KR102671918B1 - Floorings having excellent anti-pollution property - Google Patents

Abstract

The present invention relates to a flooring material with excellent stain resistance and wax affinity and a method of manufacturing the same. The flooring material uses a small amount of silicone additive in the surface treatment layer and creates a fine wrinkle structure at a high frequency on the surface of the surface treatment layer. It has the advantage of realizing excellent stain resistance and wax affinity.

Description

Floorings having excellent anti-pollution property and wax affinity

The present invention relates to a flooring material with excellent stain resistance and wax affinity and a method of manufacturing the same. Specifically, the composition of the surface treatment layer, which is the top layer of the flooring, is controlled and a fine wrinkle structure is implemented at a high frequency on the surface to provide excellent stain resistance and wax affinity. It relates to a flooring material that simultaneously exhibits affinity and a method of manufacturing the same.

In general, flooring provides a hygienic space by blocking dust and cold air from the cement floor, and is printed with beautiful patterns in various colors, so it also has a decorative effect, such as changing the indoor atmosphere to a cozy atmosphere according to the customer's taste. Such conventional flooring has a problem in that when the surface is contaminated with contaminants, the user cannot easily erase traces of contaminants, so flooring with traces of contaminants cannot perform its basic function.

Accordingly, surface treatment agents using anti-fouling additives have been developed to improve the fouling resistance of the surface. However, conventionally commonly used anti-fouling additives have the principle of controlling the fouling resistance of the surface treatment layer formed by controlling the surface tension of the surface treatment agent. In this case, the affinity for wax is significantly reduced, resulting in wax coating. There are difficult limits.

Therefore, there is an urgent need for the development of flooring materials with excellent stain resistance and wax affinity, which are trade-offs.

Republic of Korea Patent Publication No. 2014-0089074

The purpose of the present invention is to provide a flooring material that is excellent in both stain resistance and wax affinity.

Accordingly, the present invention in one embodiment,

It includes a base layer and a surface treatment layer of an acrylic resin composition;

The surface treatment layer is,

It has a surface structure containing 5 to 20 wrinkles per unit area (0.1 mm

When 3g of wax is applied to a unit area (200 mm

In addition, the present invention in one embodiment,

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

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

Provided is a method for producing the flooring, comprising a third light irradiation step of forming a surface treatment layer by irradiating light with a wavelength of 200 nm to 400 nm to the composition on which wrinkles are induced on the surface under nitrogen gas (N ₂ ) conditions. .

The flooring material according to the present invention has the advantage of realizing excellent stain resistance and wax affinity by using a small amount of silicone additive in the surface treatment layer and realizing a high frequency of fine wrinkle structures on the surface of the surface treatment layer.

Figure 1 is an image showing the results of scanning electron microscopy (SEM) analysis of the flooring specimen of Example 1 according to the present invention.
Figure 2 is an image showing the results of scanning electron microscopy (SEM) analysis of the flooring specimen of Comparative Example 5 according to the present invention.
Figure 3 is a graph showing the results of analyzing Fourier transform-infrared spectroscopy of an acrylic resin composition before and after the first light irradiation step.

Since the present invention can make various changes and have various embodiments, 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 changes, equivalents, and substitutes included in the spirit and technical scope of the present invention.

In the present invention, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, but are not intended to indicate the presence of one or more other features. It should be understood that this does not exclude in advance the possibility of the existence or addition of elements, numbers, steps, operations, components, parts, or combinations thereof.

In addition, the drawings attached to the present invention should be understood as being enlarged or reduced for convenience of explanation.

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

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.

Additionally, 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, it may be a value measured according to the center line average roughness (Ra) according to KS B 0161.

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

In general, flooring provides a hygienic space by blocking dust and cold air from the cement floor, and is printed with beautiful patterns in various colors, so it also has a decorative effect, such as changing the indoor atmosphere to a cozy atmosphere according to the customer's taste. Such conventional flooring has a problem in that when the surface is contaminated with contaminants, the user cannot easily erase traces of contaminants, so flooring with traces of contaminants cannot perform its basic function.

Accordingly, surface treatment agents using anti-fouling additives have been developed to improve the fouling resistance of the surface. However, conventionally commonly used anti-fouling additives have the principle of controlling the fouling resistance of the surface treatment layer formed by controlling the surface tension of the surface treatment agent. In this case, the affinity for wax is significantly reduced, resulting in wax coating. There are difficult limits.

Accordingly, the present invention provides a flooring material with excellent stain resistance and wax affinity and a method for manufacturing the same.

The flooring material has the advantage of realizing excellent stain resistance and wax affinity by implementing a fine wrinkle structure on the surface of the surface treatment layer at a high frequency while using a small amount of silicone additive in the surface treatment layer.

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

flooring

In one embodiment, the present invention

A flooring material including a surface treatment layer formed from an acrylic resin composition on a base material layer is provided.

