KR20210043050A - Floorings having excellent anti-pollution property - Google Patents

Abstract

The present invention relates to a flooring material having excellent stain resistance and a method for manufacturing the same, wherein the flooring material contains a polyfunctional urethane arylate oligomer and a silicone acrylate oligomer in a surface treatment layer in a specific ratio, and fine By implementing the wrinkle structure at a high frequency, it has the advantage of implementing low glossiness without additional additives and excellent stain resistance.

Description

Flooring having excellent anti-pollution property {Floorings having excellent anti-pollution property}

The present invention relates to a flooring material having excellent fouling resistance and a method of manufacturing the same, and in detail, while controlling the composition of the surface treatment layer, which is the top layer of the flooring material, a fine wrinkle structure is implemented on the surface at high frequency to realize low gloss without additional additives. And, it relates to a flooring material exhibiting high fouling resistance and a method of manufacturing the same.

In general, the flooring material provides a sanitary space by blocking dust and cold air from the cement floor, and has decorative effects such as changing the indoor atmosphere according to the taste of the customer because the beautiful patterns of various colors are printed. In such a conventional flooring material, when the surface is contaminated with contaminants, the user cannot easily erase the traces of the contaminants, so that the flooring materials having the contaminant traces cannot perform their basic functions.

In addition, as the gloss decreases, the stain resistance decreases, and functions such as cleaning are significantly reduced. Therefore, it is difficult to impart a natural gloss like a natural material while maintaining high stain resistance. Specifically, when the existing floor coverings with pollution resistance are contaminated with oily magic or other pollutants, the gloss is erased above a certain level with a 60 degree gloss-meter, but it can exhibit pollution resistance below it. There are no limits.

In order to solve this problem, an ultraviolet curing surface treatment agent for treating the surface of a flooring material has been developed. However, the surface treatment agent contains about 10% by weight of silica as a matting agent in order to lower the gloss of the floor material, and the silica is porous and has a very low apparent specific gravity, and as the content increases, fine dust, moisture, grease, etc. Because the adsorption of the material is facilitated, the contamination resistance rapidly decreases, and marks such as hand and foot sweat marks remain on the surface of the surface-treated floor material, resulting in a phenomenon in which the exterior becomes cloudy as if fogged.

Accordingly, there has been developed a flooring material that achieves low gloss even without a matting agent by sequentially irradiating ultraviolet rays of different specific wavelengths when forming the surface treatment layer. However, the flooring material can achieve a lower gloss compared to the existing flooring material, but a fine corrugated structure having a high roughness (Ra) exceeding 2 μm is induced on the surface, and contaminants are stuck on the surface and thus the fouling resistance is rather lowered. Even if it is improved or improved, there is a marginal limit to that degree.

Accordingly, there is an urgent need to develop a flooring material that realizes a low glossiness of the flooring material while excluding a matting agent including inorganic particles, and at the same time has improved fouling resistance.

Republic of Korea Patent Publication No. 2014-0089074 Republic of Korea Patent Publication No. 20180127922

An object of the present invention is to provide a flooring material having low gloss and excellent stain resistance.

Thus, the present invention in one embodiment,

A foam layer, a glass fiber layer, a printing layer, a base layer, and a surface treatment layer of an acrylic resin composition;

The surface treatment layer,

It has a surface structure including 5 to 20 wrinkles per unit area (0.1 mm X 0.1 mm),

Fourier transform-infrared spectroscopy measurements provide flooring with peaks at ^{799±2 cm -1} , 1088±0.3 cm ^-1 and 1258±0.6 cm ^-1.

In addition, the present invention in one embodiment,

A first light irradiation step of partially curing the composition by irradiating light having a wavelength of 200 nm to 400 nm in air to the acrylic resin composition applied on the base layer,

A second light irradiation step of irradiating light with a wavelength of less than 300 nm to induce wrinkles on the surface of the partially cured composition, and

A third light irradiation step of forming a surface treatment layer by irradiating light having a wavelength of 200 nm to 400 nm on the composition in which wrinkles are induced on the surface under nitrogen gas (N _{2) conditions;}

The surface treatment layer,

It has a surface structure including 5 to 20 wrinkles per unit area (0.1 mm X 0.1 mm),

In the Fourier transform-infrared spectroscopy measurement, a method of manufacturing a flooring material having peaks at ^{799±2 cm -1} , 1088±0.3 cm ^-1 and 1258±0.6 cm ^{-1 is provided.}

The flooring material according to the present invention includes a polyfunctional urethane arylate oligomer and a silicone acrylate oligomer in a specific ratio in the surface treatment layer, and implements a fine wrinkle structure on the surface of the surface treatment layer at a high frequency. It has the advantage of realizing gloss and excellent stain resistance.

1 is an image showing a scanning electron microscope (SEM) analysis result of the flooring specimen of Example 1 according to the present invention.
2 is an image showing a scanning electron microscope (SEM) analysis result of the flooring specimen of Comparative Example 5 according to the present invention.
3 is a graph showing a result of analyzing the Fourier transform-infrared spectroscopy for the flooring specimen of Example 1 according to the present invention.

In the present invention, various modifications may be made and various embodiments may be provided, 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 a specific embodiment, it should be understood to include all changes, 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 designate the presence of features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, but one or more other features. It is to be understood that the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof does not preclude in advance.

In addition, the accompanying drawings in the present invention should be understood as being enlarged or reduced for convenience of description.

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

In the present invention, "T" represents the thickness of each layer or sheet provided on the flooring, and may be the same as the unit "mm".

In addition, in the present invention, "molecular weight" refers to the "weight average molecular weight" of the polymer, and the weight average molecular weight may be a value measured through gel permeation chromatography (GPC) measurement.

In addition, in the present invention, "surface roughness" may be equated with "surface roughness" of the surface treatment layer formed on the base layer or "height of wrinkles" formed on the surface of the surface treatment layer. In addition, the surface roughness may be a value analyzed by photographing the surface with a scanning electron microscope (SEM), and in some cases, may be a value measured according to the centerline average roughness (Ra) according to KS B 0161.

The present invention relates to a flooring material having excellent stain resistance and a method of manufacturing the same.

In general, when the surface of the flooring material is contaminated with contaminants, the user cannot easily erase the traces of the contaminants, and thus there is a problem that the flooring materials having the contaminant trace cannot perform its basic functions. In addition, as the gloss decreases, the stain resistance decreases, and functions such as cleaning are significantly reduced. Therefore, it is difficult to impart a natural gloss like a natural material while maintaining high stain resistance.

