KR20210039644A - laminated film having wrinkle surface - Google Patents

Abstract

The present application relates to a laminated film usable for furniture or decorative materials. The laminated film is excellent in both matte properties and stain resistance known as a trade-off relationship in the prior art.

Description

Laminated film having wrinkle surface

The present application relates to a film having a corrugated surface. Specifically, the present application relates to a laminated film in which the trade-off relationship between the matte property secured by the surface wrinkles and the stain resistance is improved.

Deco sheets having matte properties (or low light properties) are widely used when manufacturing interior materials for buildings or films for furniture. Specifically, the matte property of the decor sheet may be achieved in a manner that causes diffuse reflection by forming irregularities on the surface.In the prior art, for example, a coating treatment agent including a matting agent (eg, silica) is applied on the substrate. It is common to use a technique of manufacturing a matte decor sheet through a treatment of a method of curing after the process.

However, when the surface irregularities are formed in order to realize the matte characteristic, there is a problem that the contamination resistance of the sheet is deteriorated because the contaminants that have penetrated between the mountains and the valleys of the irregularities are not easily removed. In addition, since general matting agents are porous and have a low apparent specific gravity, they are located on the surface of the coating, thereby increasing the surface adsorption of foreign substances (eg, fine dust, moisture, grease, etc.).

On the other hand, in order to improve stain resistance, it is advantageous to improve the curing density. For example, it may be considered to use polyfunctional oligomers in the coating treatment. However, when the amount of polyfunctional oligomer is increased, the gloss of the cured layer increases, and thus there is a problem that is not suitable for a decor sheet for the purpose of matte properties. In other words, it is not easy to provide a decorative sheet that satisfies both of them at the same time because matte properties and stain resistance are trade-off properties.

One object of the present application is to solve the problems of the prior art described above.

An object of the present application is to provide a laminated film having excellent matte properties and stain resistance at the same time, which is a trade-off relationship according to the prior art.

All of the above and other objects of the present application can be solved by the present application described in detail below.

In one example related to the present application, the present application relates to a stain-resistant laminated film comprising a base layer and a cured layer.

The cured layer has a wrinkled surface. The surface on which the wrinkles are formed is one surface opposite to one surface of the cured layer facing the substrate layer. The wrinkled surface may impart predetermined surface properties (eg, surface hardness, glossiness, stain resistance, etc.) described below to the laminated film.

In the present application, the term "surface on which wrinkles are formed" (hereinafter, referred to as S _wrinkle ) means that the cured layer includes wrinkles on at least one surface thereof, and the cured layer has three-dimensional surface irregularities due to the wrinkles. Means (see Fig. 1). For example, the surface (S _wrinkle ) has large and small ridges, valleys, and irregularities including wrinkles formed therefrom and can be visually recognized in a predetermined shape. Each of the ridges, valleys, and corrugations may have a regular or irregular shape. Such a wrinkled surface may also be referred to as a surface having a fine folding structure.

_{When observing the surface of the cured layer (S wrinkle} ) in which wrinkles are formed in the normal direction of the cured layer, ridges, valleys, wrinkles, and irregularities formed therefrom are, for example, the surface (S _{wrinkle) while undergoing the curing process described below.} ) Is observed over the entire area. That wrinkles or surface irregularities described in the present application are observed in all areas of the surface of the cured layer may be expressed as satisfying properties such as surface hardness, matte property, and stain resistance described below.

The wrinkles may be observed in a form including a line shape (eg, straight line, curved line) having a directionality. In one example, the wrinkles of the surface formed while repeating the straight and curved shapes may impart a curvature such as a mountain range shape to the surface of the cured layer.

The surface uneven structure formed by corrugations having a line shape as described above is a so-called point-wise uneven shape (Fig. 2).

In one example, the surface (Swrinkle) may include a wrinkle (Wa) that can be visually recognized in a predetermined size and shape. Specifically, the wrinkles may have a width in the range of several to tens of µm at a level of several hundred nm, and may have a line (straight or curved) shape extending to a length in the range of several to several hundred µm.

The width of the wrinkles and the length of the wrinkles can be confirmed from an image (eg, SEM) photographing the wrinkled surface as shown in the accompanying drawings. At this time, the length in the extending direction is greater than the width (see Fig. 3).

_{Specifically, the ends of the wrinkles (W a} ) extending in a straight or curved shape form a slope with a height gradually decreasing and may be incorporated into the hardened layer. _{In some cases, the end of any one wrinkle (W a} ) having the size and shape may be a starting point of another wrinkle or a connection portion with another wrinkle. In addition, when observing the cross-sectional curve near the wrinkle in the direction perpendicular to the extension direction of the wrinkle (W _a ), the width of the wrinkle is in both directions from the point or part (e.g., ridge) forming the height of the wrinkle. It forms a slope that gradually decreases in height and may be incorporated into the hardened layer. On the other hand, when a ridge and a valley adjacent thereto form a wrinkle or a part thereof, the area of the shape recognized including the valley may be viewed as the width _{of the wrinkle W a.}

In one example, the width of the wrinkle (Wa) may be 10 ㎛ or less or 5 ㎛ or less. In a specific example, the upper limit of the width of the wrinkles may be, for example, 1 μm or less. And, the lower limit of the width of the wrinkles (Wa) may be, for example, 150 nm or more, 200 nm or more, 250 nm or more, or 300 nm or more, 400 nm or more, or 500 nm or more, specifically, for example , 1 μm or more, 2 μm or more, or 3 μm or more. If the above range is satisfied, it may be advantageous for the surface formed by the wrinkles to have certain properties desired in the present application.

In one example, the length of the wrinkles (Wa) extending may be 5 μm or more or 10 μm or more, and specifically, for example, 20 μm or more, 30 μm or more, 40 μm or more, 50 μm or more, 60 It may be µm or more, 70 µm or more, 80 µm or more, or 90 µm or more, or 100 µm or more. And, the upper limit may be, for example, 500 µm or less, 450 µm or less, 400 µm or less, 350 µm or less, 300 µm or less, 250 µm or less, 200 µm or less, or 100 µm or less, and more specifically 90 µm or less , 80 µm or less, 70 µm or less, 60 µm or less, or 50 µm or less. If the above range is satisfied, it may be advantageous for the surface formed by the wrinkles to have certain properties desired in the present application.

The wrinkles (W _a ) may have a predetermined height in most of the extending length. For example, the wrinkles (W _a ) may have a height of 1 μm or more. Specifically, when observing the cross-sectional curve of the wrinkle in the direction perpendicular to the extension direction of the wrinkle, the point or part that forms the height of the wrinkle (e.g., ridge) and the point or part of the hardened layer where the width of the wrinkle is mixed ( Example: Valley) may have a height difference of at least 1 μm or more. At this time, the most of the length at which the height is observed means 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, or 95 of the length that _{the wrinkle (W a) continuously extends along its shape.} It means a length that is greater than or equal to %. When the height difference gradually decreases in the extension direction of the wrinkles, and the height is less than or equal to 1 μm, a shape in which the ends of the wrinkles are mixed into the cured layer can be observed, or the size or shape of the wrinkles (W _a ) A shape in which the contact with other wrinkles different from the is started may be observed. In the latter case, a more complex wrinkle structure may form the unevenness of the _{surface (S wrinkle).}

The wrinkle (W _a ) is observed over the entire area of the surface (S _wrinkle ), while showing a regular or irregular distribution may form a surface wrinkle or irregularities. The fact that the wrinkles or surface irregularities described in the present application are observed in the entire area of the surface of the cured layer may be expressed as satisfying the matte properties, surface hardness, and stain resistance described below.

