KR20200059905A - Decorative sheet having excellent aesthetics and anti pollution, and preparation method thereof - Google Patents

Abstract

The present invention relates to a decorative material with excellent anti-pollution properties and aesthetic effects and a manufacturing method thereof. The decorative material includes first to third areas having minute surface structures different from each other on a coating layer which is the outermost layer, thereby having the excellent anti-pollution properties. Also, the decorative material easily can lower a surface gloss and induce a gloss deviation of surfaces between the areas so that design properties can be improved through implementation of three-dimensional effects, thereby having the excellent aesthetic effects.

Description

Decorative sheet having excellent aesthetics and anti pollution, and preparation method thereof

The present invention relates to a decorative material having excellent stain resistance and aesthetic effect, and a method for manufacturing the same, in detail, by inducing surface gloss deviations including regions having different structures on the surface, the stain resistance is improved and a three-dimensional effect is realized. It relates to an excellent decorative material and its manufacturing method.

Recently, as interest in interiors has increased, the demand for decorative materials with excellent design has increased, and natural-friendly materials such as floor decoration materials are gaining popularity. These natural-friendly materials have a veneer on the inside and are surface-coated, so they have good appearance or texture, but are less susceptible to scratches and presses. In addition, when used for a long period of time, the moisture of the floor is directly transferred and the wood is rotten or warped, so it is not only dangerous, but also has a problem in that a lot of heat is lost during heating, and V is applied along the border during construction (for example, a joint). A slot or U-shaped groove is formed, and there is a limitation in that contaminants and the like are contaminated.

Accordingly, materials having improved water resistance and durability have been developed by providing a surface layer including a printed layer on which a pattern of natural veneer is designed on a base layer, or by introducing a thermosetting or thermoplastic resin layer on a plywood. However, while the materials have improved water resistance and durability, in order to create a comfortable and refined atmosphere, when the surface gloss is lowered, the stain resistance is reduced and the cleaning and other functions are significantly reduced. Granting natural luster remains a challenge to overcome.

Republic of Korea Patent Publication No. 2012-0072623 Republic of Korea Patent Publication No. 2013-0037339

An object of the present invention is to provide a decorative material having high water resistance and durability, excellent stain resistance, low surface gloss and excellent design, and a method for manufacturing the same.

Accordingly, the present invention in one embodiment,

A base layer and a coating layer;

The coating layer,

A first region having a point-like uneven structure on the surface,

A second region having a radially curved structure extending from the center to the periphery with one point on the surface as the center, and

Provided is a decorative material including a third region having a corrugated structure positioned between the first region and the second region and oriented at 70 ° to 110 ° with respect to a longitudinal direction of a surface contacting the first area on the surface.

In addition, the present invention in one embodiment,

A first region having an uneven structure having a dot shape on its surface by irradiating ultraviolet rays to the acrylic resin composition applied on the base layer; A second region having a dendrite structure, which is a radially curved structure extending from the center to the periphery with one point as the center of the surface; And forming a coating layer positioned between the first region and the second region and including a third region having a corrugated structure oriented at 70 ° to 110 ° with respect to a longitudinal direction of a surface contacting the first area on the surface. It provides a method of manufacturing a decorative material.

The decorative material according to the present invention includes first to third regions having different micro surface structures on the outermost layer of the coating layer, and thus has excellent stain resistance, can easily lower the surface gloss, and also reduces the gloss deviation of the surfaces between regions. By inducing, the design is improved through the realization of the three-dimensional effect, so it has an excellent aesthetic effect.

1 is an image taken by scanning electron microscopy (SEM) of the surface structure of each region of the decorative material prepared in Example 1.
FIG. 2 is an image obtained by scanning electron microscope (SEM) of the second region of the coating layer prepared in Example 2.
3 is a cross-sectional view showing a cross-sectional structure of a decorative material according to the present invention.
4 is a cross-sectional view showing a cross-sectional structure of an image and a second region of a second region of the coating layer taken by a scanning electron microscope (SEM).
FIG. 5 is an image of a second region of the coating layer prepared in Comparative Example 3 taken with a scanning electron microscope (SEM).

The present invention can be applied to various changes and can have various embodiments, and specific embodiments will be illustrated in the drawings and described in detail in the detailed description.

However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

In the present invention, terms such as "comprises" or "have" are intended to indicate that there are features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, and one or more other features. It should be understood that the existence or addition possibilities of fields or numbers, steps, operations, components, parts or combinations thereof are not excluded in advance.

In addition, the accompanying drawings in the present invention should be understood to be shown enlarged or reduced for convenience of explanation.

Hereinafter, the present invention will be described in detail with reference to the drawings, and the same or corresponding components will be given the same reference numbers regardless of the reference numerals, and redundant description thereof will be omitted.

In the present invention, "surface profile" refers to the degree of minute irregularities present on the surface and may be expressed as "Rz". Here, "Rz" is a straight line that does not cut the cross-section curve horizontally parallel to the average line of the part taking the reference length L as the cross-section curve of the surface, from the high to the fifth peaks of the bend and from the deep to the fifth. It measures the distance between valleys and shows the deviation. It is also called "ten point average roughness".

In addition, in the present invention, the unit “T” is a unit indicating the thickness of the layers constituting the film, sheet, or laminated film, and may be the same as the unit “mm”.

The present invention relates to a decorative material and a method for manufacturing the same.

Recently, as interest in interiors has increased, the demand for decorative materials with excellent design has increased, and natural-friendly materials such as floor decoration materials are gaining popularity. These natural-friendly materials have a veneer on the inside and are surface-coated, so they have good appearance or texture, but are less susceptible to scratches and presses. In addition, when used for a long time, the moisture of the floor is directly transferred and the wood rots or twists and cracks, which is not only dangerous, but also causes a lot of heat loss during heating. V- or U-shaped grooves along the edges during construction ( For example, a meji portion) is formed, and there is a limitation in that contaminants or the like are contaminated.

Accordingly, materials having improved water resistance and durability have been developed by providing a surface layer including a printed layer on which a pattern of natural veneer is designed on a base layer, or by introducing a thermosetting or thermoplastic resin layer on a plywood. However, while the materials have improved water resistance and durability, in order to create a comfortable and refined atmosphere, when the surface gloss is lowered, the stain resistance is reduced and the cleaning and other functions are significantly reduced. Granting natural luster remains a challenge to overcome.

Accordingly, the present invention provides a decorative material having excellent stain resistance and aesthetic effect and a method for manufacturing the same.

The decorative material according to the present invention includes first to third regions having different micro surface structures on the outermost layer of the coating layer, and thus has excellent stain resistance, can easily lower the surface gloss, and also reduces the gloss deviation of the surfaces between regions. By inducing, the design is improved through the realization of the three-dimensional effect, so it has an excellent aesthetic effect.

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

Decoration

The present invention in one embodiment,

A base layer and a coating layer;

The coating layer,

A first region having a point-like uneven structure on the surface,

A second region having a radially curved structure extending from the center to the periphery with one point on the surface as the center, and

Provided is a decorative material including a third region having a corrugated structure positioned between a first region and a second region and oriented at a specific angle with respect to a longitudinal direction of a surface contacting the first region on the surface.

The decorative material according to the present invention includes a coating layer on the base layer, and the coating layer includes regions having different specific microstructures on the surface. Specifically, as shown in FIG. 1, the decorative material has a first region having a dot-shaped uneven structure on the surface, and a second having a radially curved structure extending from the center to the periphery with one point as the center. And a third region positioned between the first region and the second region and having a corrugated structure oriented at a specific angle with respect to the longitudinal direction of the surface contacting the first region on the surface.