In order to solve these problems, UV-curing surface treatment agents containing about 10% by weight of silica as a matting agent, and floor materials having a fine wrinkle structure having a high roughness (Ra) exceeding 2㎛ on the surface have been developed. Has been done. However, the above techniques show a low glossiness on the surface, but the degree of improvement in stain resistance is insignificant.

Accordingly, the present invention provides a flooring material having low surface gloss and excellent stain resistance, and a method for manufacturing the same.

The flooring material according to the present invention contains a polyfunctional urethane arylate oligomer and a silicone acrylate oligomer in a specific ratio in the surface treatment layer, which is the top layer, and a separate additive by implementing a fine wrinkle structure on the surface of the surface treatment layer at high frequency. It has the advantage of implementing low glossiness and excellent stain resistance.

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

Flooring

The present invention in one embodiment,

It provides a flooring material provided with a surface treatment layer formed from an acrylic resin composition on a base layer.

The flooring material according to the present invention is an indoor flooring material used in homes or offices, and the surface treatment layer is a surface treatment layer of an acrylic resin composition and is located on the outermost layer of the flooring material, and the surface has a fine wrinkle structure having a certain surface roughness and shape. Has.

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

When observing the surface of the resin layer on which wrinkles are formed in the normal direction of the resin layer, ridges, valleys, wrinkles, and irregularities formed therefrom are observed, for example, over the entire area of the surface while undergoing a curing process described below. .

The wrinkles may be observed in a form including a line shape (eg, straight line, curved line) having a directionality. As an example, the wrinkles on the surface formed by repeating straight and curved shapes may give a curvature such as a mountain range shape to the surface of the resin layer. The surface uneven structure formed by corrugations having a line shape as described above is different from the so-called point-wise uneven shape formed by using particles in the composition for forming a resin layer or by using emulsion dispersion. It is clearly distinguished.

In one example, the surface may include wrinkles that can be visually recognized in a predetermined size and shape. For example, the wrinkles may have a width of nm level (less than about 1 μm) and may have a line (straight or curved) shape extending several micrometers (μm) or more. The width and/or height of the wrinkle and the length of the wrinkle extension can be confirmed from an image (eg, SEM) photographing the wrinkled surface as shown in the accompanying drawings. In addition, the length in the extending direction may be greater than the width. Specifically, the ends of the wrinkles extending in the form of a straight line or a curve form a slope that gradually decreases in height and may be incorporated into the resin layer. In some cases, the end of any one wrinkle having the size and shape may be a starting point of another wrinkle or a connection part with another wrinkle. In addition, when observing the cross-sectional curve near the wrinkle in the direction perpendicular to the extension direction of the wrinkle, the width of the wrinkle gradually decreases in both directions from the point or part (e.g., ridge) forming the height of the wrinkle. The paper is inclined and can be incorporated into the resin layer. On the other hand, when a ridge and a valley adjacent thereto form a wrinkle or a part thereof, the area of the shape recognized including the valley may be viewed as the width of the wrinkle.

As an example, the width of the wrinkles may be 900 nm or less. Specifically, the width of the wrinkles may have an upper limit of 800 nm or less, 700 nm or less, 600 nm or less, 500 nm or less, 400 nm or less, or 300 nm or less, and 150 nm or more, 200 nm or more, 250 nm It may have a lower limit of greater than or equal to 300 nm. If the above range is satisfied, it may be advantageous for the surface formed by the wrinkles to have matte properties and stain resistance.

In addition, the length at which the wrinkles extend may have an upper limit of 200 µm or less, 100 µm or less, or 50 µm or less, and a lower limit of 5 µm or more, 10 µm or more, 20 µm or more, 30 µm or more, 40 µm or more, 50 µm or more , 60 μm or more, 70 μm or more, 80 μm or more, or 90 μm or more. If the above range is satisfied, it may be advantageous for the surface formed by the wrinkles to have matte properties and stain resistance.

The corrugation may have a predetermined height over most of its extending length. For example, the wrinkles may have a height of 2 μm or less, 1.5 μm or less, 1.0 μm or less, or 0.1 to 0.9 μm, which may be equated with “surface roughness” of the surface treatment layer. Specifically, when observing the cross-sectional curve of the wrinkle in the direction perpendicular to the extension direction of the wrinkle, the point or part that forms the height of the wrinkle (e.g., ridge) and the point or part of the resin layer where the width of the wrinkle is mixed ( Example: Valley) may have a "height difference" or "surface roughness" of 2 µm or less. At this time, the most of the length at which the height is observed means a length that is 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, or 95% or more of the length that the wrinkles continuously extend along the shape. it means. When the height difference gradually decreases in the extension direction of the wrinkles, and the height is significantly lowered, a shape in which the ends of the wrinkles are mixed into the resin layer can be observed, or contact with other wrinkles whose size or shape is different from the wrinkles starts. It may be observed that the shape becomes. In the latter case, a more complex corrugated structure can form irregularities on the surface.

The wrinkles are observed over the entire area of the surface, and may form surface wrinkles or irregularities while showing a regular or irregular distribution. For example, the wrinkles on the surface may form surface irregularities while having a shape in which a plurality of wrinkles are branched in different directions from one specific point. Specifically, the wrinkles on the surface may have a shape similar to “Y” or “<”. At this time, wrinkles having a shape similar to "Y" or "<" may be densely arranged to form surface irregularities.

The present invention can increase the frequency of finer wrinkles by forming wrinkles having the above-described shape and/or size on the surface treatment layer, thereby lowering the glossiness without using a matting agent in the surface treatment layer, and wrinkles It is possible to prevent contamination of the surface by remaining contaminants in between.

As an example, the flooring material may include 5 to 20 wrinkles per unit area (0.1 mm X 0.1 mm) of the surface of the surface treatment layer (the same as 500 to 2,000 per 1 mm X 1 mm). Specifically, on the surface of the surface treatment layer of the flooring, 5 to 18, 5 to 15, 5 to 12, 5 to 10, 5 to 8, 7 to 20 per unit area (0.1 mm X 0.1 mm) , 10 to 20, 12 to 20, 15 to 20, 18 to 20, 8 to 18, 10 to 15, 12 to 18, or 8 to 14 wrinkles may be present.

Further, the surface treatment layer may be formed using a polyfunctional urethane acrylate oligomer and a silicone acrylate oligomer, and contains a silicone acrylate oligomer to implement hydrophobicity on the surface, thereby minimizing the surface wettability of contaminants.