The flooring according to the present invention is an indoor flooring used in homes, offices, etc., and the surface treatment layer is a cured layer of an acrylic resin composition and is located on the top layer of the flooring. Here, the acrylic resin composition includes acrylate-based oligomers and monomers, and contains a small amount of silicone additives along with the above components, so that it can exhibit excellent surface contamination resistance.

As an example, the flooring material has improved stain resistance and can satisfy one or more of the following conditions 1 and 2:

[Condition 1] When observing the washed flooring with the naked eye after 20 minutes of iodine contamination, there is no difference in surface color; and

[Condition 2] After 30 seconds of oil-based magic contamination, the residual contaminated area of the cleaned flooring is less than 5% of the initial contaminated area.

Specifically, the flooring material has improved resistance to iodine contamination, so when the surface is contaminated with iodine and washed after 20 minutes, marks due to iodine contamination may not be observed with the naked eye on the surface.

In addition, the flooring has improved resistance to contamination by organic substances such as oil-based markers, so when oil-based markers are applied to the surface and washed after 30 seconds, the residual contaminated area of the cleaned flooring surface will be less than 5% of the initial contaminated area. It may be, and more specifically, it may be less than 4%, less than 3%, or less than 2%.

In general, silicone additives have a low surface tension, so when used in a certain amount in the surface treatment layer, they can improve contamination by contaminants on the surface. However, in this case, there is a problem that the affinity for wax is lowered and wax wettability and coating properties are reduced. In other words, when a silicone additive is used in the surface treatment layer, there is a problem that the wax does not spread well or the applied wax peels off after drying.

However, the flooring material of the present invention can improve wax affinity, specifically wax wettability, coating properties, and adhesiveness, as well as surface stain resistance by introducing a fine wrinkle structure into the surface structure of the surface treatment layer.

Here, “surface with wrinkles” means that the resin layer includes wrinkles on at least one surface, and that the resin layer has three-dimensional surface irregularities due to the wrinkles. For example, the surface has irregularities including large and small ridges, valleys, and wrinkles formed therefrom that can be recognized as a predetermined shape. Each of the ridges, valleys, and wrinkles may have a regular or irregular shape. This wrinkled surface may also be referred to as a surface having a fine folding structure.

When observing the surface of a resin layer with wrinkles 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 going through the curing process described below. .

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

Additionally, the surface treatment layer may include wrinkles that can be visually recognized as having a predetermined size and shape. For example, the wrinkles may have a width of nm (less than about 1 μm) and have a line (straight or curved) shape extending several micrometers (μm) or more. The width and/or height of the wrinkle and the length the wrinkle extends can be confirmed from an image (eg, SEM) taken of the surface on which the wrinkle is formed, as shown in the attached drawing. Additionally, the length in the extension direction may be greater than the width. Specifically, the ends of the wrinkles extending in a straight or curved form form a slope that gradually decreases in height and may be incorporated into the resin layer. In some cases, the end of one wrinkle having the above size and shape may be the starting point of another wrinkle or a connection point with another wrinkle. In addition, when observing the cross-sectional curve near the wrinkle in the direction perpendicular to the direction of extension of the wrinkle, the width of the wrinkle gradually decreases in height in both directions starting from the point or part (e.g., ridge) that forms the height of the wrinkle. The ground forms a slope and can be mixed into the resin layer. On the other hand, when a ridge and an adjacent valley form a wrinkle or a part thereof, the visible area of the shape including the valley can 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 may have an upper limit of 150 nm or less, 200 nm or more, and 250 nm or less. It may have a lower limit of 300 nm or more. When the above range is satisfied, it may be advantageous for the surface formed by wrinkles to have improved stain resistance and wax affinity and to exhibit matte characteristics.

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

The wrinkles may have a predetermined height over most of their 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 can be equated to the “surface roughness” of the surface treatment layer. Specifically, when observing the cross-sectional curve of a wrinkle in a direction perpendicular to the direction of extension of the wrinkle, a point or part forming the height of the wrinkle (e.g., a ridge) and a point or part of the resin layer where the width of the wrinkle mix ( e.g. valleys) may have a “height difference” or “surface roughness” of less than 2 μm. The present invention controls the height and surface roughness of wrinkles within the above range to prevent contaminants remaining between wrinkles due to thick wrinkles, thereby reducing contamination resistance.

Meanwhile, the above-mentioned “most of the length at which the height is observed” refers to a length that is more than 70%, more than 75%, more than 80%, more than 85%, or more than 90%, or more than 95% of the length over which the wrinkle extends continuously along its shape. means. The height difference gradually decreases in the direction in which the wrinkle extends, and when the height is significantly lowered, the end of the wrinkle may be observed to be incorporated into the resin layer, or the point of contact with another wrinkle that is different in size or shape from the wrinkle may begin. The shape may be observed. In the latter case, a more complex wrinkle structure can form surface irregularities.