For example, in the surface (S _wrinkle ), the wrinkle (W _a ) can form surface irregularities while having a shape in which _a plurality of wrinkles (W a) are branched in different directions from one specific point. have.

For example, in the surface (S wrinkle), the wrinkle (W <sub>a ) may have a shape similar to ``</sub> Y'' or ``<'' (that is, the wrinkle may be recognized as a shape similar to ``Y'' or ``<''). Can). At this time, wrinkles having a shape similar to "Y" or "<" may be densely arranged to form surface irregularities.

For example, in the surface (S _wrinkle ), the wrinkles (W _a ) may form surface irregularities in a form in which branches in other directions are suppressed and are distributed while extending generally in one direction.

The shape and arrangement of _{the wrinkles (W a} ) forming the surface irregularities as described above are exemplary. In addition, one or more wrinkles of the shape or form described above may be observed on the surface having irregularities (S _wrinkle).

Examples of the shape of the surface wrinkles as described above can be found in FIGS. 1, 3, 4 and 5, and the like.

In one example, the surface (S _wrinkle ) may include a wrinkle (W _b ) different in size and/or shape from the wrinkle (W _{a ).} For example, it may be that the folds (W _a) crease (W _b) of wrinkles that do not meet one or more of the width, length and height. Preferably, the number of one or more of the width, length and height to be defined by the folds (W _b) to be smaller than that of the folds (W _a) defined as above. _{When a} large number of wrinkles larger than the wrinkle (W a) are observed on the surface, it may become an obstacle to securing the surface properties.

In one example, the wrinkle (W _b ) is observed over the entire area of the surface (S _wrinkle ), it may form a surface irregularities while showing a regular or irregular distribution. The fact that the wrinkles or surface irregularities described in the present application are observed in the entire area of the surface of the cured layer may be expressed as satisfying the matte properties, surface hardness, and stain resistance described below.

For example, in the surface (S _wrinkle ), the wrinkle (W _b ) can form surface irregularities while having a shape in which a plurality of wrinkles (W _{b) are branched in different directions from one specific point.} have.

For example, in the surface (S wrinkle), the wrinkle (W <sub>b ) may have a shape similar to ``</sub> Y'' or ``<'' (that is, the wrinkle may be recognized as a shape similar to ``Y'' or ``<''). Can). At this time, wrinkles having a shape similar to "Y" or "<" may be densely arranged to form surface irregularities.

For example, in the surface (S _wrinkle ), the wrinkles (W _b ) may form surface irregularities in a form in which branches in other directions are suppressed and are distributed while extending generally in one direction.

_{The shape of the wrinkles (W b} ) forming the surface irregularities as described above is exemplary. In addition, one or more wrinkles of the shape or form described above may be observed on the surface having irregularities (S _wrinkle).

Examples of the shape of the surface wrinkles as described above can be found in FIGS. 1, 3, 4 and 5, and the like.

In one example, the _{unevenness of the surface (S wrinkle} ) may be formed by the wrinkles (W _a , W _{b ).}

In one example, the wrinkle (W _b ) may form a cured layer surface (S _wrinkle ) in a state located adjacent to the wrinkle (W _{a ).} For example, when observed from the normal direction of the hardened layer, valleys or ridges may exist between _{the wrinkles (W a} ) and the wrinkles (W _{b ).}

In another example, the folds (W _b) are the folds (W _a) and physically connected to the state, e.g., the pleats (W _a) from which the height is low and the width is less wrinkled branched (W _b) It may have a shape or form, and these wrinkles (W _a , W _b ) may form a cured layer surface (S _wrinkle ). The direction or length of the wrinkles (W _b ) branching from the wrinkles (W _{a) is not particularly limited.}

Examples of the shape of the surface wrinkles as described above can be found in FIGS. 1, 3, 4 and 5, and the like.

In one example, the shape of the wrinkles on the surface of the cured layer may be the same or similar to that shown in FIG. 5. For example, the surface of the cured layer may be a surface in which only one of the wrinkles of a specific shape exemplified below is observed, or two or more of the wrinkles of a specific shape exemplified below may be observed at the same time, otherwise the following In addition to the exemplified specific shape wrinkles, other shapes of wrinkles may also be the surfaces observed (at a level that does not impair the desired surface properties).

For example, the surface may be a radially corrugated surface (see FIG. 5A). The radial shape may be a shape in which a plurality of wrinkles having the same or different directions extend from a certain point (center portion). The wrinkles forming the radial shape may include wrinkles (Wa). In addition, the wrinkles forming the radial shape may include wrinkles (Wb). Such wrinkles may be observed over the entire area of the surface of the cured layer, and may be distributed on the surface to an extent that, for example, satisfies the following surface properties while undergoing a curing process described below. In addition, in some cases, the wrinkles extending from the center with directionality may have a shape that gradually decreases in height as they move away from the center.

For example, the surface may be a Y-shaped (or Y-tile pattern) corrugated surface (see FIG. 5B). The Y-shape may have a shape in which a plurality of wrinkles having three different directions extend from a certain point (central portion). In the case of Y-type, it is sufficient if the Y-shaped curvature is observed in most of the surface area when observing the surface of the cured layer, and three corrugations with directionality must be observed from a certain point so that only the curvature with the Y-shaped shape is observed. It doesn't have to have a shape that stretches out. The wrinkles forming the Y-shape may include wrinkles Wa. In addition, the wrinkles forming the Y-shape may include wrinkles (Wb). Such wrinkles may be observed over the entire area of the surface of the cured layer, and may be distributed on the surface to an extent that, for example, satisfies the following surface properties while undergoing a curing process described below. In addition, in some cases, the wrinkles extending from the center with directionality may have a shape that gradually decreases in height as they move away from the center.

For example, the surface may be a sand wave type corrugated surface (see FIG. 5C). The sand wave type has a lower depth of field and is more evenly distributed when compared to other shapes of surface wrinkles. The wrinkles forming the sand wave shape may include wrinkles Wa. In addition, the wrinkles forming the sand wave shape may include wrinkles (Wb). Such wrinkles may be observed over the entire area of the surface of the cured layer, and may be distributed on the surface to an extent that, for example, satisfies the following surface properties while undergoing a curing process described below.

For example, the surface may be a tensioned-web corrugated surface (see FIG. 5D). In the tensioned-web type, there are wrinkles formed to be arranged in one direction, which is generally the same, and other wrinkles arranged in a direction intersecting with respect to them (they are also arranged in one direction which is generally the same. It may be in the same shape as the web (web) to be formed. At this time, the crossing angle is not particularly limited. In the case of the tensioned-web type, it can be recognized that the corrugations formed to be generally arranged in one direction extend over the entire surface area. The wrinkles forming the tensioned-web shape may include wrinkles Wa. In addition, the wrinkles forming the tensioned-web type may include wrinkles (Wb). Such wrinkles may be observed over the entire area of the surface of the cured layer, and may be distributed on the surface to an extent that, for example, satisfies the following surface properties while undergoing a curing process described below.