In this case, the Fourier transform-infrared spectroscopy (FT-IR) measurement of the flooring material may have a high intensity in a specific wave number range. Specifically, in the case of measuring the Fourier transform-infrared spectroscopy in the wavenumber range of 400 to 4,000 cm ^-1 , the flooring material has a peak at wavenumbers of ^{799±2 cm -1} , 1088±0.3 cm ^-1 and 1258±0.6 cm ^-1. The peak may have an intensity of 40 au or more, specifically 50 au or more, or 50 to 70 au when the intensity of the peak with the strongest intensity in the measured total spectral spectrum is 100 au. Here, the peaks appearing at wavenumbers of 799±2 cm ^-1 , 1088±0.3 cm ^-1 and 1258±0.6 cm ^-1 _{are the banding of Si-CH 3} , Si-O-Si and Si-CH ₃ bonds, respectively, and/ Alternatively, a peak indicative of stretching may be displayed.

In addition, the flooring material has a small size and a high frequency wrinkle structure as described above, and has a surface treatment layer using a polyfunctional urethane acrylate oligomer and a silicone acrylate oligomer as the uppermost layer, thereby chemically making the surface hydrophobic. At the same time, it is possible to physically prevent contaminants from remaining stuck in the corrugated structure of the surface, so that the following condition 1 may be satisfied:

[Condition 1] After 1 minute of oil magic contamination, the residual contamination area of the washed surface treatment layer is less than 5% of the original contamination area.

Specifically, the surface treatment layer located at the outermost part of the flooring has improved contamination resistance to organic substances such as oily magic, and thus, when washing after 1 minute after applying oil magic to the surface, the surface of the washed surface treatment layer The residual contaminated area of may be less than 5% based on the initial contaminated area, more specifically less than 4%, less than 3%, or less than 2%, and in some cases, the residual area contaminated with oily magic may be close to 0%. have.

Further, the flooring material can achieve remarkably low gloss without including a matting agent in the surface treatment layer by inducing scattering of light incident on the surface through the corrugated structure formed on the surface of the surface treatment layer.

As an example, the floor material may have a surface gloss of less than 3 when measuring 60° gloss (gloss 60° condition) using a gloss meter, and more specifically, an upper limit of 2.8 or less, 2.5 or less, 2.2 or less, 2.0 or less, 1.8 or less, 1.5 or less, 1.2 or less, or 1.0 or less, and the lower limit may be 0.1 or more, 0.5 or more, or 1 or more. For example, the average surface gloss of the flooring material is 0.1 to 2.8, 0.1 to 2.5, 0.2 to 2.2, 0.2 to 2.0, 0.5 to 1.8, 0.2 to 1.5, 0.2 to 1.7, 0.5 to 1.5, 0.8 to 1.6, 0.9 to 1.5, 0.1 to 1.4, or 1.1 to 1.5.

The surface treatment layer may have an average thickness in an appropriate range that does not affect durability. For example, the surface treatment layer may have an average thickness of 10 µm to 30 µm so as not to be torn or lost by external magnetic poles, and more specifically 10 µm to 25 µm, 10 µm to 20 µm, 10 µm to 15 µm. It may be µm, 15µm to 30µm, 20µm to 30µm, 15µm to 25µm, 18µm to 25µm, 22µm to 28µm, 11µm to 20µm, or 12µm to 18µm.

Meanwhile, the flooring material according to the present invention may further include a foam layer, a glass fiber layer, and a printing layer in addition to the substrate layer and the surface treatment layer, and specifically, a foam layer, a glass fiber layer, a printing layer, a substrate layer, and a surface treatment layer are sequentially It may have a stacked structure.

At this time, the foam layer is a layer located at the bottom of the floor material and supports the upper cured layer, the substrate layer, the printing layer, the dimensional stability layer, etc., while absorbing the impact and noise of the upper or lower part including pores of a certain size. As a layer that improves the walking feeling by reducing the amount of impact and increases the stability, foamed PVC (Poly Vinyl Chloride), foamed PE (Polyethylene), foamed PP (Polypropylene), foamed EVA (Ethylene Vinyl Acetate), and foamed urethane (Polyurethane), foamed silicone, or foamed rubber, for example, foamed SBS (Styrene Butadiene Styrene Block Copolymer), foamed BR (Butadiene Rubber), foamed NBR (Acrylonitrile Butadiene Rubber), foamed IR (Isoprene Rubber), etc. .

Here, the foam layer is not particularly limited in its components, but polyvinyl chloride (PVC), thermoplastic polyurethane (TPU), nitrile-butadiene rubber (NBR), polyvinylether, PVE), ethylene vinylacetate (EVA), polyurethane (polyurethane, PU), and the like.

In addition, the foam layer may include "closed pores", and the average size of the pores may be 100 to 900 μm. Specifically, the average size of the pores is 100 to 800 ㎛, 100 to 700 ㎛, 100 to 600 ㎛, 100 to 500 ㎛, 200 to 900 ㎛, 300 to 900 ㎛, 400 to 900 ㎛, 500 to 900 ㎛, 600 To 900 µm, 200 to 800 µm, 500 to 800 µm, 600 to 700 µm, 200 to 400 µm, or 750 to 900 µm.

In addition, the average thickness of the foam layer may be 0.5 to 10T, more specifically 0.5 to 8T, 0.5 to 6T, 0.5 to 4T, 4 to 10 T, 6 to 10 T, 8 to 10T, 3 to 6T, It may be 4 to 7T, 7 to 9T, 2 to 3T, 0.5 to 1.5T.

Furthermore, the foam layer may have a constant foam density and average thickness in order to maximize shock absorption during external impact. Specifically, the foam layer may have a foam density of 100 kg/m 3 to 500 kg/m 3 and an average thickness of 0.5 ㎜ to 5 ㎜. Specifically, the foam layer has a foam density of 100 kg/m 3 to 400 kg/m 3, 100 kg/m 3 to 300 kg/m 3, 100 kg/m 3 to 200 kg/m 3, 200 kg/m 3 to 400 kg/m 3, 250 kg/m 3 to 500 kg/m 3, 100 kg/m 3 to 500 kg/m 3, 300 kg/m 3 to 500 kg/m 3, 150 kg/m 3 to 200 kg/m 3 or 120 kg/m 3 to 160 kg/m 3 have. In addition, the foam layer has an average thickness of 0.5 mm to 4 mm, 0.5 mm to 3 mm, 0.5 mm to 2 mm, 0.5 mm to 1 mm, 1 mm to 3 mm, 2 mm to 4 mm, or 1.5 mm to 2 mm Can be

In addition, the dimensionally stable layer may be formed of a composite material in which glass fibers are impregnated with a binder resin such as polyvinyl chloride (PVC) resin, polyurethane resin, polylactic acid resin, and polyolefin resin. The dimensional stability layer thus formed can achieve excellent dimensional stability by reducing dimensional strain even under high temperature and high humidity conditions, while maintaining high level of adhesion with other layers laminated on the upper and lower sides to achieve excellent durability. At this time, the average thickness of the dimensionally stable layer may be about 0.1 mm to about 2.0 mm.