The wrinkles are observed over the entire surface and may form surface wrinkles or irregularities with regular or irregular distribution. For example, the wrinkles on the surface may have a shape in which a plurality of wrinkles branch out in different directions from one specific point, forming surface irregularities. Specifically, the wrinkles on the surface may have a shape similar to “Y” or “〈”. At this time, wrinkles similar in shape 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 in the surface treatment layer, and through this, even without using a matting agent or using a small amount of matting agent in the surface treatment layer. It can lower the gloss, prevent the surface from being contaminated by contaminants remaining between wrinkles, and improve the wax affinity of the surface.

As one 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 (equivalent to 500 to 2,000 wrinkles per 1 mm Specifically, on the surface of the surface treatment layer of the flooring, there are 5 to 18, 5 to 15, 5 to 12, 5 to 10, 5 to 8, and 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.

As another example, the flooring material has excellent wax affinity, so when 3g of wax (e.g., acrylic wax, etc.) is applied to a unit area (200 mm It may occupy 90% or more of the application area, specifically 93% or more, 95% or more, 97% or more, or 98% or more. In some cases, 1 minute after applying the wax, the area of the applied wax can be maintained 100% the same as the initial application area.

As another example, when wax is applied to the flooring material with a thickness of 7.5 ± 2.5 μm and a cross-cut test according to ASTM D3359 is performed 24 minutes later, the peeling area of the total area of the dried wax may be 5% or less, Specifically, the peeling area is 4.5% or less, 4.0% or less, 3.5% or less, 3.0% or less, 2.0% or less, 0.1 to 5%, 0.1 to 4.5%, 0.1 to 4.0%, 0.1 to 3.5%, compared to the total area. It may be 0.1 to 3.0%, 0.5 to 4.0%, 0.5 to 3.0%, 0.5 to 2.0%, 1.0 to 2.0%, 1.0 to 3.0%, 1.0 to 4.0%, 2.0 to 4.0%, or 0.1 to 2%. In some cases, no peeling of the dried wax occurs at all, so the damaged area may be less than 0.1% or close to 0%.

Furthermore, the flooring induces the scattering of light incident on the surface through the wrinkle structure formed on the surface of the surface treatment layer, resulting in a significantly low gloss even when no matting agent is used in the surface treatment layer or a small amount of less than 10% by weight of matting agent is used. can be implemented.

As an example, the flooring material may have a surface gloss of less than 3 when measuring 60° gloss (gloss 60° conditions) using a gloss meter, and more specifically, the upper limit is 2.8 or less, 2.5 or less, It may be 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 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 0.9. It may be 1.5, 0.1 to 1.4, or 1.1 to 1.5.

The surface treatment layer may have an average thickness within an appropriate range that does not affect durability. For example, the surface treatment layer may have an average thickness of 10 ㎛ to 30 ㎛, more specifically 10 ㎛ to 25 ㎛, 10 ㎛ to 20 ㎛, 10 ㎛ to 15 ㎛ to prevent tearing or loss due to external stimuli. It may be ㎛, 15㎛ to 30㎛, 20㎛ to 30㎛, 15㎛ to 25㎛, 18㎛ to 25㎛, 22㎛ to 28㎛, 11㎛ to 20㎛ or 12㎛ to 18㎛.

Meanwhile, the flooring according to the present invention may further include a non-foaming layer, a glass fiber layer, and a printed layer in addition to the base layer and the surface treatment layer, and specifically, a foam layer, a glass fiber layer, a printed layer, a base layer, and a surface. The treatment layers may have a sequentially stacked structure.

At this time, the non-foam layer is a layer located at the bottom of the flooring material and supports the upper cured layer, base material layer, printed layer, and dimensionally stable layer, while further supplementing the impact resistance, walking feeling, and strength of the flooring material. Do it.

The non-foaming layer may be formed of a polyvinyl chloride resin composition containing a polyvinyl chloride resin, and the polyvinyl chloride resin composition may contain a plasticizer (e.g. , dioctyl terephthalate) 35 to 58 parts by weight, and 80 to 100 parts by weight of filler (e.g., calcium carbonate).

The thickness of the non-foaming layer may be 200 to 2,000 ㎛. If the thickness of the non-foam layer is less than 200 ㎛, the impact resistance and walking comfort of the flooring may be reduced, and if it exceeds 2,000 ㎛, the flooring may become thicker than necessary. The transparent layer is formed on the fiber impregnated layer, and serves to increase durability, wear resistance, and elasticity, and to supplement strength.

Additionally, 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)-based resin, polyurethane-based resin, polylactic acid-based resin, or polyolefin resin. The dimensional stability layer formed in this way can achieve excellent dimensional stability by reducing dimensional strain even under high temperature and high humidity conditions, while maintaining a high level of adhesion with other layers laminated on the top and bottom, thereby realizing 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 fiber 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 It may range from 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. The present invention can achieve high strength and high durability even if it includes a glass fiber layer with a low basis weight by controlling the average diameter of the glass fibers within the above range.

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 , It can be adjusted in the range of 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, excellent hardness of the substrate can be maintained while preventing excessive increase in weight.