Here, the first region has a dot-shaped uneven structure, but the dot-shaped uneven structure appears intensively at the central portion of the first region, and has a shape in which the frequency is lowered toward the portion in contact with the third region at the central portion. Can be. As an example, the dot-shaped concave-convex structure may be present in the center of the first region at a frequency of 20 to 100 or 30 to 80 per unit area (100 nm X 100 nm), and the unit area at a region contacting the third region 0 to 20 or 1 to 15 frequencies per (100 nm X 100 nm). The uneven structure is a structure induced by the filler contained in the composition used when forming the coating layer, and the surface roughness can be controlled according to the average size of the filler. As an example, when the average size of the filler is 15 μm, the surface roughness of the first region may be about 0.5 to 4 μm.

In addition, as shown in FIG. 2, the second region has a random point on the surface as a center, and radial irregularities that extend from the center to the periphery but decrease in height from the center to the periphery are randomly distributed. It has a structure. For example, the radially curved structure may include a structure in which an arborescence structure or a dendrite structure randomly dispersing an arbitrary point on the surface as a center portion is provided.

The radially curved structure may have surface properties controlled by its size or height, specifically surface gloss and fouling resistance, and for this purpose, the radially fine curved structure may be controlled to have an average diameter within a specific range. Specifically, the average diameter of the radially curved structure indicates the average size of the individual radially curved structures present on the surface, and the averaged diameter may be 5 μm to 500 μm, more specifically 5 μm to 450 μm, 5 μm To 400 μm, 5 μm to 350 μm, 5 μm to 300 μm, 5 μm to 250 μm, 5 μm to 200 μm, 5 μm to 150 μm, 5 μm to 100 μm, 5 μm to 50 μm, 50 μm to 200 μm Μm, 50 μm to 100 μm, 100 μm to 500 μm, 100 μm to 300 μm, 100 μm to 200 μm, 80 μm to 150 μm, 20 μm to 100 μm, 25 μm to 60 μm, 40 μm to 80 μm, 80㎛ to 120㎛, 90㎛ to 110㎛, 5㎛ to 40㎛, 5㎛ to 30㎛, 5㎛ to 25㎛, 5㎛ to 20㎛, 5㎛ to 15㎛, 5㎛ to 10㎛, 10㎛ To 30㎛, 15㎛ to 30㎛, 15㎛ to 25㎛, 20㎛ to 30㎛, 1㎛ to 10㎛, 2㎛ to 10㎛, 4㎛ to 10㎛, 5㎛ to 10㎛, 7.5㎛ to 10 ㎛, 8㎛ to 10㎛¸0.5㎛ to 7.5㎛, 0.5㎛ to 5㎛, 0.5㎛ to 3㎛, 0.5㎛ to 2㎛, 0.5㎛ to 1㎛, 1㎛ to 5㎛¸1㎛ to 3㎛, 1㎛ to 2㎛, 2㎛ to 5㎛, 2㎛ to 3.5㎛, 4㎛ to 8㎛, 4㎛ to 6㎛, 5㎛ to 8㎛, 5㎛ to 6.5㎛, 6㎛ to 9㎛, 6㎛ It may be 8 μm, 7 μm to 9 μm, or 3 μm to 5 μm.

In addition, the second region may have a radially curved structure formed on the surface to have a constant surface roughness. Specifically, the coating layer may have an average value of the surface roughness "Rz" of the radially curved structure existing on the surface of 10 µm to 30 µm, and more specifically, an upper limit of 30 µm or less, 28 µm or less, 26 µm or less, 24 It may be µm or less, 22 µm or less, 20 µm or less, 18 µm or less, and the lower limit may be 10 µm or more, 12 µm or more, 14 µm or more, 16 µm or more, or 18 µm or more. For example, the surface roughness (Rz) of the radially curved structure is 10 μm to 25 μm, 10 μm to 23, 10 μm to 21 μm, 10 μm to 20 μm, 10 μm to 18 μm, 12 μm to 30 μm, 14㎛ to 30㎛, 16㎛ to 30㎛, 18㎛ to 30㎛, 20㎛ to 30㎛, 25㎛ to 30㎛, 15㎛ to 25㎛, 18㎛ to 20㎛, 14㎛ to 22㎛, 14㎛ It may be 17 μm to 15 μm, 17 μm, 16 μm to 19 μm, 18 μm to 23 μm, or 18 μm to 22 μm.

In addition, the radially curved structure may be formed at a constant frequency in a unit area, for example, a fixed number, and the number of radially curved structures may be the same as the number of central portions of the radially curved structure existing in the unit area. In addition, the radial bending structure may be 20 to 400 per unit area (1 mm X 1 mm) of the surface of the coating layer, specifically 20 to 350 per unit area (1 mm X 1 mm), 20 to 300 , 20 to 250, 20 to 200, 20 to 150, 100 to 400, 100 to 350, 150 to 350, 250 to 350, 200 to 400, 30 to 100, 25 to 180 , 25 to 150, 25 to 120, 40 to 100, 30 to 80, 20 to 50, 30 to 50, 40 to 60, 80 to 120, 140 to 180, 30 to 40 , 105 to 150, 100 to 120, 150 to 160, or 70 to 180. For example, the coating layer may have 80 to 120 dendrite shapes having an average diameter of 60 to 70 μm and a surface roughness (Rz) of 2 to 4.5 μm per unit area (1 mm X 1 mm).

In addition, the third region exists between the first region and the second region, and is oriented at a specific angle with respect to the longitudinal direction of the surface contacting the first region, specifically 70˚ to 110˚, 70˚ to 105˚ , 70˚ to 100˚, 70˚ to 95˚, 70˚ to 90˚, 70˚ to 85˚, 75˚ to 110˚¸80˚ to 110˚¸85˚ to 110˚¸90˚ to 110˚, 95 Oriented at an angle of ˚ to 110˚, 100˚ to 110˚¸80˚ to 100˚, 85˚ to 95˚ 90˚ to 105˚, 75˚ to 95˚, 84˚ to 93˚ or 88˚ to 97˚ It has a wrinkle structure.

In addition, the coating layer according to the present invention may include the above-described first to third regions with a predetermined ratio of area. For example, the coating layer may include a first area of 0.1 to 5 area%, a second area of 90 to 99.8 area%, and a third area of 0.1 to 5.0 area% of the unit area (1 m X 1 m). have. Specifically, the first region and the third region are 0.1 to 4.5 area%, 0.1 to 4.0 area%, 0.1 to 3.5 area%, 0.1 to 3.0 area%, 0.1 to 0.1% in the total unit area (1 m X 1 m) of the coating layer, respectively. 2.5 area%, 0.1 to 2.0 area%, 0.1 to 1.5 area%, 0.1 to 1.0 area%, 1.0 to 5.0 area%, 2.0 to 5.0 area%, 2.5 to 5.0 area% ¸3.0 to 5.0 area%, 4.0 to 5.0 area% %, 1.5-3.0 area%, 2.0-4.0 area% 3.0-4.5 area%, 1.0-2.0 area% or 1.5-2.5 area%; The second area is 91 to 99.8 area%, 92 to 99.8 area%, 93 to 99.8 area%, 94 to 99.8 area%, 95 to 99.8 area%, 96 to 99.8 area%, 97 to 99.8 area%, 98 to 99.8 area% %, 90-98 area%, 90-96 area%, 90-95 area%, 90-94 area%, 90-92 area%, 94-97 area%, 90-96 area%, 92-96 area%, 91 to 93 area%, 96 to 98 area%, 92 to 97 area%, 93 to 96 area%, 91 to 95 area%, 95 to 97 area% or 96 to 99 area%.

