surfaces.

[0124] Furniture may include doors, desks, chairs, or shelves, and decorative materials may refer to items that can be used as part of the furniture or on their own.

[0125] In another example of the present application, the present application relates to a coating agent, i.e., a composition, capable of providing a cured layer of the laminated film described above. The specific composition of the composition is as described above.

[0126] Hereinafter, the present specification will be described in more detail through examples. However, the following examples are intended only to illustrate the present specification and are not intended to limit the present specification.

[0127] Manufacturing example

[0128] A solvent-free type acrylic resin composition was prepared by mixing a monofunctional acrylic monomer, a polyfunctional acrylic monomer, a polyfunctional acrylic oligomer (Mw: 7,000±10), an oligomer having a silicon-containing functional group (Mw: 3,000±10), and a silicon-based additive together with an initiator as shown in Tables 1 and 2 below. At this time, the contents in Tables 1 and 2 are parts by weight.

[0129] Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 5 Monofunctional acrylic monomer 2050323232 Multifunctional acrylic monomer 25-181823 Acrylic oligomer having silicon-containing functional group 5----Multifunctional acrylic oligomer 5550505045 Silicon-based additive--544 Initiator 55555

[0130] Manufacturing Example 6 Manufacturing Example 7 Manufacturing Example 8 Manufacturing Example 9 Monofunctional acrylic monomer 10602040 Multifunctional acrylic monomer 401030 Acrylic oligomer having silicon-containing functional group----Multifunctional acrylic oligomer 50407030 Silicon-based additive 5555 Irgacure 7545555

[0131] Example

[0132] Each of the acrylic resin compositions prepared in Table 4 below was applied on a polyvinyl chloride (PVC) substrate (average thickness: 0.20 to 0.45T) measuring 10 cm × 10 cm in length, and fixed in a light curing device having a structure as shown in Fig. 1. Then, as shown in Table 3 below, the substrate was moved at a moving speed of 20±1 m / min while performing stepwise light irradiation to prepare a decorative film specimen. At this time, the average thickness of the cured layer was 8 to 15 μm. In Table 3 below, the light source used for the first light irradiation was a Mercury lamp that emits light with a wide wavelength (broad wave) with an emission spectrum of 200 to 400 nm, and 60 to 90 mJ / cm 2 was investigated by the amount of light.

[0133] The light source used in the third light irradiation was a Mercury lamp that emits light with a broad wavelength of 200 to 400 nm with an emission spectrum of 300 mJ / cm. 2 was investigated by the amount of light.

[0134] Curing conditions 1 Curing conditions 2 3 step 2 step 1st light irradiation wavelength range 200~400 nm 200 nm or less Gas condition Air condition Inert gas Distance from light source 50±1mm 100±1mm 2nd light irradiation wavelength range 172±5 nm 200~400 nm Gas condition Oxygen concentration 400 ppm or less Nitrogen atmosphere - Distance from light source 100±1mm 100±1mm 3rd light irradiation wavelength range 200~400 nm - Gas condition Air condition - Distance from light source 100±1mm

[0135] Comparative example

[0136] A decorative film specimen was manufactured in the same manner as in the examples, except that the composition was cured using the acrylic composition and curing conditions shown in Tables 5 to 7 below. At this time, the average thickness of the cured layer was 8 to 15 μm.

[0137] [Experimental Example 1]

[0138] To evaluate the properties of the decorative film according to the present invention, the surface roughness, gloss, and feel of the specimens manufactured in Examples 1 to 5 and Comparative Examples 1 to 5 were measured. The specific measurement methods are as follows, and the measured results are shown in Tables 4 to 7 below:

[0139] a) Surface roughness evaluation

[0140] The arithmetic mean roughness Ra and ten-point mean roughness Rz were measured according to ISO 4287 using a surface roughness meter (Model: 178-560-02K Model, Manufacturer: Mistutoyo).

[0141] b) Gloss evaluation

[0142] The 60° gloss (gloss 60° condition) and 85° gloss (gloss 85° condition) of the specimens of the examples and comparative examples were measured using a gloss meter.

[0143] Example 1 Example 2 Example 3 Example 4 Example 5 Acrylic composition type Manufacturing example 1 Manufacturing example 2 Manufacturing example 3 Manufacturing example 4 Manufacturing example 5 Curing condition Curing condition 1 Curing condition 1 Curing condition 1 Curing condition 1 Curing condition 1 Curing condition 1 Gloss 60° 5.2 4.0 3.2 8.9 8.5 Gloss 85° 46.2 37.3 35.4 48.1 48.6 Rz (㎛) 2.8 1.8 2.0 2.6 2.7 Ra (㎛) 0.3 9 0.2 3 0.2 9 0.3 5 0.3 8 Rz / Ra 7.1 8 7.8 3 6.9 0 7.4 3 7.1 1

[0144] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Acrylic composition type Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 5 Curing conditions Curing conditions 2 Curing conditions 2 Curing conditions 2 Curing conditions 2 Curing conditions 2 Gloss 60° 5.2 4.7 2.9 9.9 9.7 Gloss 85° 7.9 7.1 3.3 14.8 13.1 Rz (㎛) 11.7 13.5 10.3 10.4 11.5 Ra (㎛) 1.6 2 2.0 0 1.5 4 1.4 3 1.6 4 Rz / Ra 7.2 2 6.7 5 6.6 9 7.2 7 7.0 1