In addition, the average diameter of the glass fibers is 100 to 900 ㎛, 100 to 800 ㎛, 100 to 700 ㎛, 100 to 600 ㎛, 100 to 500 ㎛, 100 to 400 ㎛, 200 to 1,000 ㎛, 200 to 800 ㎛, 200 To 600 µm, 200 to 400 µm, 300 to 800 µm, 400 to 600 µm, 500 to 1,000 µm, 300 to 500 µm, or 150 to 300 µm. In the present invention, by controlling the average diameter of the glass fibers within the above range, high strength and high durability can be realized even when a glass fiber layer having a low basis weight is included.

In addition, the average weight per unit area of the glass fiber layer ^{may range from 110 to 140 g/m 2} , specifically 110 to 135 g/m ² , 110 to 130 g/m ² , 110 to 125 g/m ² , 115 to 140 g/m ² , 115 to 135 g/m ² , 115 to 130 g/m ² , or 118 to 122 g/m ² . By controlling the average weight per unit area of the glass fiber layer within the above range, it is possible to maintain excellent hardness of the substrate while preventing an excessive increase in weight.

In addition, the base layer may have a thickness of about 0.05 mm to about 2.0 mm as a transparent or translucent polyvinyl chloride (PVC) layer, and by having a thickness within the above range, the total thickness of the flooring material to be described later is not excessively increased. As described above, the pattern or pattern of the printed layer laminated on the lower side can be sufficiently protected.

In addition, the printing layer may include a white layer forming a base and a transfer layer implementing a pattern. For example, transfer printing, gravure printing, screen printing, offset printing, rotary printing, or flexographic printing, etc. It can be formed by giving a pattern in a manner. In this case, the printed layer may have an average thickness of about 1 μm to about 10 μm.

Manufacturing method of flooring material

In addition, the present invention in one embodiment,

A first light irradiation step of partially curing the composition by irradiating light having a wavelength of 200 nm to 400 nm in air to the acrylic resin composition applied on the base layer,

A second light irradiation step of irradiating light with a wavelength of less than 300 nm to induce wrinkles on the surface of the partially cured composition, and

Under nitrogen gas (N ₂ ) conditions, it provides a method for manufacturing a flooring material comprising a third light irradiation step of forming a surface treatment layer by irradiating light having a wavelength of 200 ㎚ to 400 ㎚ to the composition in which wrinkles are induced on the surface.

The manufacturing method of the flooring material according to the present invention includes a step of irradiating an acrylic resin composition with short wavelength light in a specific range under different conditions in three steps to cure it.

Specifically, the first light irradiation step is a first step of irradiating light to the composition applied on the substrate, and partially curing the composition by irradiating light having a wavelength of 200 nm to 400 nm to the acrylic resin composition in the air. Is a step of pre-curing the acrylic resin composition with a curing rate of 20 to 60% or 30 to 50%. Here, the curing rate may be confirmed through Fourier transform-infrared spectroscopy (FT-IR) measurement before and after the first light irradiation step of the acrylic resin composition, and specifically, before and after the first light irradiation step of the acrylic resin composition. After Fourier transform-infrared spectroscopy (FT-IR) measurement, it can be seen from the change in intensity of the stretching peak of the C=C bond that appears in the wavenumber range of ^{810.2±2 cm -1.}

In addition, the oxygen gas (O ₂ ) condition may be performed in general air or dry air conditions, and in some cases, oxygen gas (O ₂ ) is in nitrogen gas (N ₂ ). It can mean a mixed state. In this case, the concentration of the oxygen gas (O _{2 ) in the nitrogen gas (N 2} ) may be 30 parts by volume or less or 20 parts by volume or less with respect to 100 parts by volume of the total mixed gas, and more specifically 5 to 25 parts by volume, 10 It may be from 25 to 25 parts by volume, or from 15 to 22 parts by volume.

The present invention can significantly increase the frequency of wrinkles by preliminarily curing before forming wrinkles on the surface of the acrylic resin composition through the first light irradiation step. For example, the flooring material according to the present invention has 5 to 20 wrinkles per unit area of 0.1 mm X 0.1 mm (500 to 2,000 per unit area of 1 mm X 1 mm) on the surface of the surface treatment layer by performing the first light irradiation step. However, when the first light irradiation step is not performed, a wrinkle structure having a low frequency of 400 or less per unit area of 0.1 mm X 0.1 mm may be included.

Meanwhile, the method of applying the composition on the substrate may be performed by a method known in the art, for example, Mayer, D-bar, rubber roll, G/ It can be performed using a V roll (G/V roll), an air knife, a slot die, a microgravure, or the like.

In addition, in the second light irradiation step, the excimer generated by the irradiated light shrinks the surface of the composition and/or the surface treatment layer to form wrinkles, thereby increasing the scattering rate of light incident on the surface. The present invention can increase the scattering rate of light by shrinking the surface of the composition and/or the surface treatment layer into the above-described corrugated structure using excimer, so that the glossiness of the surface treatment layer can be reduced without the use of a matting agent. To this end, the second light irradiation step may be performed in an atmosphere _{of nitrogen (N 2} ), which is a non-reactive gas, using light having a wavelength of less than 300 nm with high energy, specifically 100 to 200 nm or 150 to 195 nm. And, in some cases, it may be carried out in _{a nitrogen (N 2 ) atmosphere containing a small amount of oxygen (O 2} ), specifically 1,000 ppm or less. In addition, the distance between the composition and the light source in the second light irradiation step may be 50 to 150 mm, specifically 50 to 120 mm, 60 to 120 mm, 80 to 130 mm, 70 to 150 mm, 100 to 150 mm, 120 It may be ~140mm, 80~110mm, 90~110mm, or 95~105mm.

In addition, the amount of light irradiation in the second light irradiation step may be 25 mJ/cm 2 to 75 mJ/cm 2, specifically 25 mJ/cm 2 to 70 mJ/cm 2 18 25 mJ/cm 2 to 50 mJ/cm 2, 50 mJ /Cm2 to 75 mJ/cm2, 40 mJ/cm2 to 60 mJ/cm2, 25 mJ/cm2 to 45 mJ/cm2, 40 mJ/cm2 to 65 mJ/cm2, 45 mJ/cm2 to 55 mJ/cm2 or 48 mJ /Cm2 to 53 mJ/cm2.