Furthermore, the coating layer may be formed to a thickness sufficient to reduce surface gloss by inducing diffuse reflection of incident light without being torn or lost by external stimuli. Specifically, the average thickness of the coating layer may have an average thickness of 50 μm or less, and more specifically, 1 μm to 45 μm, 1 μm to 40 μm, 1 μm to 30 μm, 1 μm to 20 μm, and 1 μm. To 18㎛, 1㎛ to 16㎛, 1㎛ to 14㎛, 1㎛ to 12㎛, 1㎛ to 10㎛, 10㎛ to 30㎛, 20㎛ to 40㎛, 30㎛ to 50㎛, 15㎛ to 25 Μm, 18 μm to 32 μm, 22 μm to 45 μm, 5 μm to 10 μm, 8 μm to 15 μm, 10 μm to 20 μm, 15 μm to 20 μm, 13 μm to 18 μm, 9 μm to 13 μm, 14㎛ to 16㎛, 4㎛ to 8㎛, 11㎛ to 13㎛, 12㎛ to 27㎛, 19㎛ to 24㎛, 16㎛ to 21㎛, 10㎛ to 16㎛ or 16㎛ to 20㎛ .

In addition, the average thickness of the coating layer may satisfy the condition of Equation 1 below (however, except when D _R2 = D _R3 = D _R1 ):

[Equation 1] D _R3 ≤ D _R2 ≤ D _R1

In Equation 1,

D _R1 is the average thickness of the first region,

D _R2 is the average thickness of the second region,

D _R3 is the average of the third region.

The total thickness of the coating layer according to the present invention is 50 μm or less, and the average thickness of each region may have a certain deviation. For example, as shown in FIG. 3, the first region having a dot-like concavo-convex structure on the surface (indicated by “a”) has the largest average thickness of about 20 to 50 μm, and the second region having a finely curved structure on the surface. The area (indicated by “b”) has an average thickness of about 10-20 μm, and a third area (indicated by “c”) located between the first and second areas is about 5 to 20 μm with the smallest average thickness. Can be.

In addition, the average thickness of the second region may be 20 μm or less, specifically 0.1 μm to 20 μm, 0.1 μm to 18 μm, 0.1 μm to 15 μm, 0.1 μm to 13 μm, 0.1 μm to 11 μm, 0.1 Μm to 10 μm, 0.1 μm to 8 μm, 2 μm to 15 μm, 5 μm to 15 μm, 10 μm to 15 μm, 4 μm to 8 μm, 3 μm to 6 μm, 5 μm to 10 μm, 8 μm to It may be 12 μm, 11 μm to 15 μm, 7 μm to 13 μm, 4 μm to 7 μm, or 10 μm to 13 μm. The average thickness of the coating layer referred to in the present invention may mean the average thickness (T _aver ) of the coating layer excluding the height of dendrites as shown in FIG. 3, and in some cases, the average of the coating layer excluding the height of dendrites It may mean a thickness including 1/2 of the thickness (T _aver ) and the average maximum height (R _max ) of the dendrites.

The decorative material according to the present invention is excellent in stain resistance by including the first to third regions having the above-described surface structure, surface roughness, average area and average thickness in the coating layer, and can easily lower surface gloss, and surface between regions The design can be improved by inducing gloss deviation to realize a three-dimensional effect.

As an example, the decorative material has improved surface stain resistance, and thus the degree of contamination may be 4 or higher in a slip test using oily magic as a contaminant according to KS M 3802. Specifically, when the decorative material according to the present invention is contaminated with oily magic, and after 30 seconds, the oily magic is wiped off with Kim Wipes, and the degree of surface damage of the decorative material is visually checked, the degree of contamination of the decorative material is 4 grade (first Contaminant residual area based on contaminated area: 5% or more and less than 20%) to 5 grade (initial contaminant residual area: 5% or less), and specifically 5 grade.

This is different from each other on the surface of the coating layer, which is the outermost layer of the decorative material, and includes a fine surface structure having a constant surface roughness, thereby forming an air pocket on the surface of the coating layer and impurities when adsorbing impurities, minimizing the contact area between the surface of the coating layer and impurities and It shows that removal can be facilitated.

As another example, the decorative material may include a very small amount of a matting agent in a coating layer, or, in some cases, not significantly, by inducing scattering and / or diffuse reflection of light incident on the surface through a micro surface structure formed on the surface of the coating layer. Gloss can be achieved.

Particularly, in the case of the first area having a point-shaped irregular structure and the second area occupying 90% or more of the total area, the average gloss when measuring 60 ° glossiness (gloss 60 ° condition) using a gloss meter The degree may be less than 10, more specifically, the upper limit is 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4.5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2.3 or less, and the lower limit is 0.1 Or more, 0.5 or more, 1 or more, or 1.1 or more, 2 or more, 3 or more, 4 or more, or 5 or more. For example, the average gloss of the decorative material is 0.1 to 9, 0.1 to 8, 0.1 to 7, 0.1 to 6, 2 to 6, 3 bet 5, 4 to 7, 6 to 9, 3.5 to 8, 5 to 7 , 2 to 4, 3 to 6, 0.1 to 4.8, 0.1 to 4.5, 0.1 to 4, 0.1 to 3.5, 0.1 to 3, 0.1 to 2.8, 0.1 to 2.4, 0.5 to 1.8, 3.2 to 4.7, 0.1 to 0.4, 0.5 To 4, 0.5 to 3, 1 to 2.5, 1 to 2.2, 1.7 to 2.9, 0.8 to 1.9, 1.3 to 2.2, 1.2 to 1.7, 1.8 to 2.2, 1.3 to 2.4, 3.1 to 4.7, 3.2 to 4.1, 3.4 to 3.9 , 3.1 to 3.6, 3.9 to 4.8, 3.2 to 4.1, 3.8 to 4.3 or 3.3 to 3.7.

In addition, in the third region existing between the first region and the second region, a corrugated structure oriented at a constant angle with respect to the longitudinal direction of the surface contacting the first region is relatively regularly formed, and / or scattering of incident light due to the corrugated structure and / or Alternatively, since the diffuse reflection effect is insignificant, it can be confirmed that it has a high glossiness with the naked eye, and a three-dimensional effect can be realized through variations in surface gloss between these regions, thereby exhibiting an effect of improving the design of the decorative material.

Furthermore, the decorative material according to the present invention may not only have excellent stain resistance and design, but also may have excellent non-slip properties to prevent slipping.

As an example, the decorative material may have a non-slip property and a grade of an inclination angle at which slip occurs during a ramp test according to DIN 51130 may be R10 or more, specifically R11 or more, or R10 to R11. Here, R10 represents a case where the angle of the inclination angle at which the slip occurs is 10 ° or more and less than 19 °, and R11 represents a case where the angle of the inclination angle at which the slip occurs is 19 ° or more and less than 27 °.

Meanwhile, the base layer provided in the decorative material according to the present invention serves as a base for the decorative material, supports the coating layer, and serves to absorb shock transmitted from the outside. The base layer may have an average thickness of 100 μm to 2,000 μm, specifically 100 μm to 1,500 μm, 100 μm to 1,000 μm, 100 μm to 800 μm, 100 μm to 600 μm, 100 μm to 500 μm, It may have an average thickness of 100㎛ to 400㎛, 100㎛ to 300㎛, 150㎛ to 250㎛, 200㎛ to 500㎛, 400㎛ to 600㎛ or 450㎛ to 550㎛.

In addition, the base layer is a polyvinyl chloride (PVC) base, polyethylene terephthalate (PET) base, glycol-modified polyethylene terephthalate (PETG) base, paper, wood-based board, inorganic board and synthetic resin-based board from the group consisting of It may include one or more selected.

