KR20240032801A - laminated film having wrinkle surface - Google Patents

Abstract

This application relates to laminated films. The film has a soft touch and matte characteristics and is excellent in stain resistance. In particular, the above-described surface properties can be maintained even after the laminated film is stretched.

Description

Laminated film having wrinkled surface

This application relates to a laminated film with a corrugated surface. Specifically, the present application relates to a laminated film with excellent stain resistance, matte characteristics, and touch sensitivity, and the laminated film of the present application can maintain the above characteristics even after tensile force is applied.

When manufacturing building interior materials or furniture films, deco sheets with matte characteristics (or low-glow characteristics) are widely used. For example, a technology for producing a matte decor sheet is being used by applying a coating agent containing a matting agent (e.g., silica, etc.) onto a substrate and then curing it.

The surface of a decor sheet formed through a coating treatment agent is required to have high durability as well as excellent surface hardness. At the same time, the decor sheet must also have flexible characteristics considering when it is applied to furniture, etc. However, when surface hardness is excellent, flexibility is generally lowered. Additionally, when tension is applied to the sheet, the physical properties of the sheet before tensioning may change.

Meanwhile, in relation to the realization of the matte characteristics of the decor sheet, general matting agents are porous and have a low apparent specific gravity, so they are located on the surface layer of the coating and increase the surface adsorption of foreign substances (e.g. fine dust, moisture, grease, etc.) It may also deteriorate the stain resistance of the sheet.

In addition, in recent years, in line with the trend toward higher quality decoration sheets, the demand for decoration sheets with a soft-touch surface in addition to matte characteristics is also increasing.

Therefore, it is important to develop a decor sheet that can achieve excellent tactile and matte characteristics while having stain resistance equal to or higher than that of conventional products, and that can maintain the above characteristics even when tensile force for processing is applied in actual use. It is required.

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

One purpose of the present application is to provide a film that not only has excellent surface properties such as touch, matte properties, and stain resistance, but also maintains the above surface properties even when tensile force is applied.

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

In one example related to this application, this application relates to a laminated film comprising a base layer and a cured layer.

In one example, the laminated film includes a base layer; and a cured layer located on at least one side of the base layer and having a wrinkled surface, wherein the surface of the cured layer has a roughness (Rz1) in the range of 3.5 to 10.0 ㎛ and a 60° glossiness (G1). ) is in the range of 4.0 to 6.0, and the film is left at 80° C. for 1 minute and stretched at 14% at a rate of 100 mm/min. After stretching, the roughness (Rz2) of the surface of the cured layer is in the range of 3.0 to 10.0 ㎛, and 60° The glossiness (G2) is in the range of 4.0 to 6.0, and the surface roughness reduction rate of the hardened layer calculated by the following equation 1 after stretching is 15% or less,

[Relationship 1]

Surface roughness reduction rate (%) = {(Rz1-Rz2) x 100}/Rz1

After the stretching, the increase rate of gloss of the cured layer calculated by Equation 2 below is in the range of 15% or less.

[Relational Expression 2]

Glossiness increase rate (%) = {(G2- G1) x 100}/G1

(G2 is 60° gloss after stretching)

The cured layer has a wrinkled surface. The surface on which the wrinkles are formed is a side opposite to the side of the cured layer that faces the base layer. The wrinkled surface may impart desired surface properties (e.g., surface hardness, gloss, elongation, etc.) to the laminated film as described below.

In this application, “surface with wrinkles” (hereinafter referred to as surface (Swrinkle)) means that the cured layer includes wrinkles on at least one surface, and the cured layer has three-dimensional surface irregularities due to the wrinkles. (see Figure 1). For example, the surface (swrinkle) has irregularities including large and small ridges, valleys, and wrinkles formed therefrom that can be visually recognized as having a predetermined shape. Each of the ridges, valleys, and wrinkles may have a regular or irregular shape. This wrinkled surface may also be referred to as a surface having a fine folding structure.

When observing the surface of the cured layer (Swrinkle) with wrinkles formed in the normal direction of the cured layer, ridges, valleys, wrinkles, and irregularities formed therefrom are, for example, of the surface (Swrinkle) through the curing process described below. Observed across all areas. Observation of wrinkles or surface irregularities described in the present application over the entire area of the surface of the cured layer may be expressed as satisfying the surface properties described below (e.g., matte properties, surface roughness, stain resistance, and retention of the above features after elongation). You can.

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

The surface uneven structure formed by line-shaped wrinkles as described above is a so-called point-wise uneven shape (Figure (see 2) is clearly distinguished from

In one example, the surface (Wrinkle) may include a wrinkle (Wa) that can be visually recognized as having a predetermined size and shape. Specifically, the wrinkles may have a width in the range of several to dozens of ㎛ and a line (straight or curved) shape extending to a length in the range of several to hundreds of ㎛.

The width of the wrinkle and the length to which the wrinkle extends can be confirmed from an image (eg, SEM) taken of the surface on which the wrinkle is formed, as shown in the attached drawing. At this time, the length in the extension direction is greater than the width (see Figure 3).

Specifically, the ends of the wrinkles (Wa) extending in a straight or curved shape form a slope that gradually decreases in height and may be incorporated into the hardened layer. In some cases, the end of one wrinkle Wa 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 the cross-sectional curve near the wrinkle in the direction perpendicular to the direction of extension of the wrinkle Wa, the width of the wrinkle is the height in both directions starting from the point or part (e.g., ridge) that forms the height of the wrinkle. It forms a gradually decreasing slope and can be mixed into the hardened layer. Meanwhile, when a ridge and an adjacent valley form a wrinkle or a part thereof, the area of the visible shape including the valley can be viewed as the width of the wrinkle Wa.

In one example, the width of the wrinkles Wa may be, for example, 1 ㎛ or more, 2 ㎛ or more, or 3 ㎛ or more. And, the upper limit of the width of the wrinkles Wa may be, for example, 20 ㎛ or less, 15 ㎛ or less, 10 ㎛ or less, or 5 ㎛ or less. When the above range is satisfied, it may be advantageous for the surface formed by wrinkles to have the desired properties in the present application.

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

The wrinkles Wa may have a predetermined height for most of the extending length. For example, the wrinkles Wa may have a height of 1 ㎛ or more. Specifically, when observing the cross-sectional curve of a wrinkle in a direction perpendicular to the direction of extension of the wrinkle, a point or part forming the height of the wrinkle (e.g., a ridge) and a point or part of the hardened layer where the width of the wrinkle mix ( Example: valley) may have a height difference of at least 1 ㎛. At this time, the majority of the length at which the height is observed is 70% or more, 75% or more, 80% or more, 85% or more, or 90% or more or 95% of the length where the wrinkle Wa continuously extends along its shape. It means a length greater than or equal to . The height difference gradually decreases in the direction in which the wrinkles extend, and when the height becomes 1 ㎛ or less, a shape in which the ends of the wrinkles are incorporated into the hardened layer may be observed, or the size or shape may be similar to that of the wrinkles (Wa). A shape where a contact point with another different wrinkle begins may be observed. In the latter case, a more complex wrinkle structure can form irregularities on the surface (swrinkle).