As an example, in the second light irradiation step, in order to form an excimer in the composition, light having a wavelength of 172±2 nm is dried in air or nitrogen (N ₂ ) conditions _{including 100 ppm of oxygen (O 2 ).} It can be performed by irradiating for a very short time of 1 to 2 seconds at a light amount of 52 to 57 mJ/cm 2 (ie, light irradiation).

The present invention easily controls the size and/or shape of the fine wrinkle structure formed on the surface of the surface treatment layer by controlling the gas conditions, the distance between the composition and the light source, and/or the amount of light irradiation during the second light irradiation step in the above range. can do.

Furthermore, the third light irradiation step is a step in which the composition is completely cured to 95% or more by additionally irradiating the wrinkled composition with ultraviolet rays (UV), in other words, "semi-curing", with a wavelength of 400 nm or less, specifically Is performed in _{a nitrogen (N 2} ) atmosphere using light with a wavelength of 100 to 400 nm, 200 to 400 nm, 200 to 300 nm, 300 to 400 nm, 150 to 300 nm, 200 to 250 nm, or 270 to 320 nm Can be.

, 구체적으로는 20 내지 80

또는 30 내지 70

일 수 있다.At this time, the surface temperature of the cured composition and/or the surface treatment layer is 20 to 90

, Specifically 20 to 80

Or 30 to 70

Can be

As an example, the third light irradiation step is performed by irradiating light having a wavelength of 300±10 nm to the composition and/or the surface treatment layer 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 surface treatment layer and the light source may be 100±10 mm.

The light irradiated in the present invention may be irradiated according to a known method capable of irradiating light of 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.

In addition, in the present invention, the light irradiation time may be a very short time of 1 to 2 seconds, and this light irradiation time may be controlled by the speed at which the composition moves during light irradiation, for example, the speed at which the composition coated on the substrate moves. I can. For example, the movement speed of the 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 to 40 m/min, 15 to 25 m/min, 5 to 15 m/min, 15 to 20 m/min, 35 to 40 m/min, or 18 to 22 m/min.

The present invention can exhibit a high curing rate even if a small amount of the initiator is included in the above range by stepwise using a specific range of short wavelength light under different conditions when curing the composition.

Meanwhile, the acrylic resin composition includes a polyfunctional acrylate oligomer as a main component, and the polyfunctional acrylate oligomer may include a polyfunctional urethane acrylate oligomer and a polyfunctional silicone acrylate oligomer.

Here, the urethane acrylate oligomer has high stain resistance and resistance to yellowing of the cured product, rapid radical polymerization reaction occurs due to the initiation reaction of a photoinitiator, and provides a coating film excellent in elasticity and toughness, and in particular, a vinyl chloride resin. There is an advantage of excellent adhesion to the base layer containing (PVC).

These urethane acrylate oligomers are synthesized as polyisocyanates, polyols, and acrylate compounds having a hydroxy group. In this case, the polyisocyanate is 5-isocyanate-1-(isocyanate methyl)-1,3,3-trimethylcyclohexane. , 4,4-dicyclohexylmethane diisocyanate, 1,6-diisocyanate hexane, 1,6-diisocyanate hexane derivatives, etc. can be used, and polyols include polyester polyol, polyether polyol, polycarbonate polyol, etc. It can be used, and as an acrylate compound having a hydroxy group, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and the like can be used. In addition, the urethane acrylate is a polyfunctional oligomer containing 2 or more polymerizable functional groups, and specifically, may include at least one of a bifunctional oligomer, a trifunctional oligomer, a tetrafunctional oligomer, and a 6functional oligomer. have.

The multifunctional urethane acrylate oligomer may have an average weight average molecular weight of 1,000 to 30,000, and more specifically 1,000 to 25,000, 1,000 to 20,000, 1,500 to 20,000, 1,000 to 10,000, 5,000 to 8,000, 8,000 to 12,000, 10,000 to 15,000. , It may be 15,000 to 20,000, 1,000 to 5,000, or 1,500 to 3,500. The present invention can further improve the durability of the surface treatment layer by adjusting the weight average molecular weight of the urethane acrylic oligomer within the above range.

In addition, the polyfunctional silicone acrylate oligomer has a function of lowering the surface tension of the acrylic resin composition, and the resin composition having such a reduced surface tension can form a cured product having low surface energy upon curing. Since the cured product with low surface energy has excellent stain resistance, it has the advantage that it is difficult for contaminants such as fine dust, moisture, and oil to be adsorbed on the surface.

Such polyfunctional silicone acrylate oligomers include acrylic monomers such as alkyl acrylates and alkyl (meth) acrylates, and 3-methacryloxypropyltrimethoxysilane (MPTS) having a silicon (Si)-containing functional group. It may be an oligomer obtained by polymerizing an alkoxysilane-based acrylic monomer of, or a silicone urethane acrylate polymer or a silicone polyester acrylate polymer in which a urethane acrylate polymer or polyester acrylate is modified with silicon (Si). In addition, the polyfunctional silicone acrylate oligomer may be a polyfunctional oligomer containing 2 or more polymerizable functional groups, and specifically, one of a bifunctional oligomer, a trifunctional oligomer, a tetrafunctional oligomer and a 6functional oligomer It may include more than one. In addition, the average weight average molecular weight (Mw) of the multifunctional silicone acrylate oligomer may be 500 to 20,000, specifically 500 to 30,000, 1,000 to 20,000, 1,000 to 10,000, 1,000 to 5,000, 1,500 to 3,500 or 1,000 to Can be 2,000.

Furthermore, the present invention Fourier transformation on the surface treatment layer is to contain a multi-functional silicone acrylate oligomer in the acrylic resin composition, formed by curing the above-mentioned acrylic resin composition-infrared spectroscopy (FT-IR) 799 ± 2 cm when measured ^{- 1} , 1088 ± 0.3 cm ^-1 and 1258 ± 0.6 cm ^-1 , the peak may appear at wavenumbers, the peak is 40 au or more when the intensity of the peak with the strongest intensity in the measured whole spectral spectrum is 100 au. , Specifically, it may have a strength of 50 au or more, or 50 to 70 au. Here, the peaks appearing at wavenumbers of 799±2 cm ^-1 , 1088±0.3 cm ^-1 and 1258±0.6 cm ^-1 _{are the banding of Si-CH 3} , Si-O-Si and Si-CH ₃ bonds, respectively, and/ Alternatively, a peak indicative of stretching may be displayed.