In addition, the decorative material according to the present invention may further include a separate layer between the base layer and the coating layer. Specifically, the decorative material may further include any one or more of a printed layer and a dimensionally stable layer between the base layer and the coating layer. For example, the decorative material may have a structure in which a base layer, a printing layer, and a coating layer are sequentially stacked, or a structure in which a base layer, a dimensionally stable layer, a printing layer, and a coating layer are sequentially stacked.

Here, the printing layer and the dimensionally stable layer are formed by photocuring or thermosetting each composition including at least one selected from the group consisting of, for example, a binder resin, an initiator, a curing agent, other additives, and combinations thereof, or It can be formed as a film or sheet using an extrusion method, a calendaring method, or the like. In addition, each composition may appropriately adjust the type and content of components included therein according to the properties and functions of each layer, and is not particularly limited. Specifically, the decorative material is formed by applying a predetermined composition to one surface of any one layer and then photocuring or thermally curing, or after forming each layer as a film or sheet, and then forming them as a plywood process known in the art. It may be formed using, but is not limited thereto. In addition, the binder resin may include synthetic resins, bio resins, or both, for example, polyvinyl chloride (PVC) -based resins, polyurethane-based resins, polylactic acid-based resins, polyolefin resins, and the like. .

The printing layer may be formed by applying a pattern and / or pattern in various printing methods used in the art, such as transfer printing, gravure printing, screen printing, offset printing, rotary printing, or flexo printing, The ink used at this time may include water-based ink and / or water-soluble ink containing water or the like. In addition, the average thickness of the printed layer may be 0.1㎛ to 2.0㎛, specifically 0.1㎛ to 1.8㎛, 0.1㎛ to 1.6㎛, 0.1㎛ to 1.4㎛, 0.1㎛ to 1.2㎛, 0.1㎛ to 1.0㎛ , 0.1㎛ to 0.5㎛, 0.2㎛ to 0.6㎛, 0.5㎛ to 1.0㎛, 0.6㎛ to 0.9㎛, 0.8㎛ to 1.5㎛, 1.2㎛ to 1.5㎛, 1.5㎛ to 2.0㎛, 1.8㎛ to 2.0㎛, 0.9 It may be µm to 1.2 µm, 0.6 µm to 1.6 µm, 0.4 µm to 0.9 µm, 1.1 µm to 1.7 µm, or 1.5 µm to 1.8 µm.

Method of manufacturing decorative materials

In addition, the present invention in one embodiment,

A first region having an uneven structure in a dot shape on the surface by irradiating ultraviolet rays to the acrylic resin composition applied on the base layer; A second region having a dendrite structure, which is a radially curved structure extending from the center to the periphery with one point as the center of the surface; And forming a coating layer including a third region having a corrugated structure positioned between the first region and the second region and oriented at a specific angle with respect to a longitudinal direction of a surface contacting the first region on the surface. Provide a manufacturing method.

The manufacturing method of the decorative material according to the present invention includes the steps of applying an acrylic resin composition on a base layer and irradiating UV to the applied acrylic resin composition to form a coating layer.

At this time, the base layer may be used that includes a groove having an average thickness of 100 μm to 2,000 μm, an average depth of 5 μm to 200 μm, and an average width of 2 μm to 100 μm on the surface on which the acrylic resin composition is applied. .

In general, when the resin composition is cured by applying a resin composition to a base layer having a non-flat surface, the coating layer formed is too thin to prevent sufficient scattering and / or diffuse reflection to reduce surface gloss or to have a surface structure having sufficient surface roughness because the thickness is too thick. Since it is not induced, it is difficult to control the gloss of the surface, and there is a limitation that it is difficult to impart a sense of unity in appearance. However, the present invention is to form a groove having an average depth of 5 µm to 200 µm and an average width of 2 µm to 100 µm on the surface of a substrate layer on which the acrylic resin composition for forming a coating layer is applied (for example, a floor pattern) After forming with, etc., by applying and curing the resin composition on the surface of the base layer containing the groove, the surface structure of the coating layer formed on the portion where the groove is located is implemented differently from the portion where the groove is not located to The surface gloss can be easily adjusted according to the position. For example, the coating layer formed on the base layer may induce a radial fine bend structure (second region of the coating layer) in a region where the groove is not located, and the groove is positioned at a specific angle along the micro bend structure It is possible to derive a structure (a third region and a first region of the coating layer) in which the pleated structure and the dot-shaped uneven structure are continuously formed, respectively, and the first region including the dot-shaped uneven structure and the radial fine bending structure, respectively. A low gloss or a matte may be implemented in and the second region.

To this end, the average thickness of the substrate layer may be 100 μm to 2,000 μm, specifically 100 μm to 1,500 μm, 100 μm to 1,000 μm, 100 μm to 800 μm, 100 μm to 600 μm, 100 μm to 500 It may be μm, 100 μm to 400 μm, 100 μm to 300 μm, 150 μm to 250 μm, 200 μm to 500 μm, 400 μm to 600 μm, or 450 μm to 550 μm.

In addition, the groove located on the surface of the substrate layer may have an average depth of 5 μm to 200 μm and an average width of 2 μm to 100 μm, specifically, an average depth of 5 μm to 150 μm, 5 μm to 120 μm, 5 μm to 100 μm, 5 μm to 80 μm, 5 μm to 60 μm, 5 μm to 50 μm, 10 μm to 180 μm, 10 μm to 150 μm, 10 μm to 100 μm, 10 μm to 80 μm 25 μm to 200 μm, 50 μm to 200 μm, 100 μm to 200 μm, 150 μm to 200 μm, 180 μm to 200 μm, 20 μm to 50 μm, 40 μm to 80 μm, 70 μm to 120 μm, 90 μm to 150 μm , 120 μm to 160 μm, 170 μm to 200 μm, 5 μm to 60 μm, 10 μm to 50 μm, 15 μm to 45 μm, 20 μm to 30 μm, 25 μm to 50 μm, or 35 μm to 45 μm And the average width of 2 μm to 80 μm, 2 μm to 60 μm, 2 μm to 40 μm, 5 μm to 80 μm, 5 μm to 60 μm, 5 μm to 50 μm, 10 μm to 80 μm, 10 μm to 60 μm, 10 μm to 40 μm, 10 μm to 20 μm, 25 μm to 100 μm, 50 μm to 100 μm, 70 μm to 100 μm, 20 μm to 50 μm, 40 μm to 80 μm, 75 μm to 90 μm , 5 μm to 60 μm, 10 μm to 50 μm, 15 μm to 40 μm, 20 μm to 30 μm, 10 μm to 30 μm, or 15 μm to 25 μm.

In addition, the coating layer formed on the base layer is formed through UV irradiation. Specifically, the acrylic resin composition applied on the base layer is irradiated with light having a wavelength of 250 nm or less under an inert gas condition to activate the composition. 1 light irradiation step; A second light irradiation step of irradiating the activated composition with light having a wavelength of 250 nm to 400 nm under air conditions to first cure the composition to form a coating layer; And

A third light irradiation step in which the primary cured composition is irradiated with light having a wavelength of 200 nm to 400 nm under an activating gas condition to secondaryly cure the composition to form a coating layer. It can be carried out by curing in steps.

At this time, the first light irradiation step is the first step of irradiating light to the acrylic resin composition applied on the substrate layer, the surface of the composition and / or coating layer coated with the excimer generated by the irradiated light It is a step of increasing the scattering rate and / or diffuse reflection of light incident on the surface by shrinking to form wrinkles. In the present invention, the surface of the acrylic resin composition and / or the coating layer may be shrunk to the above-described radial fine bent structure using an excimer. To this end, the first light irradiation step is a nitrogen containing a small amount of oxygen (O ₂ ) using light having a wavelength of less than 300 nm, specifically 250 nm or less, 100 to 200 nm or 150 to 195 nm having high energy ( N ₂ ). Specifically, the concentration of oxygen (O ₂ ) contained in nitrogen (N ₂ ) in the first light irradiation step may be 10 to 30,000 ppm, specifically 10 to 20,000 ppm, 10 to 5,000 ppm, 1,000 to 2,000 ppm , 2,000 to 3,000 ppm, 3,000 to 4,000 ppm, 4,000 to 5,000 ppm, 10 to 2,000 ppm, 10 to 1,000 ppm, 10 to 500 ppm, 100 to 300 ppm, 10 to 200 ppm, 50 to 150 ppm, 80 to 120 ppm, 4,000 to 6,000 ppm , 4,500 to 5,500 ppm or 4,800 to 5,200 ppm.