The wrinkles (Wa) are observed over the entire surface (Swrinkle), and may form surface wrinkles or irregularities while showing regular or irregular distribution. Observation of wrinkles or surface irregularities described in the present application over the entire area of the surface of the cured layer may be expressed as satisfying the surface properties described below (e.g., matte properties, surface roughness, stain resistance, and retention of the above features after elongation). You can.

For example, on the surface (Swrinkle), the wrinkles (Wa) may have a shape in which a plurality of wrinkles (Wa) branch in different directions from one specific point, forming surface irregularities.

For example, the wrinkle (Wa) on the surface (Swrinkle) may have a shape similar to “Y” or “〈” (i.e., the wrinkle may be recognized as a shape similar to “Y” or “〈” ). At this time, wrinkles similar in shape to “Y” or “〈” may be densely arranged to form surface irregularities.

For example, on the surface (Swrinkle), the wrinkles (Wa) may form surface irregularities in a form in which branching in other directions is suppressed and the wrinkles (Wa) are distributed while generally extending in one direction.

The shape and arrangement of the wrinkles Wa forming the surface irregularities as described above are exemplary. Additionally, one or more wrinkles of the shape or form described above may be observed on a surface having irregularities (wrinkle).

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

In one example, the surface (Swrinkle) may include a wrinkle (Wb) whose size and/or shape is different from the wrinkle (Wa). For example, a wrinkle that does not satisfy one or more of the width, length, and height of the wrinkle (Wa) may be referred to as a wrinkle (Wb). Specifically, a case where one or more of the width, length, and height is larger or smaller than that of the wrinkle Wa defined as above may be defined as the wrinkle Wb.

In one example, if many wrinkles larger than the wrinkles Wa are observed on the surface, it may be an obstacle to securing surface properties.

In one example, the wrinkles Wb are observed over the entire surface of the surface, and may form surface irregularities while showing regular or irregular distribution. Observation of wrinkles or surface irregularities described in the present application over the entire area of the surface of the cured layer may be expressed as satisfying the surface properties described below (e.g., matte properties, surface roughness, stain resistance, and retention of the above features after elongation). You can.

For example, on the surface (Swrinkle), the wrinkles (Wb) may have a shape in which a plurality of wrinkles (Wb) branch in different directions from one specific point, forming surface irregularities.

For example, the wrinkle (Wb) on the surface (Swrinkle) may have a shape similar to “Y” or “〈” (i.e., the wrinkle may be recognized as a shape similar to “Y” or “〈” ). At this time, wrinkles similar in shape to “Y” or “〈” may be densely arranged to form surface irregularities.

For example, on the surface (Swrinkle), the wrinkles (Wb) may form surface irregularities in a form in which branching in other directions is suppressed and generally extend and are distributed in one direction.

The shape of the wrinkles Wb forming the surface irregularities as described above is exemplary. Additionally, one or more wrinkles of the shape or form described above may be observed on a surface having irregularities (wrinkle).

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

In one example, the unevenness of the surface (Swrinkle) may be formed by wrinkles (Wa, Wb).

In one example, the wrinkles (Wb) may form a hardened layer surface (Swrinkle) while located adjacent to the wrinkles (Wa). For example, when observed from the normal direction of the hardened layer, a valley or ridge may exist between the wrinkles Wa and the wrinkles Wb.

In another example, the wrinkles (Wb) are physically connected to the wrinkles (Wa), for example, have a shape or form in which the wrinkles (Wb) with a low height or small width branch from the wrinkles (Wa). may have, and these wrinkles (Wa, Wb) may form the hardened layer surface (Swrinkle). The direction or length of the wrinkles Wb branching from the wrinkles Wa are not particularly limited.

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

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

For example, the surface may be a surface on which radial wrinkles are formed (see FIG. 5A). The radial shape may be a shape in which a plurality of wrinkles with the same or different directions extend from a certain point (center). The radial wrinkles may include wrinkles Wa. Additionally, the radial wrinkles may include wrinkles Wb. These wrinkles can be observed over the entire surface of the cured layer, and for example, they can be distributed on the surface to a degree that satisfies the surface properties below while going through the curing process described below. Additionally, in some cases, wrinkles extending directionally from the center may have a shape where their height gradually decreases as they move away from the center.

For example, the surface may be a surface on which Y-shaped (or Y-tile pattern) wrinkles are formed (see FIG. 5B). The Y-shape may be a shape in which a plurality of wrinkles with three different directions extend from a certain point (center). In the case of the Y-type, when observing the surface of the hardened layer, it is generally sufficient if Y-shaped curves are observed over most of the surface area, and three directional wrinkles must be formed from a certain point so that only curves with an exact Y shape are observed. It does not have to have an expanding shape. The wrinkles forming the Y shape may include wrinkles Wa. Additionally, the Y-shaped wrinkles may include wrinkles Wb. These wrinkles can be observed over the entire surface of the cured layer, and for example, they can be distributed on the surface to a degree that satisfies the surface properties below while going through the curing process described below. Additionally, in some cases, wrinkles extending directionally from the center may have a shape where their height gradually decreases as they move away from the center.

For example, the surface may be a surface on which sand wave-type wrinkles are formed (see FIG. 5C). Compared to surface wrinkles of other shapes, the sand wave type has a lower depth and is more evenly distributed. Wrinkles forming a sand wave shape may include wrinkles Wa. Additionally, the wrinkles forming the sand wave shape may include wrinkles Wb. These wrinkles can be observed over the entire surface of the cured layer, and for example, they can be distributed on the surface to a degree that satisfies the surface properties below while going through the curing process described below.

For example, the surface may be a surface with tensioned-web type wrinkles (see FIG. 5D). The tensioned-web type has wrinkles formed to be generally arranged in one direction, and other wrinkles arranged in a direction that intersects them (which are also generally arranged in one direction). It may have the same shape as a web formed by the web. At this time, the intersection angle is not particularly limited. In the case of the tensioned-web type, the wrinkles formed to be generally arranged in one direction can be recognized as extending over the entire surface area. The wrinkles forming the tensioned-web type may include wrinkles Wa. Additionally, the wrinkles forming the tensioned-web type may include wrinkles Wb. These wrinkles can be observed over the entire surface of the cured layer, and for example, they can be distributed on the surface to a degree that satisfies the surface properties below while going through the curing process described below.

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

In the hardened layer having a wrinkled surface as described above, the surface has predetermined surface characteristics.