In addition, the base layer is a transparent or translucent polyvinyl chloride (PVC) layer and may have a thickness of about 0.05 mm to about 2.0 mm. By having a thickness within the above range, the total thickness of the flooring will not be excessively increased, and as described later, As shown, the pattern or pattern of the printed layer laminated below 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, various printing methods such as transfer printing, gravure printing, screen printing, offset printing, rotary printing, or flexo printing. It can be formed by giving a pattern in this way. At this time, the printed layer may have an average thickness of about 1㎛ to about 10㎛.

Manufacturing method of flooring

In addition, in one embodiment of the present invention,

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

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

Provided is a method of manufacturing a flooring material including a third light irradiation step of forming a surface treatment layer by irradiating light with a wavelength of 200 nm to 400 nm to a composition on which wrinkles are induced on the surface under nitrogen gas (N ₂ ) conditions.

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

Specifically, the first light irradiation step is the first step of irradiating light to the composition applied on the substrate, partially curing the composition by irradiating light with a wavelength of 200 nm to 400 nm to the acrylic resin composition in the air, specifically. is a step of pre-curing the acrylic resin composition at 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. This can be seen through the change in intensity of the stretching peak of the C=C bond that appears in the wavenumber range of 809.6±1 cm ^-1 during Fourier transform-infrared spectroscopy (FT-IR) measurement.

As an example, the acrylic resin composition may satisfy the following equation 1 when subjected to Fourier-infrared spectroscopy analysis:

[Equation 1] 0.5 ≤ A _harden /A _acryl ≤0.7

In equation 1,

A _acryl refers to the area of the peak shown at a wave number of 809.6±1 cm ^-1 during Fourier-infrared spectroscopy analysis of an acrylic resin composition that has not been irradiated with light,

A _harden refers to the area of the peak shown at a wave number of 809.6 ± 1 cm ^-1 during Fourier-infrared spectroscopy analysis of the acrylic resin composition on which the first light irradiation step was performed.

Specifically, the acrylic resin composition is partially cured in the first light irradiation step, and when analyzed by Fourier-infrared spectroscopy before and after performing the first light irradiation step, the acrylic resin composition has a wave number of 809.6 ± 1 cm ^-1 , indicating stretching of the C=C bond. The peak area ratio (A _harden / A _acryl ) may range from 0.5 to 0.7, specifically 0.5 to 0.65, 0.55 to 0.7, 0.55 to 0.65, 0.58 to 0.64, or 0.61 to 0.66.

In addition, the air conditions may be performed under general air or clean dry air conditions, and in some cases, oxygen gas (O ₂ ) is mixed with nitrogen gas (N ₂ ). can do. In this case, the concentration of oxygen gas (O ₂ ) in nitrogen gas (N ₂ ) may be 30 parts by volume or less or 20 parts by volume or less based on 100 parts by volume of the total mixed gas, and more specifically, 5 to 25 parts by volume, 10 parts by volume. It may be from 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 the surface of the acrylic resin composition before forming wrinkles through the first light irradiation step. For example, the flooring material according to the present invention performs the first light irradiation step, so that 5 to 20 wrinkles per unit area of 0.1 mm However, if the first light irradiation step is not performed, it may include a wrinkle structure with a low frequency of 400 or less per unit area of 0.1 mm x 0.1 mm.

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

In addition, the second light irradiation step is a step in which excimers generated by the irradiated light shrink 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 wrinkled structure described above using excimer, so no matting agent is used or a small amount of matting agent of less than 10% by weight is used. It may also reduce the glossiness of the surface treatment layer. To this end, the second light irradiation step can be performed in a nitrogen (N ₂ ) atmosphere, a non-reactive gas, using light with a high energy wavelength of less than 300 nm, specifically 100 to 200 nm or 150 to 195 nm. In some cases, it may be performed 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 mm. It may be ~140 mm, 80-110 mm, 90-110 mm, or 95-105 mm.

In addition, the amount of light irradiation in the second light irradiation step may be 100 mJ/cm2 to 500 mJ/cm2, specifically 100 mJ/cm2 to 400 mJ/cm2¸200 mJ/cm2 to 500 mJ/cm2, 200 mJ /cm2 to 400 mJ/cm2, 250 mJ/cm2 to 350 mJ/cm2, 320 mJ/cm2 to 400 mJ/cm2, 280 mJ/cm2 to 320 mJ/cm2 or 290 mJ/cm2 to 310 mJ/cm2. .

As an example, in the second light irradiation step, in order to form an excimer in the composition, light with a wavelength of 172 ± 2 nm is applied to the composition at 295 ~ 295 under nitrogen (N ₂ ) conditions containing 100 ppm or less of oxygen (O ₂ ) It can be performed by irradiating with a light dose of 305 mJ/㎠ (i.e., light irradiation amount) for a very short time of 1 to 2 seconds.

The present invention facilitates controlling 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 within the above range when performing the second light irradiation step. can do.

