KR20210043156A - Floorings having excellent anti-pollution property - Google Patents

Abstract

The present invention relates to flooring having excellent fouling resistance and wax affinity and a manufacturing method thereof, wherein the flooring can have excellent fouling resistance and wax affinity by using a small amount of silicone additive on a surface treatment layer and realizing a micro-wrinkle structure on a surface of the surface treatment layer with a high frequency.

Description

Flooring with excellent stain resistance and wax affinity{Floorings having excellent anti-pollution property}

The present invention relates to a flooring material having excellent stain resistance and wax affinity, and a method for 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 provide excellent stain resistance and wax. It relates to a flooring material exhibiting affinity at the same time 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.

Accordingly, in order to improve the stain resistance of the surface, a surface treatment agent using a stain resistance additive has been developed. However, conventionally generally used stain resistance additives have the principle of controlling the stain resistance of the surface treatment layer formed through controlling the surface tension of the surface treatment agent. There is a difficult limit.

Accordingly, there is an urgent need to develop a flooring material having excellent stain resistance and wax affinity for flooring material in a trade-off relationship.

Republic of Korea Patent Publication No. 2014-0089074

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

Thus, the present invention in one embodiment,

Including a substrate 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),

When 3g of wax is applied to a unit area (200 mm X 200 mm), the area of the wax applied after 1 minute is 90% or more of the initial application area, providing a 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 of manufacturing the 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 flooring material according to the present invention has the advantage of implementing excellent stain resistance and wax affinity by using a small amount of silicone additives in the surface treatment layer and implementing a fine wrinkle structure on the surface of the surface treatment layer at high frequency.

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 the results of analyzing the Fourier transform-infrared spectroscopy of the acrylic resin composition before and after the first light irradiation step.

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, "molecular weight" is 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.

Further, 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 wax affinity, 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.

Accordingly, in order to improve the stain resistance of the surface, a surface treatment agent using a stain resistance additive has been developed. However, conventionally generally used stain resistance additives have the principle of controlling the stain resistance of the surface treatment layer formed through controlling the surface tension of the surface treatment agent. There is a difficult limit.

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

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

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 cured layer of an acrylic resin composition and is positioned on the uppermost layer of the flooring material. Here, the acrylic resin composition includes an acrylate-based oligomer and a monomer, and contains a small amount of a silicone additive together with the component, so that the surface may exhibit excellent stain resistance.

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

[Condition 1] When the washed floor material is visually observed after 20 minutes of iodine contamination, there is no difference in color of the surface; And

[Condition 2] After 30 seconds of oil magic contamination, the residual contamination area of the washed floor material is less than 5% of the original contamination area.

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

In addition, the floor material has improved contamination resistance to organic substances such as oil-based magic, so when washing the surface after 30 seconds have elapsed after applying oil-based magic, the residual contamination area on the surface of the washed flooring material must be less than 5% of the initial contamination 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, and when used in a certain amount in the surface treatment layer, contamination by contaminants on the surface can be improved. However, in this case, there is a problem in that the affinity for the wax is lowered and the wax wettability or coating property is deteriorated. In other words, when a silicone additive is used in the surface treatment layer, there is a problem that the wax is not applied well or the applied wax is peeled off after drying.

However, in the flooring material of the present invention, by introducing a fine wrinkle structure to the surface structure of the surface treatment layer, it is possible to improve the stain resistance of the surface and the wax affinity, specifically, wax wettability, coating property, adhesion, and the like.

Here, 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 addition, the surface treatment layer 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 wrinkles to improve stain resistance and wax affinity and exhibit matte properties.

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 wrinkles to improve stain resistance and wax affinity and exhibit matte properties.

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. According to the present invention, by controlling the height to the surface roughness of the wrinkles within the above range, it is possible to prevent contaminants from remaining between the wrinkles due to coarse wrinkles and deterioration of fouling resistance.

Meanwhile, 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 wrinkle continuously extends along its shape. 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, and through this, even if a matting agent is not used or a small amount of matting agent is used in the surface treatment layer. The glossiness can be lowered, the surface can be prevented from being contaminated by the remaining contaminants between the wrinkles, and the wax affinity of the surface can be improved.

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.

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

As another example, when performing a cross-cut test according to ASTM D3359 after 24 minutes after applying the wax to a thickness of 7.5±2.5㎛ for the flooring material, 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% of the total area, 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, peeling of the dried wax may not occur at all, and the damaged area may be 0.1% or less, close to 0%.