Specifically, the cured layer has a surface roughness (Rz1) of the wrinkled surface in the range of 3.5 to 10.0 ㎛, and a 60° glossiness (G1) of the wrinkled surface in the range of 4 to 6. Surface roughness (Rz1) refers to the surface roughness (Rz) measured on the wrinkled surface before performing stretching on the film as described below. Additionally, 60° glossiness (G1) refers to the 60° glossiness (G) measured on the wrinkled surface prior to stretching of the film as described below.

In this application, “surface roughness (Rz)” may be measured according to ISO 4281 and may also be referred to as ten point average roughness. Specifically, the surface roughness is calculated by taking the reference length (L) as the cross-sectional curve of the surface of the hardened layer and measuring the peaks (ridges) from the high side of the curved structure to the fifth in a straight line that does not cut the cross-sectional curve transversely parallel to the average line of the portion. ) and the 5th valley from the deep side are measured to show the deviation, and it is a value that expresses the degree of unevenness. At this time, the reference length (L) may be several mm, for example, in the range of about 0.1 to 1 mm, specifically about 0.8 mm.

In this application, “60° glossiness (G)” can be measured using a gloss meter according to ASTM D2457, and is a value expressing the degree of gloss of the surface (GU: gloss unit). The lower the gloss, the closer it is to matte.

In one example, the surface roughness (Rz1) of the surface on which wrinkles are formed in the cured layer is 3.6 ㎛ or more, 3.7 ㎛ or more, 3.8 ㎛ or more, 3.9 ㎛ or more, 4.0 ㎛ or more, 4.1 ㎛ or more, 4.2 ㎛ or more, 4.3 ㎛ It may be more than, 4.4 ㎛ or more, or 4.5 ㎛ or more. And, the upper limit of the surface roughness is, for example, 9.5 ㎛ or less, 9.0 ㎛ or less, 8.5 ㎛ or less, 8.0 ㎛ or less, 7.5 ㎛ or less, 7.0 ㎛ or less, 6.5 ㎛ or less, 6.0 ㎛ or less, 5.5 ㎛ or less, or 5.0 ㎛ or less. It may be ㎛ or less. If the above surface roughness is satisfied, it may be advantageous to secure the required matte characteristics.

In one example, the 60° glossiness (G1) of the wrinkled surface of the cured layer is 4.1 or more, 4.2 or more, 4.3 or more, 4.4 or more, 4.5 or more, 4.6 or more, 4.7 or more, 4.8 or more, 4.9 or more, or 5.0. It could be more than that. And, the upper limit of the 60° glossiness (G1) may be, for example, 5.9 or less, 5.8 or less, 5.6 or less, or 5.5 or less. When the surface of the cured layer of the film has a 60° glossiness (G1) in the above range, it can provide users with beautiful matte characteristics.

The film of the present application can satisfy the surface roughness and glossiness in the range described above even after tensile force is applied. In other words, the film can maintain a soft touch, excellent stain resistance, and beautiful matte characteristics even after going through the stretching process. These properties can be secured through curing a composition of a certain composition through a certain step. The specific composition and curing process of the composition are described in detail below.

Specifically, the laminated film may satisfy a roughness (Rz2) of the surface of the cured layer measured after stretching in the range of 3.0 to 10 or a glossiness (G2) in the range of 4.0 to 6.0.

In this regard, the stretching may be performed while leaving the laminated film at a temperature ranging from 70 to 90° C. for less than 5 minutes and then stretching it by 20% or less. Specifically, the temperature at which the film is left may range from 75°C to 85°C, specifically about 80°C, and the time at which the film is left at this temperature may be 4 minutes or less, 3 minutes or less, or 2 minutes or less, specifically. It could be about 1 minute. In addition, as in the examples below, the tensioning of the film was performed by operating a tensioner so that the film cut to a predetermined size could be stretched to 20% or less in the length direction, that is, the elongation could be 20% or less. . The elongation may be, for example, less than 19%, less than 18%, less than 17%, less than 16%, or less than 15%. The lower limit of the degree of stretching is not particularly limited, but may be, for example, 5% or more or 10% or more. Preferred conditions are to leave it at 80°C for 1 minute and then reduce the concentration to 14% at a speed of 100 mm/min.

In one example, the surface roughness (Rz2) of the surface of the cured layer measured after stretching as described above may satisfy the range of 3 to 10 ㎛.

When stretching occurs, surface irregularities can be alleviated (i.e., wrinkles can be released), and as a result, surface roughness can be expected to decrease compared to before stretching. However, in the present application, even if the above-described stretching is performed, the surface roughness may not decrease significantly or may be maintained at the same level compared to before stretching. This is believed to be because the hardened layer formed through the composition and process below has a dense surface, and therefore the degree of change due to surrounding stimuli (e.g., tensile force) is low. Accordingly, even after stretching, the laminated film of the present application can maintain the same soft touch and stain resistance as secured before stretching.

For example, the surface roughness (Rz2) of the surface of the cured layer after stretching may be 3.1 ㎛ or more, 3.2 ㎛ or more, 3.3 ㎛ or more, 3.4 ㎛ or more, or 3.5 ㎛ or more. And, the upper limit of the surface roughness (Rz2) is, for example, 9.5 ㎛ or less, 9.0 ㎛ or less, 8.5 ㎛ or less, 8.0 ㎛ or less, 7.5 ㎛ or less, 7.0 ㎛ or less, 6.5 ㎛ or less, 6.0 ㎛ or less, 5.5 ㎛ or less. Or it may be 5.0 ㎛ or less.

In one example, the glossiness (G2) of the surface of the cured layer measured after stretching as described above may satisfy the range of 4.0 to 6.0.

When stretching occurs, surface irregularities can be alleviated (i.e., wrinkles can be released), and as a result, the matte effect caused by wrinkles can be expected to decrease and gloss to increase compared to before stretching. However, in the present application, even if the above-described stretching is performed, the glossiness may not increase significantly or may be maintained at the same level compared to before stretching. This is believed to be because the hardened layer formed through the composition and process below has a dense surface, and therefore the degree of change due to surrounding stimuli (e.g., tensile force) is low. Accordingly, even after stretching, the laminated film of the present application can maintain the matte properties secured before stretching at the same level.

For example, the 60° glossiness (G2) of the surface of the cured layer after stretching may be 4.1 or more, 4.2 or more, 4.3 or more, 4.4 or more, 4.5 or more, 4.6 or more, 4.7 or more, 4.8 or more, 4.9 or more, or 5.0 or more. . And, the upper limit of the 60° glossiness (G2) may be, for example, 5.9 or less, 5.8 or less, 5.6 or less, or 5.5 or less.

In one example, the laminated film may satisfy a roughness (Rz2) of the surface of the cured layer measured after stretching in the range of 3 to 10 ㎛, and a glossiness (G2) in the range of 4.0 to 6.0.

In another example, the laminated film may satisfy a roughness (Rz2) of the surface of the cured layer measured after stretching in the range of 3 to 5 ㎛, and a glossiness (G2) in the range of 4.0 to 5.0.