In addition, the acrylic resin composition may include a polyfunctional urethane acrylate oligomer and a polyfunctional silicone acrylate oligomer in a predetermined ratio. For example, the polyfunctional silicone acrylate oligomer may be included in an amount of 10 to 30 parts by weight based on 100 parts by weight of a polyfunctional urethane acrylate oligomer, and specifically, 10 to 25 parts by weight based on 100 parts by weight of a polyfunctional urethane acrylate oligomer. , 10 to 22 parts by weight, 10 to 20 parts by weight, 15 to 30 parts by weight, 15 to 25 parts by weight, 12 to 22 parts by weight, or 14 to 20 parts by weight.

In the present invention, by adjusting the content of the polyfunctional urethane acrylate oligomer and the polyfunctional silicone acrylate oligomer contained in the acrylic resin composition in the same ratio as described above, the manufacturing cost is significantly increased due to a large amount of the polyfunctional silicone acrylate oligomer, and the bulky ( It is possible to prevent the acrylic resin composition from being uncured due to the bulky) silicone functional group, and at the same time, it is possible to appropriately control the surface energy of the surface treatment layer formed by curing the acrylic resin composition. In this case, when measuring the Fourier transform-infrared spectroscopy (FT-IR) of the surface treatment layer in the wavenumber range of ^{400 to 4,000 cm -1 , the values of 799 ± 2 cm -1} , 1088 ± 0.3 cm ^-1 and 1258 ± 0.6 cm ^-1 A peak may appear in the wavenumber, and the peak has an intensity of 40 au or more, specifically 50 au or more, or 50 to 70 au, when the intensity of the peak with the strongest intensity in the measured whole spectral spectrum is 100 au. I can have it. Here, the peaks appearing at wavenumbers of 799±2 cm ^-1 , 1088±0.3 cm ^-1 and 1258±0.6 cm ^-1 _{are the banding of Si-CH 3} , Si-O-Si and Si-CH ₃ bonds, respectively, and/ Alternatively, a peak indicative of stretching may be displayed.

In addition, the C=O bonding peak of the urethane acrylate oligomer found at a wavenumber of ^{1728±2 cm -1} when measuring the Fourier transform-infrared spectroscopy (FT-IR) for the surface treatment layer in the wavenumber range of 400 to 4,000 cm ^{-1 and} The ratio of the Si-O-Si bonding peak of the silicon acrylate oligomer identified at a wavenumber of 1088±0.3 cm ^{-1 may be 0.85 to 1.10, and specifically 0.9 to 1.05.} The peak may be controlled according to the content ratio of the polyfunctional urethane acrylate oligomer and the polyfunctional silicone acrylate oligomer included in the surface treatment layer.

Further, the acrylic resin composition according to the present invention may further include a polyfunctional acrylate monomer and a monofunctional acrylate monomer in addition to the polyfunctional urethane acrylate oligomer and the polyfunctional silicone acrylate oligomer.

Here, the monofunctional and polyfunctional acrylate monomers are compounds containing a linear or branched alkyl group having 1 to 7 carbon atoms and an acrylic group, and may be classified into monofunctionality and polyfunctionality according to the number of acrylic groups contained in the compound. For example, when there are two or more acrylic groups in the compound, it may be classified as polyfunctional, and the polyfunctional acrylate monomer used in the present invention is one of a bifunctional monomer, a trifunctional monomer, a tetrafunctional monomer, and a 6 functional monomer. It may contain more than one species.

As an example, as the polyfunctional acrylate monomer, 1,6-hexanediol diacrylate (HDDA), tetraethylene glycol diacrylate, tripropylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol Diacrylate, pentaerythritol triacrylate, trimethylolpropaneethoxytriacrylate, and at least one selected from the group consisting of hexamethyldiamine diacrylate, and in some cases, the acrylate monomer and 2 Functional urethane acrylate, trifunctional urethane acrylate, or tetrafunctional urethane acrylate can be used in combination.

In addition, the monofunctional acrylic monomer is a compound containing one acrylic group in the compound, for example, methyl (methacrylate, including an alkyl group having 1 to 2 carbon atoms), ethyl (methacrylate ( ethyl(meth)acrylate, including an alkyl group having 2 to 3 carbon atoms), propyl (propyl(meth) acrylate, including an alkyl group having 3 to 4 carbon atoms), butyl (butyl(meth)acrylate, including 4 carbon atoms) ~5 alkyl group included), pentyl (methacrylate (pentyl(meth)acrylate, including C5-C6 alkyl group), and hexyl(meth)acrylate (hexyl(meth)acrylate, including C6-C7 alkyl group) It may include one or more selected from the group consisting of.

In addition, the monofunctional acrylic monomer may include a monomer including one or more reactive functional groups in some cases. Specifically, the monomer containing at least one reactive functional group may be an acrylic monomer containing a reactive functional group such as a hydroxy group, an amine group, or an amide group.

For example, the monofunctional acrylic monomer is 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate, 8-hydroxyoctyl acrylate, It contains at least one hydroxy-containing acrylic monomer selected from the group consisting of 2-hydroxyethylene glycol acrylate, 2-hydroxypropylene glycol acrylate, and caprolactone modified hydroxyl acrylate (CHA). I can.

In addition, the monofunctional acrylic monomer is 1, selected from the group consisting of 1,3-dimethylamylamine, 3-amino ethyl acrylate, 2- (dimethylamino) ethyl acrylate, and 2- (diethylamino) ethyl acrylate. It may contain an acrylic monomer containing more than a kind of amino group.

In addition, the monofunctional acrylic monomer is acrylamide, (meth)acrylamide, N-methylacrylamide, N-methyl (meth)acrylamide, N-dimethylacrylamide, N-dimethyl (meth)acrylamide, and N-moiety It may include one or more amide group-containing acrylic monomers selected from the group consisting of oxy methyl (meth) acrylamide.

In the present invention, the viscosity of the surface treatment agent can be appropriately lowered by containing the monofunctional acrylic monomer as described above in the surface treatment agent.

The acrylic resin composition used in the present invention may include 20 to 40 parts by weight and 110 to 150 parts by weight of a monofunctional acrylate monomer and a polyfunctional acrylate monomer, respectively, based on 100 parts by weight of the polyfunctional urethane acrylate oligomer.

As an example, the acrylic resin composition may include 30 to 35 parts by weight and 125 to 140 parts by weight of a monofunctional acrylate monomer and a polyfunctional acrylate monomer, respectively, based on 100 parts by weight of a polyfunctional urethane acrylate oligomer. .