Furthermore, the flooring material induces scattering of light incident on the surface through the corrugation structure formed on the surface of the surface treatment layer, so that even if a matting agent is not used in the surface treatment layer or a small amount of matting agent is used in the surface treatment layer, it is significantly lower. Can be implemented.

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.

On the other hand, the flooring according to the present invention may further include a non-foaming layer, a glass fiber layer, and a printing layer in addition to the base layer and the surface treatment layer, and specifically, a foam layer, a glass fiber layer, a printing layer, a base layer and a surface. It may have a structure in which the treatment layers are sequentially stacked.

At this time, the non-foaming layer is a layer located at the bottom of the flooring material and supports the upper cured layer, the substrate layer, the printing layer, the dimensional stability layer, etc., 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 is based on 100 parts by weight of a polyvinyl chloride resin having a polymerization degree of 900 to 1200, and a plasticizer (for example, , Dioctyl terephthalate) may contain 35 to 58 parts by weight, and 80 to 100 parts by weight of a filler (eg, calcium carbonate).

The thickness of the non-foaming layer may be 200 to 2,000 μm. When the thickness of the non-foaming layer is less than 200 μm, the impact resistance and walking feeling of the flooring material may be deteriorated, and if it exceeds 2,000 μm, the flooring material may be thicker than necessary. The transparent layer is formed on the fiber-impregnated layer, and serves to increase durability, abrasion resistance, and elasticity, and to supplement strength.

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 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. After Fourier transform-infrared spectroscopy (FT-IR) measurement, it can be seen from the change in the intensity of the stretching peak of the C=C bond that appears in the wavenumber range of ^{809.6±1 cm -1.}

As an example, the acrylic resin composition may satisfy Equation 1 below in Fourier-infrared spectroscopy analysis:

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

In Equation 1,

A _acryl refers to the area of a peak represented by a wave number of ^{809.6±1 cm -1} when Fourier-infrared spectroscopy analysis of an acrylic resin composition is not irradiated with light,

A _harden means the area of a peak represented by a wave number of ^{809.6±1 cm -1} when Fourier-infrared spectroscopy analysis of the acrylic resin composition in which the first light irradiation step has been performed is performed.

^{Specifically, the acrylic resin composition partially cured in the first light irradiation step, and 809.6±1 cm -1} wavenumber indicating the stretching of the C=C bond during Fourier-infrared spectroscopy analysis before and after the first light irradiation step. The peak area ratio (A _harden /A _acryl ) of the range may be 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 condition may be performed under general air or clean dry air conditions, and in some cases, oxygen gas (O ₂ ) refers to a state in which nitrogen gas (N _{2) is mixed.} can do. 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 wrinkle structure using excimer, so that a matting agent is not used or a small amount of matting agent of less than 10% by weight is used. It is also possible to reduce the glossiness of the surface treatment layer. 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 100 mJ/cm 2 to 500 mJ/cm 2, and specifically 100 mJ/cm 2 to 400 mJ/cm 2 18 200 mJ/cm 2 to 500 mJ/cm 2, 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 having a wavelength of 172±2 nm in the composition is 295 ~ 295 ~ under nitrogen (N _{2 ) containing oxygen (O 2) of 100 ppm or less.} It can be performed by irradiating for a very short time of 1 to 2 seconds with an amount of light of 305 mJ/cm 2 (ie, the amount of 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.

At this time, the surface temperature of the cured 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, in the third light irradiation step, light having a wavelength of 300±10 nm to the composition and/or the surface treatment layer is 100 to 3,000 mJ/cm 2, specifically, 1 to 900 mJ/cm 2 _{It may be carried out by irradiation in a nitrogen (N 2} ) atmosphere for a very short time of 2 seconds, in which 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 may include a polyfunctional acrylate oligomer, a polyfunctional acrylate monomer, and a monofunctional acrylate monomer.

Specifically, the acrylic oligomer means an oligomer obtained using a monomer containing an acrylic group, and the monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth) 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. have. For example, the acrylic oligomer is methyl acrylate, (meth) acrylate, ethyl acrylate, benzyl acrylate or a mixture thereof polymerized, methyl acrylate oligomer, (meth) acrylate oligomer, methyl (meth) acrylic Rate oligomers, ethyl acrylate oligomers, benzyl acrylate oligomers, benzyl (meth) acrylate oligomers, and the like may be included.