In one example, the surface may have irregularities formed by randomly dispersing radial or Y-shaped corrugated structures.

In the cured layer having a wrinkled surface (S _wrinkle ) as described above, the surface has predetermined surface characteristics. For example, the film of the present application improves the trade-off relationship between stain resistance and matte, and has excellent surface hardness.

Specifically, the laminated film may have a 60° gloss (G) of 5.5 or less or 5.0 or less on the surface of the cured layer.

In the present application, "60° glossiness (G)" can be measured using a gloss meter according to ASTM D2457, and is a numerical value representing the degree of gloss of the surface (GU: gloss unit). The lower the gloss, the closer to matte.

Specifically, the upper limit of the 60° glossiness (G) of the wrinkled surface in the cured layer is, for example, 4.9 or less, 4.8 or less, 4.7 or less, 4.6 or less, 4.5 or less, 4.4 or less, 4.3 or less, 4.2 or less, It can be 4.1 or less or 4.0 or less. Although not particularly limited, the lower limit of the 60° gloss (G) may be, for example, 3.0 or more, 3.5 or more, or 4.0 or more. When the surface of the cured layer of the film has a glossiness (G) of 60° in the above range, it can provide beautiful matte properties to the user.

In another example, the roughness (Rz) of the surface of the cured layer may be in the range of 3.0 to 10 μm.

In the present application, "surface roughness (Rz)" can be measured according to ISO 4281, and is a numerical value expressing the degree of irregularities. Specifically, the surface roughness Rz may be referred to as ten point average roughness. Specifically, the surface roughness takes a reference length (L) as the cross-sectional curve of the surface of the cured layer, and is a straight line that does not cut the cross-sectional curve horizontally in parallel to the average line of the portion, and the peaks (ridges) from the highest to the fifth and The deviation is indicated by measuring the gap between the valleys from the lower to the fifth. At this time, the reference length L may be at the level of several mm, for example, in the range of about 0.1 to 1 mm, specifically about 0.8 mm.

Specifically, the roughness (Rz) of the surface of the cured layer is 3.1 µm or more, 3.2 µm or more, 3.3 µm or more, 3.4 µm or more, 3.5 µm or more, 3.6 µm or more, 3.7 µm or more, 3.8 µm or more, 3.9 µm or more, 4.0 It may be µm or more, 4.1 µm or more, 4.2 µm or more, 4.3 µm or more, 4.4 µm or more, or 4.5 µm or more. In addition, the upper limit of the surface roughness is, for example, 9.5 µm or less, 9.0 µm or less, 8.5 µm or less, 8.0 µm or less, 7.5 µm or less, 7.0 µm or less, 6.5 µm or less, 6.0 µm or less, 5.5 µm or less, or 5.0 It may be less than or equal to µm. When the surface of the cured layer of the film has a surface roughness (Rz) within the above range, the contamination resistance of the film can be prevented from adhering to the surface by reducing the surface contact area and contaminants caused by the user's touch or external factors. It can be beneficial to improve

In one example, the laminated film may have a surface hardness of 0.5 N or more, measured with respect to the surface of the cured layer on which the wrinkles are formed.

In the present application, "surface hardness" may be measured according to ISO 4586-2, as described in the following Examples. The surface hardness indicates the hardness of the surface and is a value related to the durability of the film.

In one example, the surface hardness may be 0.51 N or more, 0.52 N or more, 0.53 N or more, 0.54 N or more, 0.55 N or more, 0.56 N or more, 0.57 N or more, 0.58 N or more, 0.59 N or more, or 0.60 N or more. . The upper limit is not particularly limited, but may be, for example, 0.70 N or less or 0.65 N or less. When the surface hardness of the film is satisfied, a laminated film having excellent mechanical properties and durability can be provided.

When the above-described surface wrinkle structure and bending thereof exist, matte properties can be ensured, but it is known that the stain resistance is generally poor. However, in the present application, a matte property and stain resistance are simultaneously secured through a predetermined treatment for the composition described below. For example, as confirmed in the following experimental examples, the present application may have a matte characteristic, and excellent stain resistance test results according to the DIN68861-1 standard.

In the specific example of the present application, the cured layer having the above properties may be obtained through curing treatment of a composition having a predetermined configuration. Specifically, the cured layer may include a cured product of a curable composition.

In one example, the treatment agent used in the present application, that is, the coating composition may be a photocurable solvent-free composition. That is, the composition may not contain a solvent, for example, 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 the process efficiency. In addition, through the use of the solvent-free composition, it is possible to prevent deterioration of the surface characteristics required in the film of the present application due to air bubbles 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.

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 following photocuring treatment is performed on the resin composition having a predetermined configuration, a cured layer having a wrinkled surface as described above may be prepared.

In one example, the reactive oligomer may be urethane (meth)acrylate. The urethane (meth)acrylate may function advantageously in securing the strength of the cured layer and securing the flexibility of the cured layer through the elasticity peculiar to urethane bonding.

The urethane acrylate usable in the present application may be prepared to satisfy the following functionalities and/or molecular weights by polymerizing compounds such as isocyanate, alcohol, and acrylate according to a known method. For example, in a polyisocyanate having three or more isocyanate groups, an acrylate containing three or more acrylic groups having a hydroxyl group in the molecule is reacted under a metal catalyst and a radical polymerization inhibitor until the isocyanate (NCO) disappears, and then , Urethane acrylate may be prepared by adding 5 to 30% by weight of an ultraviolet curable monomer. Alternatively, a urethane acrylate that satisfies the following functionalities and/or molecular weights may be selected and used from among commercially available products.

In one example, the urethane (meth) acrylate oligomer may have a weight average molecular weight (Mw) of 10,000 or less. For example, the molecular weight of the urethane (meth)acrylate may be 9,000 or less, 8,000 or less, 7,000 or less, 6,000 or less, or 5,000 or less. In addition, the lower limit of the urethane (meth)acrylate oligomer weight average molecular weight (Mw) may be, for example, 5,00 or more, specifically 1,000 or more, 2,000 or more, 3,000 or more, 4,000 or more, or 5,000 or more. When the molecular weight exceeds the above range, the curing density may decrease, and the cured structure may not be dense, and thus stain resistance may be lowered.

In one example, the composition may include two or more urethane (meth)acrylate oligomers having different weight average molecular weights (Mw) from each other.

In one example, the composition may include a first urethane (meth)acrylate having a weight average molecular weight (Mw) in the range of 3,000 to 10,000. Specifically, the lower limit of the molecular weight of the first urethane (meth) acrylate may be, for example, 4,000 or more, 5,000 or more, 6,000 or more, 7,000 or more, 8,000 or more, or 9,000 or more, and the upper limit thereof is 9,000 or less, 8,000 or less, It may be 7,000 or less, 6,000 or less, 5,000 or less, or 4,000 or less. When the above range is used, it may be advantageous in densifying a cured structure to provide a high-hardness film.