In one example, the laminated film may satisfy a surface roughness reduction rate (%) of the cured layer of 15% or less after stretching the film. The surface roughness reduction rate (%) of the hardened layer can be obtained by the following equation 1.

[Equation 1]

Surface roughness reduction rate (%) = {(Rz1 - Rz2) x 100}/Rz1

In Equation 1, Rz1 is the surface roughness (Rz) of the cured layer before stretching, and Rz2 is the surface roughness (Rz) of the cured layer after stretching. At this time, Rz1 and Rz2 may each have the range described above.

The surface roughness reduction rate may be, for example, 14% or less, 13% or less, 12% or less, 11% or less, or 10% or less, and the lower limit may be, for example, 0.1% or more, 1% or more, or 5% or more. there is.

A film that satisfies the surface roughness reduction rate (%) as described above can maintain the effect of securing surface roughness even after stretching.

In one example, the film may satisfy an increase rate (%) of 60° glossiness of the cured layer of 15% or less after stretching the film. The 60° glossiness (G) increase rate of the cured layer can be obtained using Equation 2 below.

[Equation 2]

60 ° gloss increase rate (%) = {(G2- G1) x 100}/G1

In Equation 1, G1 is the 60° glossiness (G) of the cured layer before stretching, and G2 is the 60° glossiness (G) of the cured layer after stretching. At this time, G1 and G2 may each have the range described above.

The gloss increase rate may be, for example, 14% or less, 13% or less, 12% or less, 11% or less, or 10% or less, and the lower limit may be, for example, 0.1% or more, 1% or more, or 5% or more. You can.

In an embodiment of the present application, a cured layer having the above properties can be obtained through curing a composition of a predetermined composition. Specifically, the cured layer may include a cured product of the curable composition.

In one example, the treatment agent used in this application, i.e., the coating composition, may be a photocurable solvent-free composition. That is, the composition may not contain solvents, such as organic solvents or aqueous solvents. When a solvent-free composition is used, the solvent drying process can be omitted, thereby increasing process efficiency. In addition, through the use of a non-solvent composition, it is possible to prevent deterioration of the surface properties required for the film of the present application due to bubbles generated as 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 including an oligomer component (A) and a monomer component (B). That is, after the photocuring treatment as described below is performed on a resin composition of a predetermined configuration, a cured layer having a wrinkled surface as described above can be produced.

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

The urethane acrylate that can be used in the present application may be manufactured by polymerizing compounds such as isocyanate, alcohol, and acrylate according to a known method to satisfy the following functionality and/or molecular weight. For example, a polyisocyanate having 3 or more isocyanate groups is reacted with an acrylate having a hydroxyl group in the molecule and containing 3 or more acrylic groups under a metal catalyst and a radical polymerization inhibitor until the isocyanate (NCO) disappears. , Urethane acrylate can be produced by adding 0 to 30% by weight of a UV curable monomer. Alternatively, urethane acrylate that satisfies the following functionality and/or molecular weight can be selected and used from commercial products.

In one example, the urethane (meth)acrylate oligomer may have a weight average molecular weight (Mw) of 30,000 or less. For example, the molecular weight of urethane (meth)acrylate may be 30,000 or less, 27,000 or less, 24,000 or less, 21,000 or less, 18,000 or less, specifically, for example, 19,000 or less, 18,000 or less, 17,000 or less, 16,000 or less, or 15,000 or less. It may be below. In addition, the lower limit of the weight average molecular weight (Mw) of the urethane (meth)acrylate oligomer is, for example, 1,000 or more, 2,000 or more, 3,000 or more, 4,000 or more, 5,000 or more, 6,000 or more, 7,000 or more, 8,000 or more, 9,000 or more. Or it may be 10,000 or more. When urethane (meth)acrylate that satisfies the weight average molecular weight of the above range is appropriately used, appropriate flexibility and hardness (durability) can be imparted to the cured layer. In particular, the inclusion of urethane (meth)acrylate oligomers in this weight average molecular weight range can greatly contribute to improving the elongation of the cured layer.

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

In one example, the composition may include a first urethane (meth)acrylate having a weight average molecular weight (Mw) in the range of 10,000 to 30,000. Specifically, the lower molecular weight limit of the first urethane (meth)acrylate may be, for example, 11,000 or more, 12,000 or more, 13,000 or more, 14,000 or more, 15,000 or more, 16,000 or more, or 17,000 or more, and the upper limit is 25,000 or less, 24,000 or more. It may be 23,000 or less, 22,000 or less, 21,000 or less, 20,000 or less, 19,000 or less, 18,000 or less, 17,000 or less, or 16,000 or less. When using urethane (meth)acrylate that satisfies the above range, it can be advantageous to improve hardness (durability) and flexibility.

In one example, the composition may further include urethane (meth)acrylate having a lower molecular weight than the first urethane (meth)acrylate. Specifically, the composition may include, in addition to the first urethane (meth)acrylate having a weight average molecular weight (Mw) of 10,000 to 30,000, a second urethane (meth)acrylate having a weight average molecular weight (Mw) of less than 10,000. You can.

The lower molecular weight limit of the second urethane (meth)acrylate may be, for example, 1,000 or more, specifically 1,500 or more, 2,000 or more, 2,500 or more, or 3,000 or more. And the upper limit of the molecular weight may be, for example, 9,000 or less or 8,000 or less, and more specifically, 5,000 or less, 4,500 or less, 4,000 or less, and 3,500 or less. If only the first urethane (meth)acrylate with a relatively high molecular weight is used, the cured density may decrease and the cured structure may not be dense. To compensate for this, a second urethane (meth)acrylate having a relatively low weight average molecular weight can be used. In addition, if only the second urethane (meth)acrylate with a low molecular weight is used, it may be disadvantageous in securing flexibility, but in the present application, the above-mentioned surface properties are secured by using the first and second urethane (meth)acrylate simultaneously. can do.

In one example, the urethane (meth)acrylate oligomer may include one or more photopolymerizable functional groups. Specifically, the urethane (meth)acrylate oligomer may be a monofunctional oligomer or a multifunctional oligomer having two or more functional groups. The number of functional groups of the multifunctional oligomer is not particularly limited, but considering technical issues, it may be, for example, within the range of 6 to 10 or within the range of 6 to 9.

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.

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

In one example, the first urethane (meth)acrylate oligomer may have 2 or 3 or more functional groups. In an embodiment, the number of functional groups of the first urethane (meth)acrylate oligomer may be within the range of 6 to 10 or within the range of 6 to 9, specifically 6, 7, 8, or 9.

In one example, the second urethane (meth)acrylate oligomer may have 2 or 3 or more functional groups. In an embodiment, the number of functional groups of the first urethane (meth)acrylate oligomer may be within the range of 6 to 10 or within the range of 6 to 9, specifically 6, 7, 8, or 9.