Furthermore, the third light irradiation step is a step of additionally irradiating ultraviolet (UV) rays to the composition in which wrinkles are formed to completely cure the composition to 95% or more, that is, "hardening", with a wavelength of 400 nm or less, specifically. is carried out 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. It can be.

At this time, the surface temperature of the hardened composition and/or the surface treatment layer may be 20 to 90°C, specifically 20 to 80°C or 30 to 70°C.

As an example, the third light irradiation step is performed by applying light with a wavelength of 300 ± 10 nm to the composition and/or the surface treatment layer at a light quantity of 100 to 3,000 mJ/cm2, specifically 500 to 900 mJ/cm2. It can be performed by irradiating in a nitrogen (N ₂ ) atmosphere for a very short time of 2 seconds, where the distance between the composition and/or surface treatment layer and the light source can be 100 ± 10 mm.

The light irradiated in the present invention can be irradiated according to a known method that can irradiate light of the required wavelength in each step. For example, light with a wavelength of 400 nm or less, which is 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 upon light irradiation, for example, the speed at which the composition coated on the substrate moves. You can. For example, the moving speed of the composition and/or the composition-coated substrate may be 1 to 50 m/min, specifically 5 to 40 m/min, 10 to 40 m/min, and 20 to 40 m/min. 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 uses a specific range of short-wavelength light step by step under different conditions when curing the composition, so that a high curing rate can be achieved even if a small amount of the initiator is included in the above range.

Meanwhile, the acrylic resin composition may include a multifunctional acrylate oligomer, a multifunctional acrylate monomer, and a monofunctional acrylate monomer.

Specifically, the acrylic oligomer refers to an oligomer obtained using a monomer containing an acrylic group, and the monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. It may be one or more (meth)acrylates selected from the group consisting of acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, and benzyl acrylate. there is. For example, the acrylic oligomer may be methyl acrylate, (meth)acrylate, ethyl acrylate, benzyl acrylate, or a mixture thereof, such as methyl acrylate oligomer, (meth)acrylate oligomer, or methyl (meth)acrylate. It may include late oligomer, ethyl acrylate oligomer, benzyl acrylate oligomer, benzyl (meth)acrylate oligomer, etc.

In addition, the weight average molecular weight of the acrylic oligomer may be 100 to 50,000, more specifically 500 to 30,000; 1,000 to 10,000; 5,000 to 10,000; 6,000 to 8,000; It may be 1,000 to 5,000 or 1,500 to 2,500. The present invention can further improve the durability of the cured layer by adjusting the weight average molecular weight of the acrylic oligomer within the above range.

In addition, the monofunctional and multifunctional acrylate monomers are compounds containing a straight or branched chain alkyl group having 1 to 7 carbon atoms and an acrylic group, and can be classified into monofunctional and multifunctional depending on the number of acrylic groups contained in the compound. For example, if the compound has two or more acrylic groups, it can be classified as multifunctional, and the multifunctional acrylate monomer used in the present invention is one of two functional monomers, three functional monomers, four functional monomers, and six functional monomers. It may include more than one species.

As an example, the multifunctional acrylate monomers include 1,6-hexanediol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, triethylene glycol diacrylate, and dipropylene glycol diacrylate. , pentaerythritol triacrylate, trimethylolpropane ethoxy triacrylate, and hexamethyldiamine diacrylate, and in some cases, the acrylate monomer and difunctional urethane. Acrylate, tri-functional urethane acrylate, or tetra-functional 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 (methyl(meth)acrylate, including an alkyl group having 1 to 2 carbon atoms), ethyl (methacrylate ( ethyl(meth)acrylate, containing an alkyl group with 2 to 3 carbon atoms), propyl (propyl(meth)acrylate, containing an alkyl group with 3 to 4 carbon atoms), butyl (butyl(meth)acrylate, with 4 carbon atoms) Contains an alkyl group of ~5), pentyl (meth)acrylate (contains an alkyl group of 5 to 6 carbon atoms), and hexyl (meth)acrylate (contains an alkyl group of 6 to 7 carbon atoms) It may include one or more types selected from the group consisting of.

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

For example, the monofunctional acrylic monomer includes 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutylacrylate, 6-hydroxyhexyl acrylate, 8-hydroxyoctylacrylate, It may contain one or more hydroxy-containing acrylic monomers selected from the group consisting of 2-hydroxyethylene glycol acrylate, 2-hydroxypropylene glycol acrylate, and caprolactone modified hydroxyl acrylate (CHA). You 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 more than one type of acrylic monomer containing an amino group.

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

The present invention can appropriately lower the viscosity of the surface treatment agent 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 50 to 70 parts by weight and 40 to 70 parts by weight of monofunctional acrylate monomer and polyfunctional acrylate monomer, respectively, based on 100 parts by weight of polyfunctional acrylate oligomer.

As an example, the acrylic resin composition contains 57 to 70 parts by weight and 50 to 63 parts by weight of monofunctional acrylate monomer and polyfunctional acrylate monomer, respectively, based on 100 parts by weight of polyfunctional urethane acrylate oligomer, specifically. It may contain 61 to 68 parts by weight and 51 to 60 parts by weight, respectively.