In addition, the distance between the composition and the light source in the first light irradiation step may be 5 to 100 mm, specifically 5 to 80 mm, 5 to 60 mm, 5 to 40 mm, 10 to 70 mm, 10 to 50 mm, 10 It may be ˜30 mm, 20-80 mm, 20-60 mm, 20-50 mm, 20-30 mm, 25-75 mm, 50-80 mm, 40-60 mm or 45-55 mm.

In addition, in the first light irradiation step, the light irradiation amount may be 1 mJ / cm 2 to 100 mJ / cm 2, specifically 1 mJ / cm 2 to 80 mJ / cm 2, 1 mJ / cm 2 to 60 mJ / cm 2 / Cm2 to 40 mJ / cm2, 1 mJ / cm2 to 35 mJ / cm2, 1 mJ / cm2 to 30 mJ / cm2 to 1 mJ / cm2 to 20 mJ / cm2, 1 mJ / cm2 to 10 mJ / cm2, 5 mJ / Cm2 to 10 mJ / cm2, 5 mJ / cm2 to 15 mJ / cm2, 5 mJ / cm2 to 20 mJ / cm2, 5 mJ / cm2 to 25 mJ / cm2, 5 mJ / cm2 to 35 mJ / cm2, 5 mJ / Cm2 to 50 mJ / cm2, 15 mJ / cm2 to 25 mJ / cm2, 25 mJ / cm2 to 35 mJ / cm2, 25 mJ / cm2 to 50 mJ / cm2, 40 mJ / cm2 to 60 mJ / cm2, 35 mJ / Cm2 to 85 mJ / cm2, 45 mJ / cm2 to 75 mJ / cm2, 60 mJ / cm2 to 70 mJ / cm2, 70 mJ / cm2 to 100 mJ / cm2, 2 mJ / cm2 to 15 mJ / cm2, 4 mJ / Cm 2 to 12 mJ / cm 2, 5 mJ / cm 2 to 17 mJ / cm 2, 3 mJ / cm 2 to 12 mJ / cm 2, 5 mJ / cm 2 to 8 mJ / cm 2, 9 mJ / cm 2 to 17 mJ / cm 2 or 9 mJ / Cm 2 to 13 mJ / cm 2. The first light irradiation step is to control the concentration of oxygen (O ₂ ) to the above range to facilitate the contraction with a radially fine curved structure on the surface of the composition and / or cured layer, as well as to facilitate the oxygen molecules (O ₂ ) It is possible to induce the effect of cleaning the surface of the cured layer through the conversion of ozone (O ₃ ).

As an example, the first light irradiation step is a nitrogen (N ₂ ) condition containing 1,000ppm of oxygen (O ₂ ) of light having a wavelength of 172 ± 2nm in the composition in order to form an excimer in the acrylic resin composition. It can be performed by irradiating for a very short time of 1 to 2 seconds with a light amount of 9 to 11 mJ / cm 2.

In the present invention, the average diameter, height and / or the random radial fine bending structure formed on the surface of the coating layer is controlled by controlling the gas conditions, the distance between the acrylic resin composition and the light source, and the amount of light irradiation when performing the first light irradiation step. The frequency can be easily controlled.

Further, the second light irradiation step is a step of curing by applying ultraviolet (UV) energy to the surface-shrinked composition and / or coating layer, and a wavelength of 250 to 400 nm, specifically 250 to 380 nm, 280 to 380 nm , 250 to 350 nm, or 280 to 320 nm wavelength light can be performed by irradiating under air conditions. The present invention can improve the curing rate of the acrylic resin composition and / or coating layer by using light having a wavelength of 250 to 400 nm in the air condition of the second light irradiation step, as well as ozone (O ₂ ) of oxygen molecules (O ₂ ) O ₃ ) It is possible to induce the effect of cleaning the surface of the coating layer through conversion. At this time, the surface temperature of the cured composition and / or coating layer may be 20 to 90 ° C, specifically 20 to 80 ° C or 30 to 70 ° C.

As an example, the second light irradiation step is performed by irradiating the composition and / or coating layer with light having a wavelength of 300 ± 5 nm in an air condition with a light amount of 20 to 800 mJ / cm 2 for a very short time of 1 to 2 seconds. In this case, the distance between the acrylic resin composition and / or the coating layer and the light source may be 0.5 to 10 mm.

In addition, the third light irradiation step is a step of performing a true curing by additionally irradiating ultraviolet rays (UV) to the cured composition and / or the cured layer, and a wavelength of 400 nm or less, specifically 100 to 400 nm, 200 The wavelengths of 400 nm, 200-300 nm, 300-400 nm, 150-300 nm, 200-250 nm, or 270-320 nm may be performed in a nitrogen (N ₂ ) atmosphere using light.

As an example, the third light irradiation step may be performed by irradiating the composition and / or the cured layer with light having a wavelength of 300 ± 5 nm at a light amount of 100 to 3,000 mJ / cm 2 for a very short time of 1 to 2 seconds. In this case, the distance between the composition and / or the cured layer and the light source may be 50 ± 10 mm.

The light irradiated in the present invention may be irradiated according to a known method capable of irradiating light having a wavelength required in each step. For example, light having a wavelength of 400 nm or less in the UV region may be irradiated using a mercury or metal halide lamp or the like.

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

The manufacturing method of the decorative material according to the present invention can form a coating layer on the substrate layer by irradiating UV, and thus, when forming the coating layer through conventional thermal drying and / or thermal curing, the curability according to the heat shrinkage rate of the substrate layer is reduced. Not only can it be prevented from occurring, but a coating layer can be directly formed on the base layer, which simplifies the process.

As an example, the decorative material produced through the method for manufacturing a decorative material according to the present invention may exhibit a curvature of 1 T or less at a temperature of 22 ± 2 ° C. when evaluating structural stability, specifically 0.9 T or less, Curling of 0.9T or less, 0.8T or less, 0.7T or less, 0.6T or less, or 0.5T or less may occur, and in some cases, curling does not occur at all, so that 0T curling may occur.

Meanwhile, the acrylic resin composition may include a urethane acrylic oligomer, an acrylic monomer having a hydrophilic functional group, a polyfunctional acrylic monomer, and an initiator.

Specifically, the urethane acrylic oligomer means an oligomer containing an acrylic group as a polymerizable functional group together with a urethane group, a radical polymerization reaction rapidly occurs by an initiation reaction of a photoinitiator, and a coating film having excellent elasticity and toughness is produced, and polychlorination There is an advantage of excellent adhesion to the base layer made of vinyl (PVC) or the like. The urethane acrylate is synthesized as an acrylate compound having a polyisocyanate, polyol, and hydroxy group, wherein the polyisocyanate is 5-isocyanate-1- (isocyanatemethyl) -1,3,3-trimethylcyclohexane, 4,4-dicyclohexylmethane diisocyanate, 1,6-diisocyanatehexane, 1,6-diisocyanatehexane derivatives, and the like can be used, and polyols include polyester polyol, polyether polyol, polycarbonate polyol, and the like. In addition, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, etc. may be used as the acrylate compound having a hydroxy group. In addition, the urethane acrylate may be a multifunctional oligomer containing two or more polymerizable functional groups, and specifically includes at least one of a bifunctional oligomer, a trifunctional oligomer, a tetrafunctional oligomer, and a 6 functional oligomer. can do.