Furthermore, the acrylic resin composition may further include a polymer bead to soften the texture or texture of the surface. Specifically, the polymer beads include one or more polymers selected from the group consisting of polyurethane, polyethylene, polypropylene, polyamide, polymethyl (meth) acrylate, polycarbonate, polymethyl urea, and polytetrafluoroethylene. May be a bead. In addition, the average particle size of the polymer beads may be 5 µm to 25 µm, specifically 5 µm to 20 µm, 5 µm to 18 µm, 8 µm to 18 µm, 8 µm to 15 µm, 11 µm to 16 µm , 7 µm to 11 µm or 14 µm to 17 µm. In the present invention, by controlling the average particle size of the filler within the above range, it is possible to implement a soft and moist texture on the surface without affecting the wrinkle structure formed on the surface of the surface treatment layer.

In addition, the polymer beads may be included in an amount of 5 to 15 parts by weight based on 100 parts by weight of the solid content of the acrylic resin composition for the texture and feel of the surface treatment layer, and specifically, 5 to 12 parts by weight based on 100 parts by weight of the solid content of the acrylic resin composition. It may be included in parts by weight, 5 to 10 parts by weight, 7 to 15 parts by weight, 10 to 15 parts by weight, 7 to 13 parts by weight, or 9 to 11 parts by weight.

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.

Preparation Examples 1 to 3. Preparation of acrylic resin composition

Urethane acrylate oligomer (bifunctional oligomer, Mw: 2,000), silicone acrylate oligomer (bifunctional oligomer, Mw: 10,000), trifunctional urethane acrylate, hydroxypropyl acrylate, 1,6-hexanediol diacrylate ( HDDA), polyurethane beads (average diameter: 8 to 15 µm), a dispersant and an initiator were mixed together as shown in Table 1 below to prepare a solvent-free type acrylic resin composition.

Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Bifunctional Urethane Acrylate Oligomer 34.5g 30g 25.5g Bifunctional silicone acrylate oligomer 1g 5.5g 10g Trifunctional urethane acrylate 10g 10g 10g Bifunctional acrylate 30g 30g 30g Monofunctional acrylate 10g 10g 10g Polyurethane beads 10g Dispersant 1g Photoinitiator 3.5g total 100g 100g 100g

Example 1.

Glass fiber layer and transparent polyvinyl chloride in which glass fibers are impregnated with PVC resin on a polyvinyl chloride (PVC) foam sheet (average thickness: 1T, average pore size: 300-400 µm) each having a size of 10 cm X 10 cm in length. The (PVC) substrate was laminated, and the acrylic resin composition prepared in Preparation Example 2 was applied on a transparent polyvinyl chloride (PVC) substrate, respectively, and fixed to a light curing device. Thereafter, as shown in Table 2 below, light irradiation was performed in stages while moving the substrate at a moving speed of 20±1 m/min to prepare a flooring specimen. At this time, the average thickness of the surface treatment layer was 15 ± 1㎛.

Curing condition 1 First light irradiation Wavelength range 250~400 ㎚ Irradiation 100±2 mJ/㎠ Distance from light source 50±1㎜ Gas condition Dry air condition (O ₂ concentration: 20±2 vol.%) Second light irradiation Wavelength range 172±5 nm Irradiation 50±5 mJ/㎠ Distance from light source 100±1㎜ Gas condition N ₂ condition 3rd light irradiation Wavelength range 250~400 ㎚ Irradiation 700±10 mJ/㎠ Distance from light source 100±1㎜ Gas condition N ₂ condition

Comparative Examples 1 to 6.

A flooring specimen was prepared in the same manner as in Example 1, except that the composition was cured under the curing conditions shown in Tables 3 and 4 below. At this time, the average thickness of the surface treatment layer was 15 ± 1㎛.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Type of acrylic composition Composition of Preparation Example 1 Composition of Preparation Example 3 Composition of Preparation Example 2 Composition of Preparation Example 2 Composition of Preparation Example 2 Curing condition Curing condition 1 Curing condition 1 Curing condition 2 Curing condition 3 Curing condition 4

Curing condition 2 Curing condition 3 Curing condition 4 First light irradiation Wavelength range - - - Irradiation - - - Distance from light source - - - Gas condition - - - Second light irradiation Wavelength range - - 172±5 nm Irradiation - - 50±5 mJ/㎠ Distance from light source - - 100±1㎜ Gas condition - - N ₂ condition Article 2-5 light irradiation Wavelength range 250~400 ㎚ - 250~400 ㎚ Irradiation 300±5 mJ/㎠ - 300±5 mJ/㎠ Distance from light source 100±1㎜ - 100±1㎜ Gas condition Air condition - Air condition 3rd light irradiation Wavelength range 250~400 ㎚ 250~400 ㎚ 250~400 ㎚ Irradiation 700±10 mJ/㎠ 700±10 mJ/㎠ 700±10 mJ/㎠ Distance from light source 100±1㎜ 100±1㎜ 100±1㎜ Gas condition N ₂ condition N ₂ condition N ₂ condition

Experimental Example 1.

In order to confirm the surface structure of the surface treatment layer, which is the outermost layer of the flooring according to the present invention, a scanning electron microscope (SEM) analysis was performed on the flooring specimens prepared in Example 1 and Comparative Example 5, and the results are shown in FIG. And shown in 2.

Referring to Figures 1 and 2, it was found that the specimen of Example 1 according to the present invention includes a fine wrinkle structure on the surface with a certain size and frequency, and the wrinkle structure has an irregular straight line and a curved line. It can be seen that it has the same curvature as the mountain range shape. In addition, the wrinkles were found to have an average width of 8±0.5 μm, a height of about 1 to 2 μm, and extend within about 10 to 50 μm. In addition, it was confirmed that the wrinkles were uniformly formed at a high frequency and existed about 5 to 20 per area of 0.1 mm X 0.1 mm.

In contrast, the specimen of Comparative Example 5 includes wrinkles having a mountain range shape in which irregular straight lines and curves are repeated, but the wrinkles are thick and high, and have a shape in which a plurality of wrinkles branch in different directions from one specific point. It was confirmed that there were about 5 to 8 wrinkles per area of mm X 1 mm.

From these results, when the first light irradiation step is performed before the second light irradiation step of irradiating light with a wavelength of less than 200 nm, the upper surface of the acrylic resin composition is partially cured and the excimer formed in the second light irradiation step is an acrylic resin. It can be seen that the size of the wrinkle structure can be reduced and the frequency of the wrinkle structure can be increased by weakening the degree of formation of the wrinkle structure on the surface of the composition.

Experimental Example 2.

In order to evaluate the components and surface properties of the surface treatment layer located on the top layer of the flooring according to the present invention, Fourier transform-infrared spectroscopy was measured in the wavenumber range ^{of 400 to 4,000 cm -1 for the flooring specimen of Example 1,} The results are shown in FIG. 3.