In one example, the number of functional groups of the first urethane (meth)acrylate oligomer may be smaller than the number of functional groups of the second urethane (meth)acrylate oligomer. For example, when the number of functional groups of the first urethane (meth)acrylate oligomer is in the range of 6 to 9, the number of functional groups of the second urethane (meth)acrylate oligomer is in the range of 6 to 9. It may be larger than the number of functional groups of an acrylate oligomer. As described above, when urethane (meth)acrylate satisfies a predetermined number of functional groups and a predetermined molecular weight range, the effect of improving flexibility by securing a flow site can be obtained while increasing the level of curing. As a result, the use of urethane acrylate as described above can contribute to providing a film with excellent surface hardness, flexibility, and stain resistance.

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

The composition may include 20 to 70 parts by weight of the oligomer component (A) based on 100 parts by weight of the 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 be in the range of 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, 1.2 or more, 1.4 or more, 1.6 or more, or 1.8 or more, and the upper limit may be, for example, 1.9 or less, 1.8 or less. , may be 1.7 or less, 1.6 or less, or 1.5 or less. The weight ratio can be appropriately adjusted considering excellent hardness, flexibility, and stain resistance.

If the cured layer is mainly formed by photocuring oligomers, flexibility may be insufficient and it may be disadvantageous to secure the surface properties described above. Accordingly, the composition includes reactive monomer components in addition to oligomers. In addition, the reactive monomer component functions like a kind of solvent and can lower the viscosity of the composition (compared to the case where it contains only the oligomer component), thereby improving the coating processability for the base layer.

In one example, a monofunctional or polyfunctional monomer may be used as the reactive monomer component (B). For example, the composition may include 30 parts by weight or more or 35 parts by weight or more of the reactive monomer component (B) out of 100 parts by weight of the oligomer component (A) and the monomer component (B). When the above range is satisfied, it is advantageous to increase the reaction rate of the composition and increase the curing density to secure surface hardness in the range described above.

The upper limit of the content of the reactive monomer component (B) can be appropriately adjusted in consideration of the effects of using urethane (meth)acrylate described above. For example, out of 100 parts by weight 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 or less. Hereinafter, the reactive monomer component (B) may be used in an amount of 50 parts by weight or less or 45 parts by weight or less.

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. Monomers with polar functional groups are advantageous for speeding up the curing reaction and increasing the curing density. Specifically, the reactive monomer may be a (meth)acrylic monomer having a polar functional group.

Although not particularly limited, hydroxy group-containing (meth)acrylic monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxybutyl (meth)acrylate. 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, a functional group containing nitrogen in the molecule may include, 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, but is limited thereto. That is not the case. 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-methylacrylamide, (meth)acryl Amide, alkyl (meth)acrylamide, dialkyl (meth)acrylamide, hydroxy alkyl (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. can be used. .

In the case of monomers having alkylene oxide, for example, alkoxy alkylene glycol (meth)acrylic acid ester, alkoxy dialkylene glycol (meth)acrylic acid ester, or alkoxy polyethylene glycol (meth)acrylic acid ester may be used, but in particular, 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, the ratio (w3/w1) between the content (W1) of the first urethane (meth)acrylate and the content (w3) of the reactive monomer (B) component may be in the range of 1.0 to 3.0. When the above content range is satisfied, it is advantageous to appropriately secure coating processability, surface hardness, and flexibility.

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, the ratio (w3/w2) between the content (W2) of the second urethane (meth)acrylate and the content (w3) of the reactive monomer (B) component may be in the range of 1.0 to 2.5. When the above content range is satisfied, it is advantageous to appropriately secure coating processability, surface hardness, and flexibility.

In one example, the reactive monomer component (B) in 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. Multifunctional monomers increase curing strength and provide 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 tricyclodecane dimethanol di(meth)acrylate. 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 monomer; Trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propylated trimethylolpropane tri(meth)acrylate ) trifunctional (meth)acrylate monomers such as acrylate, glyceryl propylated tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, etc.; Tetrafunctional (meth)acrylate monomers such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, etc.; penta-functional (meth)acrylate monomers such as dipentaerythritol penta(meth)acrylate, dipentaerythritol hydroxypenta(meth)acrylate, etc.; A pentafunctional (meth)acrylate monomer such as dipentaerythritol hexa(meth)acrylate may be used.

The number of functional groups of the multifunctional monomer may be appropriately selected in consideration of gloss. For example, if the number of functional groups is too high, glossiness may increase. In one example, the number of functional groups of the multifunctional monomer component may be in the range of 2 to 5, 2 to 4, or 2 to 3.

As described above, when using a reactive monomer, specifically a reactive monomer 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, a problem of deterioration of contamination resistance may occur. Therefore, by using a predetermined amount of a component with a larger number of functional groups, such as multifunctional (meth)acrylate, it is possible to increase curing density and reduce the possibility of polar functional groups being exposed to the surface of the cured layer, thus preventing deterioration of contamination resistance. For example, the composition may include 5 parts by weight or more or 10 parts by weight or more of the multifunctional (meth)acrylate monomer based on 100 parts by weight of the oligomer component (A) and the monomer component (B).

In one example, the composition may include 15 parts by weight or less of the multifunctional (meth)acrylate monomer, based on 100 parts by weight of the oligomer component (A) and the monomer component (B). Specifically, the content of the multifunctional (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. If the content of the multifunctional monomer exceeds the above range, the viscosity may increase, resulting in poor coating processability of the cured composition, and the gloss of the cured layer may increase, making it difficult to secure the desired matte properties of the laminated film.

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 initiator is not particularly limited, and known commercial products can also be used.

The content of the initiator is not particularly limited. For example, the composition may include 10 parts by weight or less of an initiator based on 100 parts by weight of the oligomer component (A) and the monomer component (B) combined. 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 part by weight or 0.5 part by weight. As explained below, in the present application, stepwise curing is performed when curing the cured layer, so curing efficiency is excellent even when a small amount of 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, the type is not particularly limited, and known commercial products can also be used.

The content of the light stabilizer is not particularly limited. For example, the composition may include 10 parts by weight or less of a light stabilizer, based on 100 parts by weight of the 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 part by weight or 0.5 part by weight. Light stabilizers can prevent damage to laminated films caused by ultraviolet rays.

In one example, the composition for forming the cured layer may not contain a matting agent 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 by increasing the scattering rate of light on the surface of the film. However, the use of a matting agent brings about the problem of increased contamination resistance, as explained previously. However, since the cured layer of the present application has the above-mentioned surface characteristics, it can effectively implement matte characteristics. Therefore, sufficient matte characteristics can be achieved in the film of the present application without using a matting agent that was used to achieve a matte effect in the prior art.