In one example, the composition may further include a urethane (meth) acrylate having a lower molecular weight than the first urethane (meth) acrylate. Specifically, the composition may include a second urethane (meth)acrylate having a weight average molecular weight (Mw) of less than 3,000 in addition to the first urethane (meth)acrylate having the weight average molecular weight (Mw).

The lower limit of the molecular weight of the second urethane (meth) acrylate may be, for example, 500. Specifically, the molecular weight may be 1,000 or more, 1,500 or more, 2,000 or more, or 2,500 or more. And the upper limit of the molecular weight may be, for example, 2,500 or less, 2,000 or less, or 1,500 or less. The use of a second urethane (meth)acrylate with a low molecular weight is advantageous to provide a high hardness film.

In one example, the urethane (meta) acrylate oligomer may include one or more photopolymerizable functional groups. Specifically, the urethane (meth) acrylate oligomer may be a monofunctional oligomer or a polyfunctional oligomer having two or more functional groups. The number of functional groups of the polyfunctional oligomer is not particularly limited, but when considering fouling resistance, surface hardness, wrinkle formation for matte properties, flexibility, etc., for example, it may be within the range of 2 to 15 or within the range of 2 to 10. have.

In one example, the composition may include two or more urethane (meth) acrylate oligomers having different numbers of functional groups.

In another example, the composition may include two or more polyfunctional urethane (meth) acrylate oligomers having different numbers of functional groups from each other.

In another example, the composition may contain two or more polyfunctional urethane (meta) acrylate oligomers having three or more functional groups.

In one example, the number of functional groups in the first urethane (meta) acrylate oligomer may be 2 or 3 or more. In a specific embodiment, the number of functional groups of the first urethane (meth) acrylate oligomer is within the range of 2 to 15 or within the range of 2 to 10, specifically 2, 3, 4, 5, 6, 7, 8 , Or may be 9.

In one example, the second urethane (meta) acrylate oligomer may have 2 or 3 or more functional groups. In a specific embodiment, the number of functional groups of the first urethane (meta) acrylate oligomer is within the range of 2 to 15 or within the range of 2 to 10, specifically 2, 3,4, 5, 6, 7, 8 , Or may be 9.

In one example, the number of functional groups of the second urethane (meta) acrylate oligomer may be smaller than the number of functional groups of the first urethane (meta) acrylate oligomer. For example, when the number of functional groups of the second urethane (meta) acrylate oligomer is in the range of 3 to 8, the number of functional groups of the first urethane (meta) acrylate oligomer is in the range of 5 to 10, and the second urethane (meta) It may be greater than the number of functional groups of the acrylate oligomer. As described above, when the urethane (meta) acrylate satisfies a predetermined number of functional groups and a predetermined molecular weight range, high hardness can be provided by increasing the curing level through the use of a high functional first urethane (meta) acrylate, At the same time, it is possible to secure an appropriate level of flow site by using a low-functional second urethane (meta) acrylate and prevent excessive deterioration of the moldability. As a result, the use of urethane acrylate as described above can contribute to providing a film excellent in surface hardness, stain resistance, and moldability.

When the number and/or molecular weight of the above functional groups are satisfied, the specific structure of the urethane (meta) acrylate oligomer is not particularly limited.

The composition may contain a urethane (meta) acrylate oligomer in the range of 20 parts by weight to 80 parts by weight, among 100 parts by weight of the combined oligomer component (A) and the monomer component (B).

In one example, the content ratio (w1/w2) between the weight (w1) of the first urethane acrylate and the weight (w2) of the urethane acrylate may range from 0.8 to 2.0. Specifically, the lower limit of the content ratio (w1/w2) may be, for example, 0.9 or more, 1.0 or more, or 1.2 or more, 1.4 or more, 1.6 or more, or 1.8 or more, and the upper limit is, for example, 1.9 or less, 1.8 or less , 1.7 or less, 1.6 or less, or may be 1.5 or less. The weight ratio may be appropriately adjusted in consideration of excellent surface hardness and flexibility, and stain resistance.

The composition includes a reactive monomer component in addition to the oligomer. In addition, the reactive monomer component can function like a solvent to lower the viscosity of the composition (rather than when only the oligomer component is included), thereby improving the coating processability for the substrate layer.

In one example, a monofunctional or polyfunctional monomer may be used as the reactive monomer component (B). For example, the composition may comprise 20 parts by weight or more, 25 parts by weight or more, 30 parts by weight or more, or 35 parts by weight or more of the reactive monomer component (B ) Can be included. When the above range is satisfied, it is advantageous to increase the reaction rate of the composition and increase the curing density to secure the surface hardness in the above-described range.

The upper limit of the content of the reactive monomer component (B) may be appropriately adjusted in consideration of the effect of using the above-described urethane (meta) acrylate. For example, in 100 parts by weight of the sum of the oligomer component (A) and the monomer component (B), 80 parts by weight or less, 75 parts by weight or less, 70 parts by weight or less, 65 parts by weight or less, 60 parts by weight or less, 55 parts by weight Hereinafter, 50 parts by weight or less or 45 parts by weight or less of the reactive monomer component (B) may be used.

In one example, the reactive monomer may be a (meth)acrylic monomer.

In one example, the reactive monomer may be a monomer (b-1) having a polar functional group such as a hydroxy group, a nitrogen-containing functional group, or an alkylene oxide group. The monomer having a polar functional group is advantageous for increasing the curing reaction rate and increasing the curing density. Specifically, the reactive monomer may be a (meth)acrylic monomer having a polar functional group.

Although not particularly limited, examples of the hydroxy group-containing (meth) acrylic monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6- Hydroxyalkyl (meth)acrylates such as hydroxyhexyl (meth)acrylate or 8-hydroxyoxyl (meth)acrylate may be used.

In the case of a nitrogen-containing functional group, as a functional group containing nitrogen in the molecule, for example, an amine group, an imine group, an amide group, a nitrile group, a nitro group, an azo group, an imide group, or an azide group may be exemplified, but are limited thereto. It is not. In one example, when a (meth) acrylic monomer having a nitrogen-containing functional group is used, the specific type is not particularly limited, but, for example, (meth) acrylonitrile, N-methyl acrylamide, (meth) acryl Amide, alkyl (meth)acrylamide, dialkyl (meth)acrylamide, hydroxyalkyl (meth)acrylamide, N-butoxy methyl (meth)acrylamide, N-vinyl pyrrolidone, N-vinyl caprolactam, 2-aminoethyl (meth)acrylate, 3-aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate or N,N-dimethylaminopropyl (meth)acrylate, etc. may be used. .

In the case of a monomer having an alkylene oxide, for example, an alkoxy alkylene glycol (meth)acrylic acid ester, an alkoxy dialkylene glycol (meth)acrylic acid ester or an alkoxy polyethylene glycol (meth)acrylic acid ester may be used. It is not limited.