In addition, the weight average molecular weight of the urethane acrylic oligomer may be 100 to 10,000, more specifically 500 to 5,000, 1,000 to 3,000 or 1,500 to 2,000. The present invention can further improve the durability of the decorative material by adjusting the weight average molecular weight of the urethane acrylic oligomer to the above range.

Further, the acrylic monomer having a hydrophilic functional group may be an acrylic monomer containing a hydroxyl group (-OH group), a carboxyl group (-COOH group), an amine group (-NH ₂ group) and the like as a hydrophilic functional group. Specifically, as the acrylic monomer having a hydrophilic functional group, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxy Hydroxyoctyl (meth) acrylate, hydroxyethylene glycol (meth) acrylate or hydroxypropylene glycol (meth) acrylate, acrylic acid, methacrylic acid, (meth) acryloyloxyacetic acid, (meth) acryloyloxy Propyl acid, (meth) acryloyloxybutyl acid, acrylic acid duplex, itaconic acid, maleic acid and caprolactone modified hydroxyacrylate (caprolactone modified hydroxyl acrylate, CHA) Can be. For example, the acrylic monomer having a hydrophilic functional group may include hydroxyethyl methacrylate and hydroxypropyl acrylate.

In addition, the acrylic resin composition is 30 to 90 parts by weight of an acrylic monomer having a hydrophilic functional group, based on 100 parts by weight of the total urethane acrylic oligomer, specifically, 30 to 80 parts by weight, based on 100 parts by weight of the total urethane acrylic oligomer, 30 to 70 parts by weight, 30 to 60 parts by weight, 30 to 50 parts by weight, 30 to 40 parts by weight, 45 to 90 parts by weight, 50 to 90 parts by weight, 60 to 90 parts by weight, 70 to 90 parts by weight, 80 to 80 parts by weight 90 parts by weight, 45 to 80 parts by weight, 50 to 75 parts by weight, 65 to 90 parts by weight, 60 to 80 parts by weight, 67 to 83 parts by weight, 59 to 73 parts by weight, or 68 to 72 parts by weight .

As an example, the acrylic monomer having a hydrophilic functional group may include 30 parts by weight and 40 parts by weight, respectively, based on 100 parts by weight of the total urethane acrylic oligomer when hydroxyethyl (meth) acrylate and hydroxypropylacrylate are included. Can be.

In addition, the polyfunctional acrylic monomer is a monomer containing two or more polymerizable functional groups, and such polyfunctional acrylic monomers include 1,6-hexanediol diacrylate, tetraethylene glycol diacrylate, and tripropylene glycol diacrylate, And one or more selected from the group consisting of triethylene glycol diacrylate, dipropylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropaneethoxytriacrylate, and hexamethyldiamine diacrylate. For example, the acrylic resin composition according to the present invention may include tetraethylene glycol diacrylate, tripropylene glycol diacrylate, and hexamethyldiamine diacrylate as a multifunctional acrylic monomer.

In addition, the acrylic resin composition may include 50 to 150 parts by weight based on 100 parts by weight of the total urethane acrylic oligomer, specifically 50 to 140 parts by weight, 50 parts by weight based on 100 parts by weight of the total urethane acrylic oligomer, 50 To 130 parts by weight, 50 to 120 parts by weight, 50 to 110 parts by weight, 50 to 100 parts by weight, 50 to 90 parts by weight, 50 to 80 parts by weight, 75 to 150 parts by weight, 90 to 150 parts by weight, 100 to 150 parts by weight Parts by weight, 120 to 150 parts by weight, 130 to 150 parts by weight, 75 to 95 parts by weight, 90 to 105 parts by weight, 105 to 120 parts by weight, 115 to 130 parts by weight, 120 to 140 parts by weight, 135 to 150 parts by weight , 70 to 110 parts by weight, 85 to 120 parts by weight, 80 to 100 parts by weight, 90 to 100 parts by weight, 92 to 98 parts by weight, 81 to 98 parts by weight, 92 to 109 parts by weight, 45 to 65 parts by weight, 50 It may include a polyfunctional acrylic monomer in 60 to 60 parts by weight or 55 to 60 parts by weight.

As an example, the acrylic monomer having a polyfunctional acrylic functional group is a polyfunctional acrylic monomer, and includes tetraethylene glycol diacrylate, tripropylene glycol diacrylate, and hexamethyldiamine diacrylate. 100% of total urethane acrylic oligomer It may contain 40 parts by weight, 40 parts by weight and 10 parts by weight with respect to parts.

Furthermore, the acrylic resin composition according to the present invention may further include a filler having a high hardness in order to improve the durability of the decorative material at the same time as serving as a seed of the dendrite shape formed on the surface of the coating layer. For example, as the filler, one that can improve the surface hardness without affecting adhesion to the substrate layer and / or adhesion to ink droplets when forming the printed layer after curing of the acrylic resin composition can be used. Specifically, colloidal silica, alumina, glass beads, organic beads (polymer particles, etc.) may be used as the filler, and their average particle sizes are 1 μm to 10 μm, 3 μm to 7 μm, and 1 μm to 5 μm. , 5㎛ to 9㎛ or 6㎛ to 8㎛.

In addition, the filler may be included in 15 parts by weight or less based on 100 parts by weight of the composition so as not to impair the printability of the coating layer and the adhesion with the base layer. For example, the filler may contain 12 parts by weight or less with respect to 100 parts by weight of the composition, and more specifically, the content of the filler has an upper limit of 12 parts by weight or less, 11 parts by weight or less, 10 parts by weight or less, 8 parts by weight It may be less than or equal to 6 parts by weight, or less than or equal to 5 parts by weight, and may have a lower limit of 0.01 or more parts, 0.05 or more parts, 0.1 or more parts, 0.5 or more parts, or 1 or more parts. For example, the filler is 0.1 to 15 parts by weight, 0.1 to 14 parts by weight, 0.1 to 13 parts by weight, 0.1 to 12 parts by weight, 0.5 to 11 parts by weight, 1 to 5 parts by weight, 3 to 7 parts by weight, 5 It may be included as 12 to 12 parts by weight, 7 to 14 parts by weight, 3 to 11 parts by weight, 6 to 12 parts by weight, 9 to 14 parts by weight, 8 to 12 parts by weight, or 9 to 11 parts by weight.

In the present invention, by controlling the average particle size and content of the filler to the above range, it is possible to prevent the workability from being lowered due to an increase in viscosity due to excessive filler in the acrylic resin composition. In addition, it prevents cracking of the coating layer, and increases the adhesion between the coating layer and other layers to improve durability.

In addition, the acrylic resin composition used in the present invention may not contain a solvent, and even if it does not contain a solvent, the viscosity of the composition is low and thus the workability may be excellent when forming a coating layer. Specifically, the viscosity of the acrylic resin composition is 500 cps or less at 25 ° C, specifically 400 cps or less, 300 cps or less, 250 cps or less, 200 cps or less, 100 to 500 cps, 100 to 400 cps, 100 to 300 cps , 100 to 250 cps, 100 to 400 cps, 150 to 350 cps, 200 to 350 cps, may have a low viscosity of 250 to 350 cps or 280 to 300 cps, even if some fillers are included to improve the durability of the coating layer It can exhibit a low viscosity of 500 cps or less. Since the acrylic resin composition according to the present invention has a low viscosity of 500 cps or less, it is easy to work without mixing solvents, and thus has an environmentally friendly advantage.