In addition, even if a matting agent is used, the matting agent may not be used in the same amount as was used to realize matte properties in the prior art. That is, according to the present application, the amount of matting agent used can be significantly reduced. For example, the composition contains 5 parts by weight or less, specifically 4 parts by weight or less, 3 parts by weight, 2 parts by weight or less, or 1 part by weight, based on 100 parts by weight of the oligomer component (A) and the monomer component (B). It may contain a matting agent component by weight. Accordingly, the film of the present application has the advantage of preventing problems such as a decrease in stain resistance due to the use of a matting agent.

In one example, a composition for forming a cured layer that does not contain a particulate matting agent as an additive or uses a small amount such as the above amount may have a low viscosity, for example, a viscosity of 500 cps or less at room temperature. Specifically, if an excessive amount of additives in the form of particles are used to achieve a matte effect, the viscosity of the composition increases, and as a result, coating workability on the base layer is poor. However, in the present application, since the matting agent is not used or can be used in significantly less amount than in the prior art as described above, the composition for forming the cured layer is, for example, 450 cps or less, 400 cps or less, 350 cps or less, 300 cps at room temperature. It may have a viscosity of less than or equal to 250 cps. The lower viscosity limit of the composition may be, for example, at least 150 cps, at least 200 cps, at least 250 cps, at least 300 cps, at least 350 cps, or at least 400 cps. At this time, room temperature refers to a temperature in a particularly reduced or non-heated state, and is a temperature in the range of about 18 to 32 ℃, specifically a temperature in the range of 22 to 28 ℃, a temperature in the range of 23 to 27 ℃, or about 25 ℃. It can mean the temperature of . Additionally, the viscosity can be measured according to a known method using a Brookfield viscometer.

The thickness of the hardened layer is not particularly limited as long as the above surface characteristics are satisfied. For example, the thickness of the cured layer may be 3 ㎛ or more, 5 ㎛ or more, 10 ㎛ or more, or 15 ㎛ or more, provided that the surface properties are satisfied. Also, for example, the thickness of the cured layer is 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 ㎛. It may be below.

The type of 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 it is not particularly limited, considering the suppression of whitening phenomenon, mechanical properties such as impact resistance, ease of processing, and chemical resistance, it is preferred to use glycol-modified polyethylene tehrephthalate (PETG) among polyethylene terephthalate (PET). This may be desirable.

The thickness of the base layer is also not particularly limited. For example, the thickness of the base 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 base layer is 3,000 ㎛ or less, 2,000 ㎛ or less, or 1,000 ㎛ or less, specifically 900 ㎛ or less, 800 ㎛ or less, 700 ㎛ or less, 600 ㎛ or less, 500 ㎛ or less, 400 ㎛ or less, or It may be 300 ㎛ or less.

As described above, the present application can provide a laminated film that has excellent surface hardness, stain resistance, and flexibility, and has a soft touch and matte appearance. A laminated film having such characteristics can be obtained by performing a predetermined curing treatment described below on a composition having the above-described structure.

The above-mentioned laminated film can be used for furniture or decorative materials having curves, corners, and/or flat surfaces. Examples of such furniture include doors, desks, chairs, or shelves, and decorative materials may include items that can be used as part of the furniture or on their own.

In another example related to this application, this application relates to a method of providing the above laminated film. The method may include applying a photocurable composition containing a photocurable oligomer component (A) and a reactive monomer component (B) directly on the base layer, followed by primary and secondary curing.

Primary curing and 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 of light irradiated, light irradiation amount, and/or light irradiation time, etc. It can be done. At this time, the primary curing is performed under conditions that can form wrinkles while shrinking the surface of the cured layer applied on the base layer. Specific conditions are explained below.

The specific composition of the composition applied on the base layer is as described above. Additionally, the type and characteristics of the base layer are the same as those 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 base layer using a known method.

The method includes a first light irradiation step of irradiating relatively short wavelength light (L1) to the composition applied on the base layer under inert gas conditions; and a second light irradiation step of curing the composition by irradiating light (L2) with a longer wavelength than the light (L1) under air conditions. Specifically, the method includes a first light irradiation step of irradiating light (L1) of a predetermined wavelength to a composition applied on a base layer under inert gas conditions to form wrinkles on the surface of the applied composition; and a second light irradiation step of forming a cured layer, which is a cured product of the composition, by irradiating light (L2) with a longer wavelength than the light (L1) under air conditions.

The device for irradiating light in each step is not particularly limited. For example, in the case where light with a wavelength of 300 nm or less is irradiated in the first irradiation step and light with a wavelength of 400 nm or less is irradiated in the second irradiation step, Known mercury or metal halide lamps can be used.

In the first light irradiation step, light is irradiated to the composition applied on the base layer, and the excimer generated by the irradiated light shrinks the surface of the applied composition (or the composition cured by light irradiation). This is the step to form wrinkles. The wrinkled surface increases the scattering of light incident on the surface, thereby imparting matte characteristics. 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, high energy light with a wavelength of 300 nm or less, for example, light with a wavelength of 200 nm or less may be irradiated. Specifically, light with 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 in 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 can be, for example, He, Ne, Ar, and/or N2.

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 (O2) is 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, and 600 ppm. It may be 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 could be more than that.

In one example, the inert atmosphere may be formed so that the concentration of oxygen in nitrogen gas (N2) satisfies the above range.

When the first light irradiation is performed under inert atmosphere conditions as described above, it is advantageous to secure the wrinkles and surface properties described above. For example, when the first light irradiation is performed in an inert atmosphere where the oxygen concentration exceeds the above range, wrinkles such as those mentioned above are difficult to form, and the above surface properties cannot be provided. For example, wrinkles may not be formed evenly over the entire surface to satisfy the characteristics described above, 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 to the above range, an appropriate amount of light can reach the composition at an appropriate intensity, and as a result, a surface with wrinkles of the shape and size described above is formed, It is advantageous to ensure the described level of surface properties (e.g. surface roughness, glossiness).

In one example, the amount of light irradiated in the first light irradiation step may be 1 mJ/cm2 or more than 5 mJ/cm2. Specifically, the lower limit of the light irradiation amount in the first 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 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. , may be 30 mJ/cm2 or less or 25 mJ/cm2 or less. In the first light irradiation step, when the light irradiation amount is adjusted to the above range, it is advantageous to form a surface with the above-described wrinkles and secure surface properties (e.g., surface roughness, glossiness) of the above-described level.

In one example, the time for which light is irradiated in the first light irradiation step is 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. It could be more than that. In the first light irradiation step, when the time for irradiating light is adjusted to the above range, a surface with wrinkles of the above-described shape and size is formed, and surface properties (e.g., surface roughness, glossiness) of the above-described degree are formed. ) is advantageous in securing.

At this time, the light irradiation time can be controlled by adjusting the movement speed of the resin composition irradiated with light. For example, when the device shown in FIG. 6 is used, the light irradiation time can be controlled while appropriately adjusting the moving speed of the base layer coated with the composition on the conveyor belt within the range of 1 to 50 m/min.