In one example, the content of the reactive monomer (B) component included in the composition may be equal to or greater than the content of the first urethane (meth)acrylate. Specifically, a ratio (w3/w1) between the content (W1) of the first urethane (meta) acrylate and the content (w3) of the reactive monomer (B) component may range from 1 to 1.5. When the content range is satisfied, it is advantageous in securing appropriate coating processability, securing surface hardness according to an increase in curing density, and securing stain resistance at the same time.

In one example, the content of the reactive monomer (B) component included in the composition may be equal to or greater than the content of the second urethane (meth)acrylate. Specifically, a ratio (w3/w2) between the content (W2) of the second urethane (meta) acrylate and the content (w3) of the reactive monomer (B) component may range from 1.5 to 2.5. When the content range is satisfied, it is advantageous in securing appropriate coating processability, securing surface hardness according to an increase in curing density, and securing stain resistance at the same time.

In one example, the composition may further include a polyfunctional monomer (b-2). Specifically, the composition may further include a monomer having two or more reactive functional groups. For example, a polyfunctional (meth)acrylate monomer having two or more functional groups may be used. The polyfunctional monomer increases the curing strength and imparts durability to the cured layer.

Although not particularly limited, the polyfunctional (meth)acrylate monomers include cyclohexane dimethanol di(meth)acrylate, hexanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, and tri 2, such as ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc. Functional (meth)acrylate monomers; Trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propylated trimethylolpropane tri(meth) ) Trifunctional (meth)acrylate monomers such as acrylate, glycerylpropylated tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, etc.; Tetrafunctional (meth)acrylate monomers such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate; 5-functional (meth)acrylate monomers such as dipentaerythritol penta(meth)acrylate and dipentaerythritol hydroxypenta(meth)acrylate; 5-functional (meth)acrylate monomers such as dipentaerythritol hexa(meth)acrylate and the like may be used.

In one example, the number of functional groups of the polyfunctional monomer component may be in the range of 2 to 5, in the range of 2 to 4, or in the range of 2 to 3.

As described above, in the case of using a reactive monomer, specifically, a reactive monomer (b-1) having a polar functional group, it is advantageous to secure the curing density, but as the frequency of exposure of the polar functional group to the surface of the cured layer increases, contaminants are adsorbed. There is a problem that contamination resistance deteriorates. Therefore, it is possible to improve the contamination resistance by lowering the possibility of exposure to the surface of the cured layer of the polar functional group while increasing the curing density by using a component having a larger number of functional groups such as polyfunctional (meth)acrylate (b-2) in a predetermined amount.

In one example, the content ratio (b-1:b-2) of the (meth)acrylic monomer (b-1) and the polyfunctional monomer (b-2) having a polar functional group is in the range of 5:1 to 3:1 I can. When the content of the polyfunctional monomer (b-2) is less than the above range, the stain resistance improvement effect is insufficient. In addition, when the content of the polyfunctional monomer (b-2) exceeds the above range, the viscosity increases and the coating processability of the cured composition is poor, and the gloss of the cured layer increases, so that the desired matte property may not be secured. .

As long as the above range is satisfied, the content ratio of the polyfunctional monomer (b-2) in the total composition is not particularly limited.

For example, the composition contains 5 parts by weight or more or 10 parts by weight or more of the polyfunctional (meta) acrylate monomer (b-2) in 100 parts by weight of the sum of the oligomer component (A) and the monomer component (B). Can include. When the content of the polyfunctional monomer (b-2) is less than the above range, the stain resistance improvement effect is not sufficient.

In addition, the composition contains 20 parts by weight or less or 15 parts by weight or less of the polyfunctional (meta) acrylate monomer (b-2) in 100 parts by weight of the sum of the oligomer component (A) and the monomer component (B). can do. Specifically, the content of the polyfunctional (meth)acrylate monomer may be, for example, 14 parts by weight or less, 13 parts by weight or less, 12 parts by weight or less, 11 parts by weight or less, or 10 parts by weight or less. When the content of the polyfunctional monomer exceeds the above range, the viscosity increases and the coating processability of the cured composition is poor, and the gloss of the cured layer may increase, resulting in poor matte properties.

The composition may further include an initiator (C). As long as it is an initiator that can be used in the curing process described below, the type of the initiator is not particularly limited, and a known commercial product may be used.

The content of the initiator is not particularly limited. For example, the composition may contain 10 parts by weight or less of an initiator based on 100 parts by weight of the combined oligomer component (A) and the 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 0.5 parts by weight. As described below, in the present application, since the stepwise curing is performed when curing the cured layer, the curing efficiency is excellent even when a small amount of an initiator is used.

The composition may further include a light stabilizer (D). As long as it is a light stabilizer that can be used in the curing process described below, its kind is not particularly limited, and a known commercial product may be used.

The content of the light stabilizer is not particularly limited. For example, the composition may contain 10 parts by weight or less of a photostabilizer based on 100 parts by weight of the combined oligomer component (A) and the 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. And, 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 by ultraviolet rays.

In one example, the composition for forming the cured layer may not contain a matting agent component or may be used in a small amount.

Specifically, the matting agent has a particle shape and can impart a matte effect to the film in a manner that increases the scattering rate of light on the surface of the film. However, the use of a matting agent brings the problem of increased fouling resistance, as described above. However, since the cured layer of the present application has the above-described surface characteristics, it can effectively implement matte characteristics. Accordingly, sufficient matte properties can be implemented in the film of the present application without using the matting agent used to implement the matte effect in the prior art.

In addition, even if a matting agent is used, the matting agent used for realizing the matte property in the prior art may not be used. That is, according to the present application, it is possible to significantly reduce the content of the matting agent. For example, the content of the matting agent component is 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 composition consisting of the remaining components excluding the matting agent component It may be less than or equal to part. Accordingly, the film of the present application has an advantage of preventing problems such as deterioration of contamination resistance due to the use of a matting agent.

In one example, a composition for forming a cured layer that does not contain a particle-shaped matting agent as an additive or uses as little as the above content may have a low viscosity, for example, a viscosity of 500 cps or less at room temperature. Specifically, when an excessive amount of an additive in the form of particles is used for realizing the matte effect, the viscosity of the composition increases, and thus the coating workability for the substrate layer is not good. However, in the present application, since the matting agent is not used or can be used significantly less than the prior art as described above, the composition for forming the cured layer is 450 cps or less, 400 cps or less, 350 cps or less, 300 cps or less, or 250 cps or less at room temperature. It may have a viscosity of less than or equal to cps. The lower limit of the viscosity of the composition may be, for example, 100 cps or more, 150 cps or more, 200 cps or more, 250 cps or more, 300 cps or more, 350 cps or more, or 400 cps or more. At this time, room temperature refers to a temperature in the range of about 18 to 32 °C, specifically, a temperature in the range of 22 to 28 °C, a temperature in the range of 23 to 27 °C, or about 25 °C. It can mean the temperature of. In addition, the viscosity can be measured according to a known method using a Brookfield viscometer.

