KR20200027138A - Non-foaming floorings with excellent in iodine resistance and having radial flexure structure on surface - Google Patents

Abstract

The present invention relates to a non-foaming flooring material having a radial flexure structure on the surface, thereby having excellent fouling resistance. The non-foaming flooring material uses a specific range of short-wavelength light in an acrylic resin composition by stages under different conditions to have a high curing density, can realize low gloss by comprising a cured layer having the radial flexure structure on the surface thereof, and thus can realize excellent fouling resistance (in particular, iodine resistance), thereby being able to be usefully used in industrial flooring materials requiring excellent fouling resistance.

Description

Non-foaming floorings with excellent in iodine resistance and having radial flexure structure on surface}

The present invention relates to a non-foaming flooring having a radially curved structure on a surface and a method for manufacturing the same, in detail, when curing, a specific range of short wavelength light is used in stages under different conditions to induce a radially curved structure on the surface, leading to excellent resistance It relates to a non-foaming flooring material exhibiting contamination and a method for manufacturing the same.

In general, the flooring material provides a hygienic space by blocking dust and cold air from the cement floor, and the beautiful patterns of various colors are printed to change the atmosphere of the room according to the customer's taste and have a decorative effect. This conventional flooring has a problem that the flooring having a trace of the contaminant cannot perform its basic functions because the user cannot easily erase the trace of the contaminant when the surface is contaminated with the contaminant.

In order to overcome this problem, by forming a surface treatment layer on the top layer of the flooring to impart contamination resistance of the flooring. However, conventional flooring materials use various types of fillers in the surface treatment layer as additives to improve specific performance. When inorganic particles such as silica are used as fillers to achieve scratch resistance or to reduce gloss, additives are added. Since most of the fillers are porous and have a very low apparent specific gravity, the adsorption of fine dust, moisture, grease, etc. becomes easy as the content increases, and the stain resistance is rapidly reduced, and marks such as hand and foot sweat marks are surface treated. It remains on the surface of the flooring, which causes the appearance to become cloudy, like fog.

Therefore, there is an urgent need to develop a flooring material with improved stain resistance so that contaminants are not easily attached to the flooring material regardless of whether a filler containing inorganic particles or the like is used.

Republic of Korea Patent Publication No. 2014-0089074

An object of the present invention is to provide a non-foaming type flooring material having improved stain resistance so that contaminants are not easily attached to the surface of the flooring material regardless of whether a filler containing inorganic particles or the like is used.

Thus, in one embodiment of the present invention,

Base layer; And

The surface includes a cured layer of an acrylic resin composition having a dendrite shape which is a radially curved structure extending from the center to the periphery with one point as the center,

The radial bending structure satisfies any one or more of conditions 1 and 2,

In infrared (IR) spectroscopy, the ratio of the intensity of the first peak (I _p1 ) in the range of 810 ± 10 cm ^-1 and the intensity of the second peak (I _p2 ) in the range of 1720 ± 10 cm ^-1 ( I _p1 / I _p2 ) provides a non-foaming flooring of 0.020 to 0.055:

[Condition 1] The average diameter of the radially curved structure is 5 µm to 500 µm; And

[Condition 2] The radially curved structure is lower in height from the center to the periphery, but the average height of the center is 1 μm to 30 μm.

In addition, the present invention in one embodiment,

A first light irradiation step of activating the composition by irradiating light having a wavelength of less than 300 nm to an acrylic resin composition located on the base layer under inert gas conditions;

A second light irradiation step of irradiating the activated composition with light having a wavelength of 200 nm to 400 nm under air conditions to firstly cure the composition; And

A third light irradiation step of irradiating light having a wavelength of 200 nm to 400 nm under an inert gas condition to the primary cured composition to secondary-cure the composition to form a cured layer,

Infrared (IR) spectroscopy of the cured layer, the intensity of the first peak (I _p1 ) in the range of 810 ± 10 cm ^{-1 and} the intensity of the second peak (I _p1 ) in the range of 1720 ± 10 cm ^-1 _It provides a method for producing a non-foaming flooring having a ratio of _p2 ) (I _p1 / I _p2 ) of 0.020 to 0.055.

The non-foaming flooring according to the present invention can implement a low gloss by including a cured layer having a high cured density and a radially curved structure on the surface of the acrylic resin composition using a specific range of short wavelength light step by step under different conditions. In addition, since it implements excellent stain resistance (especially iodine resistance), it can be usefully used in industrial flooring materials that require excellent stain resistance.

1 is a structural diagram showing an example of an optical curing apparatus used in the manufacture of a cured layer according to the present invention.
2 and 3 are images obtained by scanning electron microscopy (SEM) on the surface of the cured layer of the non-foaming floors prepared in Examples 1 and 3.
FIG. 4 is a scanning electron microscope (SEM) image of the surface of the cured layer of the non-foaming floor prepared in Comparative Example 3.

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

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

In the present invention, the terms "comprises" or "having" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.