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 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, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate , Pentaerythritol triacrylate, trimethylolpropaneethoxytriacrylate, and hexamethyldiamine diacrylate. In some cases, at least one selected from the group consisting of the acrylate monomer and the bifunctional urethane An acrylate, a trifunctional urethane acrylate, or a 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 contain 50 to 70 parts by weight and 40 to 70 parts by weight of a monofunctional acrylate monomer and a polyfunctional acrylate monomer, respectively, based on 100 parts by weight of the polyfunctional acrylate oligomer.

As an example, the acrylic resin composition comprises 57 to 70 parts by weight and 50 to 63 parts by weight, specifically, a monofunctional acrylate monomer and a polyfunctional acrylate monomer, respectively, based on 100 parts by weight of a polyfunctional urethane acrylate oligomer. 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 an ultraviolet-curable liquid silicone additive to improve stain resistance of the surface treatment layer, and as such silicone additive, for example, a high molecular weight amphiphilic silicone additive may be used. . At this time, the molecular weight of the silicone additive may be 30,000 to 90,000.

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

When using a silicone additive, there is a problem that the surface tension of the acrylic resin composition is lowered, so that 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, by controlling the content of the silicone additive within the above range, the surface tension of the acrylic resin composition is appropriately lowered. While improving stain resistance, it is possible to minimize the decrease in wax affinity. In addition, it is possible to prevent the cure rate from being significantly lowered due to an excessive amount of the silicone additive.

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

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), a monofunctional acrylate monomer, a matting agent, 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 Manufacturing 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 Second acrylate monomer (trifunctional) 10g 10g 10g 10g Monofunctional acrylate monomer 25g 25g 25g 25g Silicone additives 0g 0.1g 1g 6g Quencher 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 having a width of 10 cm by a length of 10 cm and fixed to a light curing device. Thereafter, 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 First light irradiation Wavelength range 250~400 ㎚ Irradiation 100±2 mJ/㎠ Distance from light source 50±1㎜ Gas condition Conditions of clean dry air (O ₂ concentration: 20±2 vol.%) Second light irradiation Wavelength range 172±5 nm Irradiation 300±5 mJ/㎠ Distance from light source 100±1㎜ Gas condition N ₂ condition
(O ₂ concentration: 1,000 ppm or less) 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 Comparative Example 6 Type of acrylic composition Composition of Preparation Example 1 Composition of Preparation Example 2 Composition of Preparation Example 4 Composition of Preparation Example 1 Of Preparation Example 3
Composition Of Preparation Example 3
Composition Curing condition Curing condition 1 Curing condition 1 Curing condition 1 Curing condition 2 Curing condition 2 Curing condition 3

Curing condition 2 Curing condition 3 First light irradiation Wavelength range 250~400 ㎚ - Irradiation 100±2 mJ/㎠ - Distance from light source 50±1㎜ - Gas condition Clean dry air condition
(O ₂ concentration: 20±2 vol.%) - Second light irradiation Wavelength range - 172±5 nm Irradiation - 300±5 mJ/㎠ Distance from light source - 50±1㎜ Gas condition - N ₂ condition
(O ₂ concentration: 1,000 ppm or less) 3rd light irradiation Wavelength range 250~400 ㎚ 250~400 ㎚ Irradiation 700±10 mJ/㎠ 700±10 mJ/㎠ Distance from light source 100±1㎜ 100±1㎜ Gas 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 6, 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 6 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, it can be seen that when the first light irradiation step is performed, 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 the change of 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 of 10 cm x 10 cm long, and the Fourier transform in the wavenumber range ^{of 400 to 4,000 cm -1 targeting the specimen-infrared spectroscopy} Was measured. Then, after performing the first light irradiation step on the specimen, the ^{Fourier transform-infrared spectroscopy in the wavenumber range of 400 to 4,000 cm -1} was re-measured, and the results are shown in FIG. 3.

Referring to FIG. 3, it can be seen that the first light irradiation step controls the size and frequency of the wrinkle structure formed on 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 in the Fourier transform-infrared spectroscopy (FT-IR) measurement before the first light irradiation step.} It can be seen that it has a stretching peak of C=C bonds appearing in the wave number range of, and the intensity of the peak decreases after the first light irradiation step. More specifically, since the intensity of the peak decreases after the first light irradiation step, the ratio _{of the peak area (A harden} ) after the first light irradiation step to the _{peak area (A acryl ) before the first light irradiation step (A harden} /A _acryl ) can be confirmed that is 0.5 to 0.7. This means that the acrylic resin composition undergoes curing of about 30% to 50% after the first light irradiation step.