If the surface characteristics as described above are satisfied, the thickness of the cured layer is not particularly limited. For example, the thickness of the cured layer may be 3 µm or more, 5 µm or more, 10 µm or more, or 15 µm or more, assuming satisfaction of the surface characteristics. Further, for example, the thickness of the cured layer is 100 µm or less, 90 µm or less, 80 µm or less, 70 µm or less, 60 µm or less, 50 µm or less, 40 µm or less, 30 µm or less, 20 µm or less, or 15 µm It can be below.

The type of the base layer to which the above composition is directly applied is not particularly limited. For example, the base layer may include polyvinyl chloride (PVC) or polyethylene terephthalate (PET). Although not particularly limited, in consideration of the suppression of whitening, mechanical properties such as impact resistance, ease of processing, and chemical resistance, among polyethylene terephthalate (PET), glycol-modified polyethylene tehrephthalate (PETG) is used. It may be desirable.

The thickness of the base layer is also not particularly limited. For example, the thickness of the substrate layer may be 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. . And, for example, the thickness of the substrate layer is 3,000 µm or less, 2,000 µm or less, or 1,000 µm or less, specifically 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 It may be 300 μm or less.

As described above, the present application can provide a laminated film having excellent stain resistance and matte properties, and excellent surface hardness. A laminated film having such characteristics can be obtained by performing a predetermined curing treatment described below with respect to the composition having the above-described configuration.

The above-described laminated film may be used for furniture or decorative materials having curved, corner and/or flat surfaces. Such furniture may include, for example, a door, a desk, a chair, or a shelf, and the decorative material may be used as a part of the furniture or may encompass articles that can be used alone.

In another example related to the present application, the present application relates to a method of providing the laminated film. The method may include a process of first and second curing after applying a photocurable composition including a photocurable oligomer component (A) and a reactive monomer component (B) directly on a substrate layer.

The primary curing and the secondary curing may be referred to as a first light irradiation step and a second light irradiation step, respectively, and these curings have the same or different wavelength, light irradiation amount, and/or light irradiation time of the irradiated light. Can be done. At this time, the first curing is performed under conditions capable of forming wrinkles while shrinking the surface of the cured layer applied on the substrate layer. Specific conditions are described below.

The specific configuration of the composition applied on the substrate layer is as described above. In addition, the types and characteristics of the base layer are the same as described above.

The method of applying the composition on the base layer is not particularly limited. For example, Mayer, D-bar, rubber roll, G/V roll, air knife, slot die, etc. The composition may be applied on the substrate layer using a known method.

The method includes a first light irradiation step of irradiating _{light (L 1} ) having a relatively short wavelength to the composition applied on the substrate layer under inert gas conditions; And a second light irradiation step of curing the composition by irradiating light (L ₂ ) having a longer wavelength than the light (L _{1) under air conditions.} Specifically, the method includes a first light irradiation step of irradiating a composition coated on a substrate layer with light (L ₁ ) of a predetermined wavelength under an inert gas condition to form wrinkles on the surface of the applied composition; And a second light irradiation step of forming a cured layer that is a cured product of the composition by irradiating light (L ₂ ) having a longer wavelength than the light (L _{1) under air conditions.}

The device for irradiating light in each step is not particularly limited, for example, when irradiating light with a wavelength of 300 nm or less in the first irradiation step, and irradiating light with a wavelength of 400 nm or less in the second irradiation step, A known mercury or metal halide lamp may be used.

In the first light irradiation step, the composition applied on the substrate layer is irradiated with light, and the surface of the composition (or the composition cured by light irradiation) to which the excimer generated by the irradiated light is applied is contracted. This is a step to form wrinkles. The wrinkled surface increases scattering of light incident on the surface so that a matte property can be imparted. The wrinkled surface may have surface roughness and gloss characteristics as described above. Accordingly, in the present application, the matting agent may not be used, or even if the matting agent is used, it may be used in a significantly smaller amount compared to the prior art to achieve a matte effect.

In one example, in the first light irradiation step, light having a wavelength of 300 nm or less having high energy, for example, light having a wavelength of 200 nm or less, may be irradiated. Specifically, 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 may be irradiated at the first light irradiation stage. In one example, the upper limit of the wavelength of light irradiated in the first light irradiation step may be, for example, 200 nm or less, 190 nm or less, or 180 nm or less.

The first light irradiation step may be performed in an inert atmosphere. The gas used to create an inert atmosphere may be, for example, He, Ne, Ar, and/or N ₂ .

In one example, the inert atmosphere in which the first light irradiation step is performed may be an atmosphere in which _{the concentration of oxygen (O 2} ) is about 4,000 ppm or less. Specifically, the upper limit of the concentration of oxygen 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 It may be less than, 500 ppm or less, 400 ppm or less, or 300 ppm or less. And the lower limit is, 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 It can be more than that.

In one example, the inert atmosphere may be formed such that the concentration of oxygen in the _{nitrogen gas N 2 satisfies the above range.}

When the first light irradiation is performed under the inert atmosphere conditions as described above, it is advantageous in securing the above-described wrinkles and surface characteristics. For example, when the first light irradiation is performed in an inert atmosphere in which the concentration of oxygen exceeds the above range, wrinkles such as those mentioned above are difficult to be formed, and the surface characteristics as described above cannot be provided. For example, wrinkles are not formed evenly over the entire surface area so as to satisfy the above-described properties, but may be rarely observed on the surface.

In one example, when performing the first 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 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, The upper limit may be, for example, 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 within the above range, an appropriate amount of light can reach the composition with an appropriate intensity, and as a result, a wrinkled surface of the shape and size described above is formed, and the It is advantageous to obtain the described degree of surface properties (eg surface roughness, glossiness).

In one example, the irradiation amount of light irradiated in the first light irradiation step may be 1 mJ/cm2 or 5 mJ/cm2 or more. Specifically, the lower limit of the light irradiation amount in the first light irradiation step may be, for example, 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 And the upper limit is, for example, 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/cm 2 or less or 25 mJ/cm 2 or less. In the first light irradiation step, when the amount of light irradiation is adjusted within the above range, a wrinkled surface of the above-described shape and size is formed, and surface characteristics (eg, surface roughness, glossiness) of the above-described degree are secured. It is advantageous to do.

In one example, the time that the light is irradiated in the first light irradiation step may be at the level of several seconds, for example, the upper limit may be 10 seconds or less or 5 seconds or less, and the lower limit is, for example, 0.5 seconds or more or 1 second. It can be more than that. In the first light irradiation step, when adjusting the irradiation time of light within the above range, a wrinkled surface of the above-described shape and size is formed, and surface characteristics (e.g., surface roughness, glossiness) of the above-described degree are formed. It is advantageous in securing ).

In this case, the light control time may be controlled in a manner of adjusting the moving speed of the resin composition to be irradiated with light. For example, when the device as shown in FIG. 6 is used, the light irradiation time can be controlled while appropriately adjusting the moving speed of the substrate layer coated with the composition on the conveyor belt within the range of 1 to 50 m/min.

In the second light irradiation step, the coating composition is coated on the substrate layer and wrinkled on the surface through the first light irradiation step, and light energy of a wavelength different from that of the first light irradiation step is applied to cure the coating composition and cure. This is the step of forming a layer.