3, it can be seen that the flooring material according to the present invention includes a silicone acrylate oligomer and has hydrophobicity on the surface.

Specifically, referring to the Fourier transform-infrared spectral graph for the flooring specimen prepared in Example 1, the specimen has peaks at wavenumbers ^{of 799±2 cm -1} , 1088±0.3 cm ^-1 and 1258±0.6 cm ^-1. It can be seen that the peak has a high intensity of 50 to 65 au when the intensity of the peak with the strongest intensity in the measured total spectral spectrum is 100 au. At this time, the peaks appearing at wavenumbers of ^{799±2 cm -1} , 1088±0.3 cm ^-1 and 1258±0.6 cm ^-1 _{are the banding of Si-CH 3} , Si-O-Si and Si-CH ₃ bonds, respectively, and/ Or, as a peak indicating stretching, it means that the surface of the flooring material of the present invention contains a silicone acrylate oligomer.

Further, the specimen is a urethane acrylate oligomer and the C = O bond peak (P _urethane) in the urethane acrylate oligomer is confirmed that the silicon acrylate oligomer in the 1728 ± 2 cm ^-1, including a predetermined frequency content in the coated layer and It was found that the ratio of the Si-O-Si bonding peak (P _silicone ) of the silicone acrylate oligomer found at a wavenumber of 1088±0.3 cm ^-1 _{(P urethane} /P _silicone ) was about 0.88 to 0.93. This indicates that the silicone acrylate oligomer contained in the surface treatment layer has a constant content ratio with the urethane acrylate oligomer.

Experimental Example 3.

In order to evaluate the gloss and stain resistance of the flooring according to the present invention, gloss, stain resistance and non-slip properties were measured for the specimens prepared in Example 1 and Comparative Examples 1 to 5. The specific measurement method is as follows, and the measured results are shown in Table 5 below:

A) Glossiness evaluation

For the specimens of Examples and Comparative Examples, 60° gloss (gloss 60° condition) was measured using a gloss meter.

B) Pollution resistance II (smoothness) evaluation

Conduct the test in accordance with KS M 3802, but draw a line of about 10 cm on the surface using a vod marker as a contaminated material, and after 30 seconds, the line drawn with Kimwipes is rubbed off and left unerased based on the initial contaminated area. Areas (e.g., traces or smears) were visually checked, and the results were classified according to the following criteria:

- Level 1: The remaining area based on the initial contaminated area is more than 90%,

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

- Grade 3: The remaining area based on the initial contaminated area is 20% or more and less than 60%,

- Grade 4: The remaining area based on the initial contaminated area is 5% or more and less than 20%,

- Grade 5: The remaining area is less than 5% based on the original contaminated area.

Gloss Evaluation Example 1 2.3±0.05 Level 5 Comparative Example 1 2.5±0.1 Level 3 Comparative Example 2 2.2±0.1 Level 5 Comparative Example 3 8.5±0.5 Level 5 Comparative Example 4 20.0±1.0 Level 5 Comparative Example 5 1.6±0.05 Level 2

As shown in Table 5, it can be seen that the flooring material according to the present invention has a remarkably low gloss of 3 or less, and exhibits excellent stain resistance.

Specifically, it was found that the flooring specimen of Example 1 had a gloss of less than 2.5 under a gloss 60° condition even without a matting agent, and had excellent stain resistance and had an oily magic contamination and a contamination area of less than 5% after washing.

From these results, the flooring material according to the present invention contains a polyfunctional urethane arylate oligomer and a silicone acrylate oligomer in a specific ratio in the surface treatment layer, and implements a fine wrinkle structure on the surface of the surface treatment layer at a high frequency. It can be seen that it realizes low gloss without additives and has excellent stain resistance.

Claims (11)

A foam layer, a glass fiber layer, a printing layer, a base layer, and a surface treatment layer of an acrylic resin composition;
The surface treatment layer,
It has a surface structure including 5 to 20 wrinkles per unit area (0.1 mm X 0.1 mm),
Flooring with peaks at ^{799±2 cm -1} , 1088±0.3 cm ^-1 and 1258±0.6 cm ^-1 as measured by Fourier transform-infrared spectroscopy.
The method of claim 1,
A flooring material having a surface roughness (Ra) of 2 μm or less of the surface treatment layer.
The method of claim 1,
Flooring with an average thickness of the surface treatment layer of 10 µm to 30 µm.
The method of claim 1,
Flooring with a surface gloss of less than 3 under Gloss 60° conditions.
The method of claim 1,
The foaming density of the foam layer is 100 kg / ㎥ to 500 kg / ㎥ flooring material.
The method of claim 1,
Flooring with an average thickness of the foam layer of 0.5 mm to 5 mm.
A first light irradiation step of partially curing the composition by irradiating light having a wavelength of 200 nm to 400 nm in air to the acrylic resin composition applied on the base layer,
A second light irradiation step of irradiating light with a wavelength of less than 300 nm to induce wrinkles on the surface of the partially cured composition, and
A third light irradiation step of forming a surface treatment layer by irradiating light having a wavelength of 200 nm to 400 nm on the composition in which wrinkles are induced on the surface under nitrogen gas (N _{2) conditions;}
The surface treatment layer,
It has a surface structure including 5 to 20 wrinkles per unit area (0.1 mm X 0.1 mm),
Fourier transform-infrared spectroscopy measurement, a method for producing a flooring material having peaks at ^{799 ± 2 cm -1} , 1088 ± 0.3 cm ^-1 and 1258 ± 0.6 cm ^-1.
The method of claim 7,
The content of the polyfunctional silicone acrylate oligomer is 5 to 20 parts by weight based on 100 parts by weight of the polyfunctional urethane acrylate oligomer.
The method of claim 7,
The acrylic resin composition,
Based on 100 parts by weight of polyfunctional urethane acrylate oligomer,
10 to 30 parts by weight of a polyfunctional silicone acrylate oligomer,
20 to 40 parts by weight of a monofunctional acrylate monomer, and
A method for producing a flooring material comprising 110 to 150 parts by weight of a polyfunctional acrylate monomer.
The method of claim 7,
The acrylic resin composition is a polymer comprising at least one polymer selected from the group consisting of polyurethane, polyethylene, polypropylene, polyamide, polymethyl (meth)acrylate, polycarbonate, polymethyl urea, and polytetrafluoroethylene A method of manufacturing a flooring material further comprising a bead.
The method of claim 10,
The content of the polymer beads is 5 to 15 parts by weight based on 100 parts by weight of the solid content of the acrylic resin composition.

Images