In the second light irradiation step, light energy of a different wavelength from the first light irradiation step is applied to the coating composition coated on the base layer and wrinkles are formed on the surface through the first light irradiation step to cure the coating composition. This is the step of forming layers.

In one example, in the second light irradiation step, light with a wavelength in the range of 200 to 400 nm may be irradiated. Specifically, the second light irradiation step is 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. This may be an investigation step. 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, which is cured to a certain level by the first light irradiation step and has wrinkles formed on its surface, can be cured in the (applied) thickness direction 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 with a higher wavelength than the first irradiation step in the wavelength range described above.

The second light irradiation step is performed in an air atmosphere. The curing rate of the composition can be improved through an air atmosphere, and the surface of the cured layer can be cleaned as oxygen molecules (O2) are converted to ozone (O3) 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 50 mm or less, 40 mm or less, 30 mm or less, or 20 mm or less. there is. 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 or less. It may be below, and the 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, the distance between the composition and the light source when performing the second light irradiation step may be smaller than that during the first light irradiation step. When the distance between the composition and the light source is adjusted to the above range during the second light irradiation, it is advantageous to increase the degree of curing of the entire cured layer.

In one example, the amount of light irradiated in the second light irradiation step may be greater than the amount of light irradiated in the first light irradiation step. For example, the amount of light irradiated in the second light irradiation step is 150 mJ/cm2 or more, specifically 160 mJ/cm2 or more, 170 mJ/cm2 or more, 180 mJ/cm2 or more, 190 mJ/cm2 or more, 200 mJ/cm2 or more. 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 is, for example, 500 mJ/cm2 or less or 400mJ/cm2 or less, specifically, for example, 350 mJ/cm2 or less, 340 mJ/cm2 or less, 320 mJ/cm2 or less, 310 mJ/cm2 or less, or It may be less than 300 mJ/cm2. When the light irradiation amount is adjusted to the above range during the second light irradiation, it is advantageous to increase the degree of curing of the entire cured layer.

In one example, the time at which light is irradiated in the second light irradiation step may be the same as or different from the time at which light is irradiated in the first light irradiation step described above. Specifically, the time for which light is irradiated in the second light irradiation step is 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. there is.

When the first light irradiation and the second light irradiation are performed as described above, the surface of the cured layer may have a relatively dense cured density. Specifically, during the first light irradiation, light with a relatively high energy short wavelength (light of about 200 nm or less) acts in the vicinity of hundreds of nm near the surface of the coated cured layer, and then when the second light irradiation occurs, the cured layer The surface has a dense hardening density. However, because the short-wavelength light used for first light irradiation does not affect the inside of the cured layer, the cured density inside the cured layer may be relatively low. Therefore, the inside of the hardened layer with a relatively low curing density can contribute to securing flexibility, and the surface of the hardened layer with a dense cured state can maintain distinct wrinkles. As a result, a densely hardened surface with wrinkles can provide a soft touch and stain resistance, and can respond flexibly to tensile force without losing surface characteristics.

In another example related to the present application, the present application relates to a decor film or decor sheet comprising the above laminated film. The decorative film can be used as a decorative material or furniture. Furniture or decorative materials may have curves, edges, and/or flat surfaces.

Examples of furniture include doors, desks, chairs, or shelves, and decorative materials can refer to items that can be used as part of the furniture or used alone.

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

According to an example of the present application, a deco sheet is provided that not only has excellent stain resistance, but can also achieve soft touch and matte characteristics, and can maintain the above characteristics even when tensile force for processing is applied in actual use. do.

Figure 1 is an image taken of the surface of a matte film manufactured according to an example of the present application.
Figure 2 is an image taken of the surface of a matte film manufactured according to the prior art. Specifically, Figure 2 is a photograph of the surface of a matte film manufactured using a matting agent.
Figure 3 is for explaining wrinkles formed on the surface of a matte laminate manufactured according to an example of the present application. In Figure 3, the colored dotted lines are marks for visually explaining the wrinkles (Wa and/or Wb).
Figure 4 is a photograph of various surface shapes that a laminated film manufactured according to an example of the present application may have.
Figure 5 shows some representative surface irregularities of the hardened layer formed according to an example of the present application. Figure 5(a) shows wrinkles with a radial structure, Figure 5(b) shows wrinkles with a Y-shaped structure, Figure 5(c) shows wrinkles with a sand wave-type structure, and Figure 5(d) shows wrinkles with a sand wave-type structure. The wrinkles of a tensioned-web type structure are shown.
Figure 6 schematically shows a device for performing curing according to an example of the present application.
Figure 7 is a photograph of the surface of a specimen for Examples (Figures 7a and 7b) and Comparative Examples (Figures 7c and 7d).

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 examples below.

[Experimental Example 1]

(1) Preparation of composition for forming a cured layer

50 parts by weight of urethane (meth)acrylate oligomer, 40 parts by weight of monofunctional (meth)acrylic monomer having the above-described polar functional group (hydroxy group or nitrogen-containing functional group), 10 parts by weight of hexanediol di(meth)acrylate, initiator. A composition (viscosity: about 300 cps) containing 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 ㎛) was prepared.

At this time, the oligomer component is a first urethane (meth)acrylate oligomer (weight average molecular weight is in the range of about 10,000 to 20,000, and the number of functional groups is 2 to 10) and a second urethane (meth)acrylate oligomer (molecular weight is about 2 to 10). The weight ratio (W1/W2) of each urethane (meth)acrylate (which ranges from 2,000 to 5,000 and has a greater number of functional groups than the first urethane (meth)acrylate) was adjusted to be 1 or more, for example, from more than 1 to 1.8.

(2) Formation of hardened layer

The composition prepared as above was applied directly onto the glycol-modified polyethylene terephthalate (PETG) (white) base layer (size: 15 cm wide, 30 cm long, 250 ㎛ thick) and applied to a light curing device with the structure shown in Figure 6. fixed to Then, as shown in Table 1 below, light irradiation was performed step by step while moving the substrate at a moving speed of 20 ± 1 m/min to prepare a laminated film with a cured layer formed on the substrate layer.

Example 1 Example 2 Example 3 Real Example 4 Comparative Example 1 Comparative example 2 Comparative example 3 Comparative example 4 1st light irradiation Wavelength range (nm) 172 180 190 150 Not performed 172 Not performed Not performed Irradiation dose (mJ/cm ² ) 18 15 16 17 18 Distance from light source (mm) 50 45 50 52 50 gas atmosphere N ₂ conditions (O ₂ 200ppm) N ₂ conditions (O ₂ 200ppm) N ₂ conditions (O ₂ 200ppm) N ₂ conditions (O ₂ 200ppm) N ₂ conditions (O ₂ 200ppm) 2nd light irradiation Wavelength range (nm) 220 250 300 380 200 Not performed 100 500 Irradiation dose (mJ/cm ² ) 280 290 285 250 280 280 280 Distance from light source (mm) 2 2 1.5 2.5 2 2 2 gas atmosphere air conditions air conditions air conditions air conditions air conditions air conditions air conditions

(3) Evaluation The surface roughness (Rz1) and 60° glossiness (G1) of the laminated film (base layer/cured layer) prepared as above were measured according to the method below. Thereafter, the laminated film was left at about 80° C. for about 1 minute, then 14% tensile was performed, and the surface roughness (Rz2) and 60° glossiness (G2) were measured again. The surface roughness and gloss measurement methods and elongation process are as follows, and the results are shown in Table 2. However, in the case of Comparative Example 2, only surface hardening occurred slightly and curing of the coating layer was impossible, and in the case of Comparative Example 3, the amount of secondary curing light was too low and the surface hardening did not occur well, so physical property evaluation could not be performed. Table 2 below shows these. * Surface roughness (Rz): The surface roughness (Rz) of the laminated film was measured based on ISO 4287.