Furthermore, the acrylic resin composition may further include a UV-curable liquid silicone additive to improve the contamination resistance of the surface treatment layer. For example, a high molecular weight amphiphilic silicone additive may be used as such silicone additive. . At this time, the molecular weight of the silicone additive may be 30,000 to 90,000.

Additionally, silicone additives may be used in small amounts. Specifically, the silicone additive may be used in an amount of 0.1 to 5 parts by weight, more specifically, 0.1 to 4 parts by weight, 0.1 to 3 parts by weight, 0.1 to 2 parts by weight, and 0.5 to 5 parts by weight, based on 100 parts by weight of the multifunctional acrylate oligomer. It can be used at 1.5 parts by weight, 0.1 to 1.1 parts by weight, or 0.7 to 1.3 parts by weight.

When silicone additives are used, there is a problem that the surface tension of the acrylic resin composition is lowered and the wax affinity of the surface treatment layer is lowered. However, the present invention introduces a fine wrinkle structure on the surface of the surface treatment layer and at the same time controls the content of the silicone additive within the above range to appropriately lower the surface tension of the acrylic resin composition to form a fine wrinkle structure on the surface of the surface treatment layer. While improving fouling resistance, the decrease in wax affinity can be minimized. In addition, it is possible to prevent the curing rate from being significantly reduced due to excessive silicone additives.

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

However, the following examples and experimental examples only illustrate the present invention, and the content of the present invention is not limited to the following examples and experimental examples.

Preparation Examples 1 to 3. Preparation of acrylic resin composition

First acrylate oligomer (bifunctional oligomer, Mw: 2,000), second acrylate oligomer (trifunctional oligomer, Mw: 7,000), first acrylate monomer (bifunctional monomer, Mw: 225), second acrylate monomer (trifunctional monomer, Mw: 296), monofunctional acrylate monomer, matting agent, and initiator were mixed together as shown in Table 1 below to prepare a solvent-free type acrylic resin composition.

Manufacturing Example 1 Production example 2 Production example 3 Production example 4 First acrylate oligomer (bifunctional) 20g 20g 20g 20g Second acrylate oligomer (trifunctional) 20g 20g 20g 20g First acrylate monomer (bifunctional) 14g 13.9g 13g 8g Secondary acrylate monomer (trifunctional) 10g 10g 10g 10g Monofunctional acrylate monomer 25g 25g 25g 25g silicone additive 0g 0.1g 1g 6g matting agent 8g photoinitiator 3g total 100g 100g 100g 100g

Example 1.

The acrylic resin composition obtained in Preparation Example 3 was applied to a polyvinyl chloride (PVC) substrate measuring 10 cm wide Then, as shown in Table 2 below, light irradiation was performed step by step while moving the substrate at a moving speed of 9 ± 0.5 m/min to prepare an SLS type non-foaming tile flooring specimen. At this time, the average thickness of the cured layer was 20 ± 1㎛.

Curing condition 1 1st light irradiation Wavelength range 250~400㎚ dose 100±2 mJ/㎠ Distance from light source 50±1㎜ gas conditions Clean dry air conditions (O ₂ concentration: 20±2 vol.%) Second light irradiation wavelength range 172±5㎚ dose 300±5 mJ/㎠ Distance from light source 100±1㎜ gas conditions N ₂ condition
(O ₂ concentration: 1,000 ppm or less) Third light irradiation wavelength range 250~400㎚ dose 700±10 mJ/㎠ Distance from light source 100±1㎜ gas conditions N ₂ condition

Comparative Examples 1 to 6.

Flooring specimens were 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 Comparative Example 6 Acrylic composition types Composition of Preparation Example 1 Composition of Preparation Example 2 Composition of Preparation Example 4 Composition of Preparation Example 1 Production Example 3
composition Production example 3
composition Curing conditions Curing conditions 1 Curing conditions 1 Curing conditions 1 Curing condition 2 Curing condition 2 Curing condition 3

Curing condition 2 Curing condition 3 1st light irradiation Wavelength range 250~400㎚ - dose 100±2 mJ/㎠ - Distance from light source 50±1㎜ - gas conditions Clean dry air conditions
(O ₂ concentration: 20±2 vol.%) - Second light irradiation wavelength range - 172±5㎚ dose - 300±5 mJ/㎠ Distance from light source - 50±1㎜ gas conditions - N ₂ condition
(O ₂ concentration: 1,000 ppm or less) Third light irradiation wavelength range 250~400㎚ 250~400㎚ dose 700±10 mJ/㎠ 700±10 mJ/㎠ Distance from light source 100±1㎜ 100±1㎜ gas conditions 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, scanning electron microscopy (SEM) analysis was performed on the flooring specimens prepared in Example 1 and Comparative Example 6, and the results are shown in Figure 1 and 2.