In addition, the method of applying the acrylic resin composition on the substrate may be performed by a method known in the art, for example, Mayer (Mayer), D-bar (D-bar), rubber roll (rubber roll) , G / V roll, air knife, slot die, or the like.

In addition, in the method of manufacturing a decorative material according to the present invention, before forming the coating layer on the base layer, the method may further include forming at least one of a printing layer and a dimensionally stable layer on the base layer.

Here, the step of forming the printing layer and / or the dimensionally stable layer may be photo-cured for each composition including at least one selected from the group consisting of, for example, a binder resin, an initiator, a curing agent, and other additives and combinations thereof. It may be formed by thermosetting, or may be formed as a film or sheet using an extrusion method, a calendaring method, or the like. In addition, each composition may appropriately control the type and content of components included therein according to the properties and functions of each layer, and is not particularly limited. Specifically, the decorative material is formed by applying a predetermined composition to one surface of one layer and then curing or heat curing, or forming each layer as a film or sheet, and then forming them as a plywood process known in the art. It may be formed using, but is not limited thereto. In addition, the binder resin may include synthetic resin, bio resin, or both, for example, polyvinyl chloride (PVC) -based resin, polyurethane-based resin, polylactic acid-based resin, polyolefin resin, and the like. . In addition, the step of forming the printing layer is a step of printing a printing layer on the coating layer using water-soluble ink and / or water-based ink commonly used in the art, inkjet printing, gravure printing, screen printing, offset printing, It may be performed by rotary printing, flexo printing, or a combination printing method.

Hereinafter, the present invention will be described in more detail by examples and experimental examples.

However, the following examples and experimental examples are merely illustrative of the present invention, and the contents of the present invention are not limited to the following examples and experimental examples.

Example 1.

15 parts by weight of bifunctional urethane acrylate oligomer (weight average molecular weight: 1,400), 5 parts by weight of bifunctional aliphatic urethane acrylate oligomer, 15 parts by weight of hydrophobic urethane acrylate oligomer (weight average molecular weight: 7,000), hydrophilic functional group 25 parts by weight of the acrylic monomer and 20 parts by weight of the polyfunctional acrylic monomer (bifunctional) were mixed, and 1.5 parts by weight of benzophenone and igacure 754 were added as photoinitiators. Then, 10 parts by weight of a filler having an average size of 15 ± 3 μm was mixed to obtain an acrylic resin composition.

A sheet made of polyvinyl chloride (PVC), calendered, having a size of 100 cm x 100 cm, and a grooved sheet having an average depth of 22 to 25 μm and an average width of 16 to 19 μm on one side ( Average thickness: 0.5 mm) was prepared as a base layer. The prepared acrylic resin composition was applied on the prepared sheet. Then, under a nitrogen (N ₂ ) gas atmosphere (oxygen concentration of 30,000 ppm or less), the composition was irradiated with light of 172 ± 0.5 nm at a distance of 50 ± 1 cm from the composition (first light irradiation). Then, under air conditions, 300 ± 20 nm of light was irradiated at a distance of 100 ± 1 cm from the composition with a light amount of 600 mJ / cm 2 (second light irradiation) and 1,200 mJ / cm 2 under a nitrogen gas atmosphere. The decorative material was manufactured by forming a coating layer by light irradiation (third light irradiation) with a light amount of. Here, the amount of light irradiated during the first light irradiation and the average thickness of each area of the acrylic resin composition applied on the base layer are shown in Table 1 below.

Light quantity Average thickness Entire coating layer Area 1 Second area Area 3 Example 1 10 ± 1 mJ / ㎠ 12 ~ 16㎛ 30 ~ 35㎛ 12 ~ 16㎛ 8 ~ 12㎛ Example 2 7 ± 1 mJ / ㎠ 12 ~ 16㎛ 30 ~ 35㎛ 12 ~ 16㎛ 8 ~ 12㎛

Example 3.

The formation of a printing layer (average thickness: 1 μm) on the ink receiving layer by an inkjet printing method using four water-soluble inks showing black, red, blue, yellow and green color before forming the coating layer on the base layer Except, it was carried out in the same manner as in Example 1 to prepare a decorative material.

Example 4.

A polyethylene terephthalate film (average thickness: 30 μm) was heat-laminated at 150 ± 2 ° C. on the coating layer, and a transparent layer was further formed to prepare a decorative material in the same manner as in Example 1.

Comparative Example 1.

A decorative material was manufactured in the same manner as in Example 1, except that the first light irradiation step was not performed.

Comparative Example 2.

It was carried out in the same manner as in Example 1, except that the surface was free of grooves, and a calendered polyvinyl chloride (PVC) sheet (average thickness: 0.5 mm) having a width of 100 cm x 100 cm was used as the base layer. To prepare a decorative material. The average thickness of the coating layer uniformly formed on the surface of the decorative material was about 18 μm.

Comparative Example 3.

A decorative material was manufactured in the same manner as in Example 1, except that only the first light irradiation step and the third light irradiation step were performed without performing the second light irradiation step.

Experimental Example 1

To confirm the surface structure of the coating layer of the decorative material according to the present invention, scanning microscopy (SEM) analysis was performed on the decorative materials prepared in Examples 1 and 2 and Comparative Examples 1 and 3, and the results are shown in FIGS. 1 and 2 And 5.

1 and 2, it can be seen that the first to third regions having different surface structures are formed in the outermost coating layer of the decorative material according to the present invention. At this time, the first region includes a dot-shaped uneven structure, the second region includes a radial fine bend structure, and the third region has a wrinkle structure having an orientation of 80 to 100 ° in the longitudinal direction of the second region. Appeared to contain. In addition, it was confirmed that the second region was formed in an area where the groove of the base layer was not located and occupied about 90% or more of the total area, and the first area and the third area were formed along the groove of the base layer, respectively. It was confirmed that within about 5% of the.

In addition, in the case of the second region, as the amount of light irradiation in the first photo-curing step increases, the size of the random radial micro-bending structure formed on the surface becomes smaller as the fine bending is formed stronger, and the height of the center is reduced. The frequency was found to increase. Specifically, in the case of Example 1, the average size of the radially curved structure is 70 ± 2 μm, the height of the center is 12 ± 1 μm, and includes 40 to 60 pieces per unit area (1 mm X 1 mm), and Example In the case of 2, the average size of the radially curved structure was 50 ± 2 μm, the height of the center was 19 ± 1 μm, and it was found to include 140 to 165 dendrites per unit area (1 mm X 1 mm).

In comparison, it was found that the coating layer of the decorative material of Comparative Example 1, which did not perform the first light irradiation step, does not have a fine curved structure on the surface. It was confirmed that the decorative material of Comparative Example 2 using a base layer that does not include grooves on the surface formed only a radial fine curved structure in the coating layer. This means that the surface structure of the coating layer is changed by the grooves formed in the base layer.

In addition, referring to FIG. 5, the specimen of Comparative Example 3, which performed the first light irradiation step but did not perform the second light irradiation step under the air condition in which oxygen is present, includes a curved structure on the surface, but the degree of bending is large and the center portion is large. Since it does not include, it has been confirmed that it does not have a radial structure that decreases in height from the center to the periphery.

From these results, it can be seen that the surface structure of the coating layer is affected by the surface structure of the base layer on which the coating layer is formed. Along with this, the first light irradiation step of irradiating light having a wavelength of 250 nm or less generates an excimer, and the generated excimer generates short wavelength UV to rapidly accelerate surface hardening of the composition and / or coating layer, and thus the composition and / or It can be seen that shrinkage occurs on the surface of the coating layer. In addition, it can be seen that the generated shrinkage is controlled by a dendrite shape under the influence of oxygen in the air in the second light irradiation step.

Experimental Example 2.