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

* Tensile: Referred to ASTM D638 method. Specifically, using a high-temperature tensile machine, tension was performed on specimens that were cut from the sheets manufactured in Examples and Comparative Examples into a dog-bone shape with a length of 120 mm and a width of 20 mm. Specifically, the jig was maintained at a distance of 100 mm, 10 mm at both ends of the specimen were fixed, and the elongation in the longitudinal direction was 14% using a high-temperature tensile machine with the temperature of the UTM chamber maintained at 80 ± 1 ℃. The tensioner was operated to allow this. The surface shapes before and after tensioning of Example 1 are shown in Figures 7a and 7c, respectively. Additionally, the surface shapes of Comparative Example 1 before and after tensioning are shown in Figures 7b and 7d, respectively.

Surface roughness (Rz1) Glossiness (G1) Surface roughness (Rz2) Glossiness (G2) Surface roughness reduction rate Glossiness increase rate Example 1 4.0㎛ 4.3 3.6㎛ 4.7 10% 9.3% Example 2 3.8 4.5 3.5 4.8 7.9% 6.7% Example 3 4.0 4.3 3.7 4.6 7.5% 7.0% Example 4 4.2 4.1 3.9 4.4 7.1% 7.3% Comparative Example 1 2.6㎛ 24 2.2㎛ 26 15.4% 8.3% Comparative example 2 - - - - - - Comparative Example 3 - - - - - - Comparative example 4 2.5 25 2.1 28 16% 12%

Comparing Figures 7a and 7c, even if the same treatment agent is used, the presence or absence of fine wrinkles is determined depending on the presence or absence of first light irradiation, and the surface gloss varies due to this phenomenon. In addition, referring to FIGS. 7A and 7B, it is possible to form an ultra-matte surface by forming fine wrinkles on the surface during the first light irradiation. In addition, the wrinkles on the surface are not easily stretched or straightened even after stretching, so the rate of change in Rz and surface gloss is 15 or less compared to before stretching. As shown in Table 2 above, comparing Comparative Example 1 and Example, the first light irradiation was performed. If not, there are no factors that will significantly change after stretching, so the rate of change in gloss and roughness is low, but it is difficult to turn the initial gloss into ultra-matte.

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

Claims (12)

Base layer; and a cured layer located on at least one side of the base layer, having a wrinkled surface, and not containing an oligomer containing a fluorine (F)-containing functional group.
After leaving the film at 80°C for 1 minute and stretching it at 14% at a rate of 100 mm/min, the reduction rate in surface roughness of the cured layer calculated by the following equation 1 is 15% or less, and the roughness of the surface of the cured layer before stretching ( Rz1) is in the range of 3.5 to 10.0 ㎛, and the roughness (Rz2) of the surface of the hardened layer after stretching is in the range of 3.0 to 10.0 ㎛,
[Relational Expression 1]
Surface roughness reduction rate (%) = {(Rz1-Rz2) x 100}/Rz1
(Rz1 is the surface roughness before stretching at 14% at a speed of 100 mm/min after leaving the film at 80 ℃ for 1 minute, and Rz2 is the surface roughness before stretching at 14% at a speed of 100 mm/min after leaving the film at 80 ℃ for 1 minute) surface roughness after stretching),
The gloss increase rate of the cured layer calculated by the following relational formula 2 after the stretching is in the range of 15% or less, the 60° glossiness (G1) of the surface of the cured layer is in the range of 4.0 to 6.0, and after stretching the film, the gloss of the cured layer surface A laminated film having a 60° glossiness (G2) in the range of 4.0 to 6.0.
[Relational Expression 2]
Glossiness increase rate (%) = {(G2- G1) x 100}/G1
(G2 is 60° gloss after stretching)
(G1 is the glossiness before stretching at 14% at a speed of 100 mm/min after leaving the film at 80 ℃ for 1 minute, and G2 is the glossiness before stretching at 14% at a speed of 100 mm/min after leaving the film at 80 ℃ for 1 minute) Glossiness after stretching) The laminated film of claim 1, wherein the cured layer includes a cured product of a curable composition, and the composition includes a urethane (meth)acrylate oligomer having a weight average molecular weight (Mw) of 30,000 or less. The laminated film according to claim 2, wherein the composition includes two or more urethane (meth)acrylate oligomers having different weight average molecular weights (Mw). The laminated film according to claim 1, wherein the cured layer includes a cured product of a curable composition, and the composition includes a urethane (meth)acrylate oligomer of 6 to 10 functionality. The laminated film according to claim 4, wherein the composition includes two or more urethane (meth)acrylate oligomers having different numbers of functional groups. The method of claim 5, wherein the composition comprises a first urethane (meth)acrylate oligomer having a weight average molecular weight (Mw) in the range of 10,000 to 30,000 and a second urethane (meth)acrylate oligomer having a weight average molecular weight (Mw) of less than 10,000. A laminated film comprising: The method of claim 1, wherein the cured layer includes a cured product of a curable composition, and the composition comprises at least 30 parts by weight of the monomer component (B) out of 100 parts by weight of the oligomer component (A) and the monomer component (B). Containing a laminated film. The laminated film according to claim 7, wherein the monomer component (B) contains a (meth)acrylic monomer. The laminated film according to claim 8, wherein the (meth)acrylic monomer has a hydroxy group, an alkylene oxide group, or a nitrogen-containing functional group. The laminated film according to claim 1, wherein the cured layer includes a cured product of a curable composition, and the composition further includes a polyfunctional monomer. A decor film comprising the laminated film according to claim 1. A first light irradiation step of irradiating light (L1) of a predetermined wavelength to the composition applied on the base layer under inert gas atmosphere conditions to form wrinkles on the surface of the applied composition; and
A second light irradiation step of forming a cured layer, which is a cured product of the composition, by irradiating light (L2) with a longer wavelength than the light (L1) under air conditions,
The method of manufacturing a laminated film according to claim 1, comprising a base layer and a cured layer, wherein the light (L2) has a wavelength within the range of 200 to 400 nm.