Looking at Figures 1 and 2, the specimen of Example 1 according to the present invention was found to contain fine wrinkle structures on the surface of a certain size and frequency, and the wrinkle structure was formed by repeating irregular straight lines and curves. You can see that it has curves similar to the shape of a mountain range. In addition, the wrinkles were found to have an average width of 8 ± 0.5 ㎛, a height of about 1 to 2 ㎛, and extending within about 10 to 50 ㎛. In addition, it was confirmed that the wrinkles were formed uniformly at a high frequency, and that there were about 5 to 20 wrinkles per area of 0.1 mm x 0.1 mm.

On the other hand, the specimen of Comparative Example 6 included wrinkles having the shape of a mountain range with repeated irregular straight lines and curves, but the wrinkles were thick and high, and had a shape in which a plurality of wrinkles branched out in different directions from one specific point. 1 It was confirmed that there were about 5 to 8 wrinkles per area of mm

From these results, it can be seen that when performing the first light irradiation step, the size and frequency of the wrinkle structure formed on the surface of the surface treatment layer can be controlled.

Experimental Example 2.

In order to confirm changes in the surface treatment layer according to the first light irradiation step, Fourier transform-infrared spectroscopy analysis was performed. Specifically, the acrylic resin composition obtained in Preparation Example 3 was applied to a polyvinyl chloride (PVC) specimen ^measuring 10 cm wide was measured. Then, after performing the first light irradiation step on the specimen, Fourier transform-infrared spectroscopy in the wavenumber range of 400 to 4,000 cm ^-1 was remeasured, and the results are shown in FIG. 3.

Looking at Figure 3, it can be seen that the first light irradiation step controls the size and frequency of the wrinkle structure formed in the surface treatment layer.

Specifically, referring to the Fourier transform-infrared spectroscopy graph for the flooring specimen prepared in Example 1, the acrylic resin composition was 810.2±2 cm ^-1 when measured by Fourier transform-infrared spectroscopy (FT-IR) before the first light irradiation step. It can be confirmed that there is a stretching peak of the C=C bond that appears in the wavenumber range of , and it can be confirmed that the intensity of the peak decreases after the first light irradiation step. More specifically, since the intensity of the peak becomes smaller after the first light irradiation step, the ratio of the peak area (A _acryl ) before the first light irradiation step to the peak area (A _harden ) after the first light irradiation step (A _harden /A _acryl ) can be confirmed to be 0.5 to 0.7. This means that the acrylic resin composition is cured by about 30% to 50% after the first light irradiation step.

Partial curing of the acrylic resin composition in the first light irradiation step weakens the extent to which the excimer formed in the second light irradiation step forms a wrinkle structure on the surface of the acrylic resin composition, thereby reducing the size of the wrinkle structure and increasing the frequency. I can see that it can be done.

Experimental Example 3.

In order to evaluate the gloss, stain resistance, and wax affinity of the flooring material according to the present invention, the gloss, stain resistance, and wax affinity were measured for the specimens prepared in Example 1 and Comparative Examples 1 to 6. The specific measurement method is as follows, and the measured results are shown in Table 5 below:

A) Glossiness evaluation

The 60° glossiness (gloss 60° condition) was measured using a gloss meter for the specimens of Examples and Comparative Examples.

B) Contamination resistance (staining resistance) evaluation

The test is performed in accordance with KS M 3802, but a line of approximately 10 cm is drawn on the surface using a board marker as a contamination material. After 30 seconds, the drawn line is removed by rubbing with a Kimwipe to remove any residue that is not erased based on the initial contamination area. Areas (e.g., traces or smears) were confirmed visually, and the results were classified according to the following criteria:

- Grade 1: Based on the initial contaminated area, the remaining area is more than 90%

- Grade 2: Based on the initial contaminated area, the remaining area is more than 60% but less than 90%.

- Grade 3: Based on the initial contaminated area, the remaining area is more than 20% and less than 60%.

- Grade 4: Based on the initial contaminated area, the remaining area is more than 5% and less than 20%.

- Grade 5: Based on the initial contaminated area, the remaining area is less than 5%

c) Wax affinity evaluation I: cross-cut

Wax was applied to the surfaces of the specimens of Examples and Comparative Examples to a thickness of 7.5 ± 2.5 μm, dried for 24 minutes, and the wax was coated on the surface treatment layer. Then, according to evaluation method A of ASTM D3359, the surface of the laminated film was cut with a knife in an Afterwards, a tape (about 75 mm (3 inches) in length) was firmly attached along the X shape to the cut surface and quickly removed to check the peeling state of the cut X shape. It was given according to the confirmed delamination condition, and the criteria were as follows:

Grade 0: X-shaped area completely peeled off;

Grade 1: Delamination of approximately 50% or more of the total area is confirmed;

Grade 2: Delamination of up to 3.2 mm (1/8 inch) is observed in a zigzag pattern on both sides of the straight section of the cut X.

Grade 3: Zigzag peeling of approximately 1.6 mm (1/6 inch) was observed on both sides of the straight line of the cut X.