Partial curing of the acrylic resin composition in the first light irradiation step as described above reduces the degree 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 I can make it

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 of the specimens prepared in Example 1 and Comparative Examples 1 to 6 were measured. 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 (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 based on the initial contaminated 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, and dried for 24 minutes to coat the wax on the surface treatment layer. Then, according to the A evaluation method of ASTM D3359, the surface of the laminated film was cut in an X shape with a knife at an angle of 30 to 45° and a length of about 40 mm (1.5 inch). Thereafter, a tape (about 75 mm (3 inches in length)) was firmly attached to the cut surface along the X-shape, and quickly peeled off to confirm the peeling state of the cut X-shape. It was given according to the confirmed peeling state, and the criteria are as follows:

Grade 0: X-shaped area completely peeled off,

Grade 1: delamination of about 50% or more of the total area was observed,

Grade 2: Separation of up to 3.2 mm (1/8 inch) on both sides of the cut X-shaped straight portion was confirmed by zigzag,

Grade 3: Separation within and outside of about 1.6 mm (1/6 inch) on both sides of the cut X-shaped straight portion was confirmed in zigzag,

Grade 4: A trace of peeling or removal of less than about 5% of the total area is identified along the straight part or intersection of the cut X-shape.

Grade 5: No delamination of the cut surface was observed.

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

At 22±2° C. on the surfaces of the specimens of Examples and Comparative Examples, 3 g of wax (a mixture containing 50-70% by weight of acrylic resin and water) was dropped, and a unit area (200 mm X 200 mm) using a sponge ) Was applied to fill all. 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.

Gloss Evaluation Wax affinity Cross-cut After 1 minute
Wax application area ratio 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 Level 1 Level 1 100% Comparative Example 4 5.0±0.1 Level 1 Level 5 100% Comparative Example 5 6.0±0.1 Level 5 Level 5 40% Comparative Example 6 3.5±0.1 Level 1 Level 5 100%

As shown in Table 5 above, it can be seen that the flooring material according to the present invention has a remarkably 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 glossiness of less than 2.0 under a gloss 60° condition even when a small amount of matting agent of less than 10% by weight was used, and excellent stain resistance was observed, and there were no visible contamination marks on the surface before and after iodine contamination. It was not confirmed, and it was found that the area of contamination after vodmaka contamination and washing was less than 5%. In addition, the flooring specimen has excellent wax affinity, so that the wax does not peel off even if the coated wax is cross-cut and detached, and the first applied area is 100% after 1 minute has elapsed after applying the wax to the surface. Confirmed to maintain.

From these results, the flooring material according to the present invention contains a polyfunctional urethane acrylate oligomer and a silicone acrylate oligomer in a specific ratio in the surface treatment layer, and a fine wrinkle structure is implemented on the surface of the surface treatment layer at high frequency, so that a separate additive It can be seen that it realizes low glossiness and has excellent stain resistance and wax affinity.

Claims (11)

Including a substrate 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),
When 3g of wax is applied to a unit area (200 mm X 200 mm), the area of the wax applied after 1 minute is at least 90% of the initial application area.
The method of claim 1,
The surface treatment layer is a flooring material, characterized in that the peeling area of the total area of the dried wax is 5% or less when performing a cross-cut test according to ASTM D3359 after 24 minutes after applying the wax to a thickness of 7.5±2.5 μm.
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 is a flooring whose residual contaminated area of the surface treatment layer washed 30 seconds after vodmaka contamination is less than 5% of the original contaminated area.
The method of claim 1,
Flooring with a surface gloss of less than 3 under Gloss 60° conditions.
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,
The base layer is a flooring material having a non-foaming layer, a glass fiber layer, and a printing layer at the bottom.
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;}
Method for producing a flooring material 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 a peak represented by a wave number of ^{809.6±1 cm -1} when Fourier-infrared spectroscopy analysis of an acrylic resin composition is not irradiated with light,
A _harden means the area of a peak represented by a wave number of ^{809.6±1 cm -1} when Fourier-infrared spectroscopy analysis of the acrylic resin composition in which the first light irradiation step has been performed is performed.
The method of claim 8,
The acrylic resin composition,
Based on 100 parts by weight of the polyfunctional acrylate oligomer,
40 to 70 parts by weight of a polyfunctional acrylate monomer; And
A method for producing a flooring material comprising 50 to 70 parts by weight of a monofunctional acrylate monomer.
The method of claim 8,
Acrylic resin composition is a method of manufacturing a flooring material further comprising a silicone additive.
The method of claim 10,
The content of the silicone additive is 0.1 to 5 parts by weight based on 100 parts by weight of the polyfunctional acrylate oligomer.

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