In one example, in the second light irradiation step, light having a wavelength within a range of 200 to 400 nm may be irradiated. Specifically, the second light irradiation step includes 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. It may be a step to investigate. The upper limit of the light wavelength irradiated in the second light irradiation step may be, for example, 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. The coating composition in which wrinkles are formed on the surface while curing is performed only to a certain level by the first light irradiation step may be cured in the thickness direction (applied) while going through the second light irradiation step in which a relatively long wavelength is irradiated.

In one example, the second irradiation step may be a step of irradiating light having a higher wavelength than the first irradiation step in the above-described wavelength range.

When performing the second light irradiation step, the temperature of the surface of the composition in which wrinkles are formed on the surface through the first light irradiation step may be 100° C. or less. That is, the composition in which wrinkles are formed on the surface through the first light irradiation step may be subjected to the second light irradiation step under the condition that the temperature of the surface is maintained at 100°C or less. The corresponding temperature condition may be appropriately performed by a person skilled in the related art. More specifically, the temperature may be, for example, 90°C or less, 80°C or less, or 70°C or more, and its lower limit is, for example, 10°C or more, 20°C or more, 30°C or more, 40°C or more, 50°C It may be greater than or equal to or greater than 60°C. When it exceeds the above range, the durability of the base layer may decrease.

The second light irradiation step is performed in an air atmosphere. The curing rate of the composition may be improved through an air atmosphere, and the surface of the cured layer may be cleaned _{while oxygen molecules (O 2} ) are converted to ozone (O _{3) during the irradiation process.}

In one example, 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 layer to the light source may be 20 mm or less. Specifically, the upper limit of the distance is, for example, 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 It may be less than or equal to, and its lower limit may be, for example, 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. In another example, when the second light irradiation step is performed, a distance between the composition and the light source may be smaller than that at the first light irradiation step. During the second light irradiation, when the distance between the composition and the light source is adjusted within the above range, it is advantageous to form a corrugated surface of the above-described shape and size, and to secure surface properties of the above-described degree. When the distance is adjusted as described above, it is advantageous to form a surface temperature of the composition in the range as described above.

In one example, an irradiation amount of light irradiated in the second light irradiation step may be greater than an irradiation amount of light irradiated in the second light irradiation step. For example, the irradiation amount of light irradiated in the second light irradiation step is 150 mJ/cm 2 or more, specifically 160 mJ/cm 2 or more, 170 mJ/cm 2 or more, 180 mJ/cm 2 or more, 190 mJ/cm 2 or more, 200 It may be mJ/cm2 or more, 210 mJ/cm2 or more, 220 mJ/cm2 or more, 230 mJ/cm2 or more, 240 mJ/cm2 or more, 250 mJ/cm2 or more, or 300 mJ/cm2 or more. And the upper limit may be, for example, 350 mJ/cm2 or less, 340 mJ/cm2 or less, 320 mJ/cm2 or less, 310 mJ/cm2 or less, or 300 mJ/cm2 or less. At the time of the second light irradiation, when the amount of light irradiation is adjusted to the above range, a surface with wrinkles of the shape and size described above is formed, and surface characteristics (eg, surface roughness, glossiness) of the above-described degree are secured. It is advantageous to do.

In one example, the time when light is irradiated in the second light irradiation step may be the same as or different from the time when light is irradiated in the first light irradiation step described above. Specifically, the light irradiation time in the second light irradiation step may be at the level of several seconds, for example, the upper limit may be 10 seconds or less or 5 seconds or less, and the lower limit may be, for example, 0.5 seconds or more or 1 second or more. have.

When the first light irradiation and the second light irradiation are performed as described above, the surface of the hardened layer may have a relatively dense hardening density. Specifically, at the time of the first light irradiation, light having a relatively high energy short wavelength (light of about 200 nm or less) acts in the vicinity of several hundred nm near the surface of the coated cured layer, and when the second light is irradiated thereafter, the cured layer The surface of will have a dense hardening density. However, since the short wavelength light used for the first light irradiation does not affect the inside of the cured layer, the curing density inside the cured layer may be relatively low. Accordingly, the inside of the cured layer having a relatively low curing density can contribute to securing flexibility, and the surface of the cured layer having a dense cured state can maintain distinct wrinkles. Further, the densely cured surface improves stain resistance and solvent resistance.

In another example related to the present application, the present application relates to a decor film or a decor sheet including the laminated film. The decor film may be used for decoration or furniture. Furniture or decor can have curves, corners and/or flat surfaces.

For example, a door, a desk, a chair, or a shelf may be used as the furniture, and the decorative material may refer to an article that is used as a part of the furniture or can be used alone.

In another example related to the present application, the present application relates to a coating treatment agent, that is, a composition capable of providing a cured layer of the laminated film as described above. The specific composition of the composition is as described above.

According to an example of the present application, there is provided a laminated film having excellent matte properties and stain resistance at the same time known as a trade-off relationship with each other in the prior art.

1 is an image photographing the surface of a matte film manufactured according to an example of the present application.
2 is an image photographing the surface of a matte film manufactured according to the prior art. Specifically, FIG. 2 is a photograph of the surface of a matte film manufactured using a matting agent.
3 is for explaining wrinkles formed on the surface of a matte laminated film manufactured according to an example of the present application. In FIG. 3, colored dotted lines are marks for visually explaining wrinkles Wa and/or Wb.
4 is a photograph of various surface shapes that a laminated film manufactured according to an example of the present application may have.
5 illustrates some of the typical irregularities on the surface of the hardened layer formed according to an example of the present application. Fig. 5(a) is a corrugation of a radial structure, Fig. 5(b) is a corrugation of a Y-shaped structure, Fig. 5(c) is a corrugation of a sand wave type structure, and Fig. 5(d) is The corrugation of a tensioned-web type structure is shown.
6 schematically shows an apparatus for performing curing according to an example of the present application.

Hereinafter, the present application will be described in detail through Examples and Comparative Examples. However, the scope of the present application is not limited by the following examples.

Examples and Comparative Examples

Example 1

(1) Preparation of a composition for forming a cured layer

Urethane (meth)acrylate oligomer 50 parts by weight, monofunctional (meth)acrylic monomer having an amide group or hydroxy group 40 parts by weight, tricyclodecane dimethanol diacrylate (TCDDA, Tricyclodecane dimethanol diacrylate) 10 parts by weight, initiator 1 -A composition comprising 3 parts by weight of 1-hydroxycyclohexyl phenyl ketone and 3 parts by weight of colloidal silica particles (particle diameter in the range of 3 to 7 μm) was prepared.

At this time, the oligomer component is the first urethane (meth)acrylate oligomer (the weight average molecular weight is in the range of about 3,000 to 4,000, the number of functional groups is 3 to 10) and the second urethane (meth)acrylate oligomer (weight average The molecular weight was in the range of 1,000 to 2,000, and the number of functional groups was adjusted so that each content ratio (W1/W2) of the first urethane (meta) acrylate) was in the range of 1 to 1.8.

(2) formation of hardened layer

The composition prepared as described above was directly applied on a glycol-modified polyethylene terephthalate (PETG) substrate (about 15 cm wide, about 30 cm long, about 300 to 500 μm thick) and applied to a light curing device having a structure as shown in FIG. Fixed. Thereafter, while moving the substrate at a moving speed of 20±1 m/min, light irradiation was performed in stages as shown in Table 1 below to prepare a laminated film having a cured layer formed on the substrate layer.