To evaluate the surface roughness, surface gloss, stain resistance and non-slip resistance of the decorative material according to the present invention, the following experiments were performed on the decorative materials prepared in Examples and Comparative Examples, and the results are shown in Table 2 below:

A) Surface roughness evaluation

The surface roughness (Rz) of the decorative material was measured based on ISO 4287.

B) Glossiness evaluation

For the specimens of Examples and Comparative Examples, a 60 ° glossiness (gloss 60 ° condition) was measured using a gloss meter. At this time, the specimens of the examples were measured three times for glossiness at an arbitrary point corresponding to the second region, and an average value was derived. In addition, the surface of the specimens was observed with the naked eye to confirm whether a three-dimensional effect was realized according to deviation in glossiness.

C) Pollution resistance evaluation

The test was carried out according to KS M 3802, but by using oily magic as a contaminant, a line of about 10 cm was drawn on the surface, and after 30 seconds, the line drawn with Kim Wipes was removed to remove the residue from being erased based on the original contamination area. The area (e.g., traces or smears) was visually checked and the results were classified according to the following criteria:

- Level 1: The remaining area based on the initial contamination area is 90% or more

- Level 2: The remaining area based on the initial contamination area is 60% or more and less than 90%

- Level 3: The remaining area based on the initial contamination area is more than 20% and less than 60%

- Level 4: Residual area based on the initial contamination area is more than 5% and less than 20%

- Level 5: Less than 5% of the remaining area based on the initial contamination area.

D) Non-slip evaluation

A ramp test according to DIN 51130 was performed to measure the inclination angle at which slip occurs, and the measured inclination angle was classified according to the following criteria to determine the non-slip grade:

- R9: The angle of the inclination angle where the slip occurs is 6 ° or more but less than 10 °

- R10: The angle of the inclination angle where the slip occurs is 10 ° or more and less than 19 °

- R11: The angle of the inclination angle where the slip occurs is 19 ° or more and less than 27 °

- R12: The angle of the inclination angle where the slip occurs is 27 ° or more and less than 35 °

- R13: The angle of the inclination angle where the slip occurs is 35 ° or more.

Surface roughness (Rz) Average gloss Pollution resistance Non-slip property Example 1 20 ± 0.1㎛ 3.5 ± 0.01 5 ratings R11 Example 2 16 ± 0.1㎛ 4.1 ± 0.01 5 ratings R10 Comparative Example 1 12 ± 0.1㎛ 8.5 ± 0.01 5 ratings R9 Comparative Example 2 20 ± 0.1㎛ 4.1 ± 0.01 5 ratings R10 Comparative Example 3 16 ± 0.1㎛ 3.5 ± 0.01 5 ratings R10

As shown in Table 2, it can be seen that the surface glossiness according to the present invention is low, and the stain resistance and non-slip resistance are excellent.

Specifically, looking at Table 2, the decorative materials of Examples 1 and 2, the specimens have a constant average roughness (Rz) of 15 µm to 21 µm, and even when a small amount of a matting agent is used, gloss at a gloss of 60 ° is 5 or less. It was found that the contamination area was less than 5% after oily magic contamination and washing due to its excellent stain resistance. It was also found that no slippage occurred at an inclination angle of less than 19 °.

In comparison, the decorative material of Comparative Example 1 was found to have a high surface gloss and a significantly low non-slip property compared to the decorative materials of Example. In addition, the decorative material of Comparative Example 2 shows the same physical properties as the decorative material of Example, but since the surface includes a coating layer containing only the second region, the three-dimensional effect according to the gloss deviation was not visually confirmed.

From these results, the first to third regions of the coating layer have different surface structures due to the grooves formed on the surface of the base layer, and at the same time, when curing the light of the composition, a specific range of short wavelength light is irradiated stepwise under different conditions to coat the surface of the coating layer. Since the surface structure formed on the control is controlled, it can be seen through these that the properties of the decorative material, such as surface gloss, contamination resistance, non-slip property, design, etc., are controlled.

110: coating layer
111: Home
120: base layer
210: coating layer
220: base layer
211: dendrite
a: first area
b: second area
c: third area

Claims (15)

A base layer and a coating layer;
The coating layer,
A first region having a point-like uneven structure on the surface,
A second region having a radially curved structure extending from the center to the periphery with one point on the surface as the center, and
A decorative material comprising a third region positioned between the first region and the second region and having a corrugated structure oriented at 70 ° to 110 ° with respect to a longitudinal direction of a surface contacting the first area on the surface.
According to claim 1,
The coating layer is in a unit area (1m X 1m),
0.1 to 5.0 area% of the first region,
A second area of 90 to 99.8 area percent, and
A decorative material comprising a third area of 0.1 to 5.0 area%.
According to claim 1,
The average thickness of the coating layer is 50 μm or less, and satisfies the following condition 1 (except D _R2 = D _R3 = D _R1 ):
[Equation 1] D _R3 ≤ D _R2 ≤ D _R1
In Equation 1,
D _R1 is the average thickness of the first region,
D _R2 is the average thickness of the second region,
D _R3 is the average thickness of the third region.
According to claim 1,
The decorative material having an average surface roughness (Rz) of the second region is 10 μm to 30 μm.
According to claim 1,
The radial bend structure has 20 to 400 decorative materials per unit area (1 mm X 1 mm) of the surface.
According to claim 1,
The decorative material having an average diameter of the radially curved structure is 5 μm to 500 μm.

A first region having an uneven structure having a dot shape on its surface by irradiating ultraviolet rays to the acrylic resin composition applied on the base layer; A second region having a dendrite structure, which is a radially curved structure extending from the center to the periphery with one point as the center of the surface; And forming a coating layer positioned between the first region and the second region and having a third region having a corrugated structure oriented at 70 ° to 110 ° with respect to the longitudinal direction of the surface contacting the first area on the surface. Method of manufacturing a decorative material.
The method of claim 7,
The base layer is a method of manufacturing a decorative material comprising a groove having an average depth of 5 μm to 200 μm and an average width of 2 μm to 100 μm on the surface on which the acrylic resin composition is applied.
The method of claim 7,
The light irradiation step,
A first light irradiation step of activating the composition by irradiating light having a wavelength of 250 nm or less to an acrylic resin composition applied on a base layer under an inert gas condition;
A second light irradiation step of irradiating the activated composition with light having a wavelength of 250 nm to 400 nm under air conditions to first cure the composition to form a coating layer; And
A method of manufacturing a decorative material comprising a third light irradiation step of forming a coating layer by irradiating light having a wavelength of 200 nm to 400 nm under an inert gas condition to a second cured composition to form a coating layer on the primary cured composition.
The method of claim 9,
The first light irradiation step is a method of manufacturing a decorative material, characterized in that is performed with a light irradiation amount of 1 mJ / ㎠ to 100 mJ / ㎠.
The method of claim 9,
The first optical step is a method of manufacturing a decorative material, characterized in that the concentration of oxygen (O ₂ ) is performed under nitrogen (N ₂ ) conditions of 10 ppm to 30,000 ppm.
The method of claim 7,
The acrylic resin composition,
Urethane (meth) acrylic oligomer 100 parts by weight;
30 to 90 parts by weight of an acrylic monomer having a hydrophilic functional group; And
Method of manufacturing a decorative material comprising 50 to 150 parts by weight of a polyfunctional acrylic monomer.
The method of claim 7,
The acrylic resin composition is a method of manufacturing a decorative material further comprising at least one filler selected from the group consisting of silica, alumina, glass beads and organic beads.
The method of claim 13,
The content of the filler is 15 parts by weight or less based on 100 parts by weight of the acrylic resin composition.
The method of claim 7,
The viscosity of the acrylic resin composition is 500 cps or less.

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