Grade 4: Traces of peeling or removal of approximately 5% or less of the total area are confirmed along the straight line or intersection of the cut X;

Grade 5: No delamination of cut surfaces observed.

d) Wax affinity evaluation II: Measurement of average size of wax droplets

At 22 ± 2°C, 3g of wax (mixture containing 50-70% by weight of acrylic resin and water) was dropped on the surfaces of the specimens of Examples and Comparative Examples, and a unit area (200 mm ) was applied to fill all of the area. After 1 minute, the area of the applied wax was measured, and the ratio of the area applied after 1 minute compared to the initial application area was calculated.

Glossiness Kkalkkumi evaluation wax affinity cross-cut After 1 minute
Wax application area rate Example 1 1.5±0.1 level 5 level 5 100% Comparative Example 1 1.5±0.1 level 2 level 5 100% Comparative Example 2 1.6±0.1 level 2 level 5 100% Comparative Example 3 1.4±0.1 1st grade 1st grade 100% Comparative Example 4 5.0±0.1 1st grade level 5 100% Comparative Example 5 6.0±0.1 level 5 level 5 40% Comparative Example 6 3.5±0.1 1st grade level 5 100%

As shown in Table 5, it can be seen that the flooring material according to the present invention has a significantly low gloss of 3 or less, and has excellent stain resistance and wax affinity at the same time.

Specifically, the flooring specimen of Example 1 had a gloss of less than 2.0 under a gloss condition of 60° even when a small amount of less than 10% by weight of matting agent was used, and had excellent stain resistance, so there were no traces of contamination on the surface with the naked eye before and after iodine contamination. It was not confirmed, and the contaminated area after board marker contamination and washing was found to be less than 5%. In addition, the flooring specimen has excellent wax affinity, so peeling of the wax does not occur even when the coated wax is cross-cut and detached, and even after 1 minute after applying the wax to the surface, 100% of the initially applied area is maintained. confirmed to be maintained.

From these results, the flooring material according to the present invention contains multifunctional urethane acrylate oligomer and silicone acrylate oligomer in a specific ratio in the surface treatment layer, and a fine wrinkle structure is implemented at a high frequency on the surface of the surface treatment layer, so that no separate additive is used. It can be seen that low gloss is achieved without any staining, and both stain resistance and wax affinity are excellent.

Claims (11)

It includes a base layer and a surface treatment layer of an acrylic resin composition;
The surface treatment layer has an average thickness of 10㎛ to 30㎛,
It has a surface structure containing 5 to 20 wrinkles per unit area (0.1 mm
When applying 3g of wax to a unit area (200 mm
According to paragraph 1,
The surface treatment layer is a flooring material characterized in that the peeling area is less than 5% of the total area of the dried wax when the wax is applied to a thickness of 7.5 ± 2.5㎛ and a cross-cut test according to ASTM D3359 is performed 24 minutes later.
According to paragraph 1,
Flooring material whose surface roughness (Ra) of the surface treatment layer is 2㎛ or less.
According to paragraph 1,
Flooring is a flooring material in which the residual contamination area of the surface treatment layer cleaned after 30 seconds of board marker contamination is less than 5% of the initial contamination area.
According to paragraph 1,
Flooring material with a surface gloss of less than 3 under gloss conditions of 60°.
delete According to paragraph 1,
The base layer is a flooring material including a non-foam layer, a glass fiber layer, and a printed layer at the bottom.
A first light irradiation step of partially curing the composition by irradiating light with a wavelength of 200 nm to 400 nm in the air to the acrylic resin composition applied on the base layer,
A second light irradiation step of inducing wrinkles on the surface of the partially cured composition by irradiating light with a wavelength of less than 300 nm, and
A third light irradiation step of forming a surface treatment layer by irradiating light with a wavelength of 200 nm to 400 nm to the composition on which wrinkles are induced on the surface under nitrogen gas (N ₂ ) conditions;
Method for producing the flooring material of claim 1 that satisfies the following formula 1:
[Equation 1] 0.5 ≤ A _harden /A _acryl ≤0.7
In equation 1,
A _acryl refers to the area of the peak shown at a wave number of 809.6±1 cm ^-1 during Fourier-infrared spectroscopy analysis of an acrylic resin composition that has not been irradiated with light,
A _harden refers to the area of the peak shown at a wave number of 809.6 ± 1 cm ^-1 during Fourier-infrared spectroscopy analysis of the acrylic resin composition on which the first light irradiation step was performed.
According to clause 8,
The acrylic resin composition is,
For 100 parts by weight of multifunctional acrylate oligomer,
40 to 70 parts by weight of multifunctional acrylate monomer; and
A method of producing a flooring material comprising 50 to 70 parts by weight of a monofunctional acrylate monomer.
According to clause 8,
A method of manufacturing a flooring material in which the acrylic resin composition further includes a silicone additive.
According to clause 10,
A method for producing a flooring material in which the content of the silicone additive is 0.1 to 5 parts by weight based on 100 parts by weight of the multifunctional acrylate oligomer.