[0145] Comparative Example 6Comparative Example 7Comparative Example 8Comparative Example 9Acrylic composition typeManufacturing Example 6Manufacturing Example 7Manufacturing Example 8Manufacturing Example 9Curing conditionCuring condition 2Curing condition 2Curing condition 2Gloss 60°8.5Uncured9.47.1Gloss 85°15.518.210.2Rz(㎛)17.522.915.5Ra(㎛)4.25.63.8Rz / Ra4.174.094.08

[0146] Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Acrylic composition type Manufacturing Example 6 Manufacturing Example 7 Manufacturing Example 8 Manufacturing Example 9 Curing condition Curing condition 1 Curing condition 1 Curing condition 1 Curing condition 1 Gloss 60° 5.5 Uncured 5.8 5.7 Gloss 85° 20.2 20.0 18.7 Rz (㎛) 4.3 4.5 3.9 Ra (㎛) 1.5 1.8 1.1 Rz / Ra 2.8 7 2.5 0 3.5 5

[0147] In terms of gloss, Comparative Examples 1 to 9 have a gloss of 60° of 15 or less and a gloss of 85° of less than 20, so that they are matte or have a rough surface feel and a rough appearance to the naked eye. However, in the Examples, the gloss of 60° is 15 or less, so that they are matte, but the gloss of 85° is 20 or more, so that it can be confirmed that the surface is smooth.

[0148] In terms of surface roughness, it was confirmed that the examples showed a tendency for the Rz / Ra value to increase compared to the existing conditions because both the Rz value and the Ra value decreased more than the comparative examples.

[0149] [Experimental Example 2]

[0150] In order to confirm the surface structure of the cured layer, which is the outermost layer of the decorative film according to the present invention, a scanning electron microscope (SEM) analysis was performed at 200x magnification on the decorative film specimens manufactured in Examples 3 and 5 and Comparative Examples 3 and 5, and the results are shown in Figs. 2 to 5. At this time, the squares indicated in Figs. 2 to 5 indicate the unit area (0.1 × 0.1 mm) for counting the number of wrinkles.

[0151] As shown in Fig. 2, the wrinkle structure of Example 3 had an average width of 3 to 8 μm and a length of about 5 to 30 μm. In addition, the wrinkles were formed very uniformly, with 10 to 30 wrinkles formed per unit area (0.1 × 0.1 mm).

[0152] As shown in Fig. 3, the wrinkle structure of Comparative Example 3 had an average width of 7 to 12 μm and a length of about 20 to 100 μm. In addition, the wrinkles were formed uniformly, with 5 to 10 wrinkles formed per unit area (0.1 × 0.1 mm).

[0153] As shown in Fig. 4, the wrinkle structure of Example 5 had an average width of 1 to 5 μm and a length of about 3 to 20 μm. In addition, the wrinkles were formed very uniformly, with 20 to 50 wrinkles formed per unit area (0.1 × 0.1 mm).

[0154] As shown in Fig. 5, the wrinkle structure of Comparative Example 5 had an average width of 5 to 10 μm and a length of about 20 to 100 μm. In addition, the wrinkles were formed uniformly, with 5 to 20 wrinkles formed per unit area (0.1 × 0.1 mm).

Claims

1. A substrate, and a cured layer having a surface structure including wrinkles on the substrate, A decorative film wherein the Rz of the above-mentioned hardened layer is 5㎛ or less, Ra is 1㎛ or less, and Rz / Ra is 5 to 20.

2. A decorative film according to claim 1, wherein the cured layer has a surface gloss of 15 or less under a gloss condition of 60°, and the cured layer has a surface gloss of 20 or more under a gloss condition of 85°.

3. A decorative film according to claim 1, wherein the cured layer includes 5 to 100 wrinkles per unit area (0.1 mm × 0.1 mm) of the surface.

4. A first light irradiation step of curing the surface of the acrylic resin composition coated on the substrate by irradiating light with a wavelength of 200 nm to 400 nm under air conditions; A second light irradiation step of inducing wrinkles on the surface of the surface-cured composition by irradiating light with a wavelength of 200 nm or less under inert gas conditions, and A third light irradiation step is included in which the composition having wrinkles induced on the surface is irradiated with light having a wavelength of 200 nm to 400 nm to photo-cure the composition and form a cured layer. A method for manufacturing a decorative film, wherein the Rz of the above-mentioned hardened layer is 5 ㎛ or less, Ra is 1 ㎛ or less, and Ra / Rz is 5 to 20.

5. In claim 4, the acrylic resin composition, 20 to 50 parts by weight of a monofunctional acrylic monomer, and A method for manufacturing a decorative film comprising 40 parts by weight or more and less than 70 parts by weight of a multifunctional acrylic oligomer.

6. In claim 5, the acrylic resin composition, 5 to 30 parts by weight of a multifunctional acrylic monomer, and A method for manufacturing a decorative film, further comprising at least one of 2 parts by weight or more and 10 parts by weight or less of a silicon-based acrylic oligomer.

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