[Table 1]

Comparative Example 1

70 parts by weight of urethane (meth)acrylate oligomer (using the same two types as in the examples), 20 parts by weight of a monofunctional (meth)acrylic monomer having an amide group or a hydroxy group, and tricyclodecane dimethanol diacrylate (TCDDA, Tricyclodecane A film was formed under the same conditions and procedures as in Example 1, except that 10 parts by weight of dimethanol diacrylate) was used.

Comparative Example 2

50 parts by weight of urethane (meth)acrylate oligomer (using the same two types as in the examples), 25 parts by weight of a monofunctional (meth)acrylic monomer having an amide group or a hydroxy group, tricyclodecane dimethanol diacrylate (TCDDA, Tricyclodecane dimethanol A film was formed under the same conditions and procedures as in Example 1, except that 25 parts by weight of diacrylate) was used.

Comparative Example 3

70 parts by weight of urethane (meth)acrylate oligomer (using the same two types as in the examples), 10 parts by weight of a monofunctional (meth)acrylic monomer having an amide group or a hydroxy group, tricyclodecane dimethanol diacrylate (TCDDA, Tricyclodecane dimethanol A film was formed under the same conditions and procedures as in Example 1, except that 20 parts by weight of diacrylate) was used.

Comparative Example 4

The same conditions as in Example 1 and the same conditions as in Example 1, except that 70 parts by weight of urethane (meth) acrylate oligomer (using the same two types as in the Example) and 30 parts by weight of tricyclodecane dimethanol diacrylate (TCDDA, Tricyclodecane dimethanol diacrylate) were used. A film was formed in the process.

Experimental example

For the laminated film (substrate layer/cured layer) prepared as described above, surface hardness, surface roughness (Rz), 60° gloss (G), and stain resistance were measured according to the following method. The measurement results are shown in Table 2.

* Surface hardness: The hardness of the laminated film was measured according to ISO 4586-2 using a scratch tester (Erichsen scratch tester 413). Specifically, the diamond tip mounted on the tester draws a circle (rotation speed: 5 times/min) with a load of 0 to 1 N and passes the film surface, and then judges the presence or absence of scratches on the film surface where the tip has passed. I did. At this time, in determining the presence of scratches, the condition for observing the presence of scratches on the film, that is, the distance between the evaluator's eyes and the film is not officially determined, but when the laminated film is positioned 10 cm in front of the evaluator's eyes and viewed in a bright place under a fluorescent lamp. The load that does not generate scratches was confirmed.

* Surface roughness (Rz): The surface roughness (Rz) of the laminated film was measured based on ISO 4287.

* 60° gloss (G): The 60° gloss (gloss 60° condition) of the laminated film according to ASTM D2457 was measured using a gloss meter.

* Pollution resistance: evaluated according to DIN68861-1 standard. The specific evaluation method is as follows. First, contaminants (Mustard/ink/coffee/wine) are soaked in a filter disk for 30 seconds and placed on the substrate, and then a small petri dish is covered thereto to prevent evaporation. Leave it for 16 hours as it is. Then, use a neutral detergent to wipe off the contaminants (for reference, the neutral detergent consists of 12.5% Sodium 4-Octylbenzene sulfonate, 12.5% Poly(ethylene glycol), 5% Ethanol, and 70% distilled water). Thereafter, the sample was left at room temperature (approximately 21 to 28°C) for 30 minutes, and if the wiped surface was damaged and fell off, 1 point, if the surface was not damaged, but the stain remains dark, 2 points, a mark of a degree that can be distinguished by the naked eye. 3 points are given if there are traces left, if there are marks found when looking closely at the surface where the contaminants have been wiped, such as tilting the sample, and 5 points if the contamination or traces as before are not observed and are clean. I did.

[Table 2]

100: light curing device
110: light irradiation room
111: first light irradiator
112: second light irradiator
120: light irradiated
130: conveyor belt
140: gas diaphragm
150: Psalm

Claims (15)

Base layer; And a cured layer located on at least one surface of the base layer and having a wrinkled surface,
The cured layer surface has a 60° gloss (G) of 5.5 or less,
The hardened layer A stain-resistant laminated film having a surface roughness (Rz) in the range of 3.5 to 10 µm. The stain-resistant laminated film according to claim 1, wherein the film has a surface hardness of 0.5 N or more measured with respect to the wrinkled surface of the cured layer. The stain-resistant laminated film according to claim 1, wherein the cured layer is a cured product of a composition comprising an oligomer component (A) and a monomer component (B). According to claim 3, wherein the composition comprises an oligomer of urethane (meth)acrylate having a weight average molecular weight (Mw) of 10,000 or less, stain-resistant laminated film. According to claim 4, wherein the composition comprises two or more urethane (meth) acrylate oligomers having a weight average molecular weight (Mw) different from each other, stain-resistant laminated film. According to claim 3, wherein the composition comprises 2 to 15 functional urethane (meth) acrylate oligomer, stain-resistant laminated film. According to claim 6, wherein the composition comprises two or more urethane (meth) acrylate oligomers having different numbers of functional groups from each other, stain-resistant laminated film. The method of claim 7, wherein the composition comprises a first urethane (meth)acrylate having a weight average molecular weight (Mw) in the range of 3,000 to 10,000 and a second urethane (meth)acrylate having a weight average molecular weight (Mw) of 500 or more and less than 3,000. Containing, stain-resistant laminated film. The stain-resistant laminated film according to claim 3, wherein the composition contains 30 parts by weight or more of the reactive monomer component (B) in 100 parts by weight of the total of the oligomer component (A) and the monomer component (B). The stain-resistant laminated film according to claim 9, wherein the reactive monomer is a monomer (b-1) having a polar functional group, and the polar functional group is a hydroxy group, an alkylene oxide group, or a nitrogen-containing functional group. The stain-resistant laminated film according to claim 10, wherein the composition further comprises a multifunctional monomer (b-2). The method of claim 11, wherein the content ratio (b-1:b-2) of the (meth)acrylic monomer (b-1) having a polar functional group and the polyfunctional monomer (b-2) is in the range of 5:1 to 3:1. Phosphorus, stain-resistant laminated film. The method of claim 12, wherein the content of the (meth)acrylic monomer (b-1) having a polar functional group is 20 parts by weight or more in 100 parts by weight of the sum of the oligomer component (A) and the monomer component (B). film. A first light irradiation step of irradiating the composition coated on the substrate layer with light (L ₁ ) of a predetermined wavelength under inert gas conditions to form wrinkles on the surface of the applied composition; And
Including a second light irradiation step of forming a cured layer that is a cured product of the composition by irradiating light (L ₂ ) of a longer wavelength than the light (L _{1) under air conditions.}
A method of manufacturing a laminated film according to claim 1 comprising a base layer and a cured layer. The method of claim 14, wherein the light (L ₂ ) includes a base layer and a cured layer having a wavelength within a range of 200 to 400 nm.

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