In addition, it is to be understood that the accompanying drawings in the present invention are shown to be enlarged or reduced for convenience of description.

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

The present invention relates to a non-foaming flooring having a radially curved structure on its surface.

Existing flooring has a problem that the flooring with a trace of the pollutant can not perform its basic function because the user can not easily erase the trace of the pollutant when the surface is soiled with contaminants. In order to overcome this problem, by forming a surface treatment layer on the top layer of the flooring, scratch resistance and scratch resistance of the flooring as well as contamination resistance are provided. However, conventional flooring materials use various types of fillers in the surface treatment layer as additives to improve specific performance. When inorganic particles such as silica are used as fillers to achieve scratch resistance or to reduce gloss, additives are added. Since most of the fillers are porous and have a very low apparent specific gravity, the adsorption of fine dust, moisture, grease, etc. becomes easy as the content increases, and the stain resistance is rapidly reduced, and marks such as hand and foot sweat marks are surface treated. It remains on the surface of the flooring, which causes the appearance to become cloudy, like fog.

Accordingly, the present invention provides a non-foaming flooring having a radially curved structure on the surface and having excellent stain resistance, and a method for manufacturing the same.

The non-foaming flooring according to the present invention can implement a low gloss by including a cured layer having a high cured density and a radially curved structure on the surface of the acrylic resin composition using a specific range of short wavelength light step by step under different conditions. In addition, since it implements excellent stain resistance (especially iodine resistance), it can be usefully used in industrial flooring materials that require excellent stain resistance.

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

Non-foaming flooring

The present invention in one embodiment,

Base layer; And

On the surface, a non-foaming flooring material including a cured layer having a dendrite shape, which is a radially curved structure extending from the center to the periphery with one point as the center, is provided.

The non-foaming flooring according to the present invention is a plastic flooring material composed of industrial ceramic tiles or rubber flooring or polyvinyl chloride (PVC) materials used in offices, and the like, in the form of a single layer sheet (SLS) tile. It can be flooring. The flooring material includes a cured layer of a composition containing an acrylic oligomer on the base layer in the outermost layer of the structure, and the cured layer has a curved structure having a specific shape on the surface. Specifically, the non-foaming type flooring material may have a cured layer having a finely curved structure on its outermost surface. The curved structure has a structure in which a random point present on the surface of the cured layer is a central portion, and a radial irregularity that extends from the central portion to the peripheral portion but decreases in height from the central portion to the peripheral portion is randomly distributed. For example, the radially curved structure may include a structure in which an arborescence structure or a dendrite structure is randomly dispersed at an arbitrary point on the surface of the cured layer.

In addition, the radial bend structure may be controlled by its size or height, surface properties, specifically, surface glossiness, fouling resistance (specifically, iodine resistance), for this purpose, the radial bend structure has the following condition 1 And 2 or more:

[Condition 1] The average diameter of the radially curved structure is 5 µm to 500 µm; And

[Condition 2] The radially curved structure is lower in height from the center to the periphery, but the average height of the center is 1 μm to 30 μm.

Specifically, the condition 1 shows the average size of the individual radially curved structures present on the surface of the cured layer, and the average diameter may be 5 μm to 500 μm, more specifically 5 μm to 450 μm, 5 μm to 400㎛, 5㎛ to 350㎛, 5㎛ to 300㎛, 5㎛ to 250㎛, 5㎛ to 200㎛, 5㎛ to 150㎛, 5㎛ to 100㎛, 5㎛ to 50㎛, 50㎛ to 200㎛ , 50㎛ to 100㎛, 100㎛ to 500㎛, 100㎛ to 300㎛, 100㎛ to 200㎛, 80㎛ to 150㎛, 20㎛ to 100㎛, 25㎛ to 60㎛, 40㎛ to 80㎛, 80 Μm to 120 μm, 90 μm to 110 μm, 5 μm to 40 μm, 5 μm to 30 μm, 5 μm to 25 μm, 5 μm to 20 μm, 5 μm to 15 μm, 5 μm to 10 μm, 10 μm to 30㎛, 15㎛ to 30㎛, 15㎛ to 25㎛, 20㎛ to 30㎛, 1㎛ to 10㎛, 2㎛ to 10㎛, 4㎛ to 10㎛, 5㎛ to 10㎛, 7.5㎛ to 10㎛ , 8㎛ to 10㎛¸0.5㎛ to 7.5㎛, 0.5㎛ to 5㎛, 0.5 ㎛ to 3㎛, 0.5㎛ to 2㎛, 0.5㎛ to 1㎛, 1㎛ to 5㎛¸1㎛ to 3㎛, 1㎛ to 2㎛, 2㎛ to 5㎛, 2㎛ to 3.5㎛, 4㎛ to It may be 8 μm, 4 μm to 6 μm, 5 μm to 8 μm, 5 μm to 6.5 μm, 6 μm to 9 μm, 6 μm to 8 μm, 7 μm to 9 μm, or 3 μm to 5 μm.

In addition, the condition 2 represents the average value of the maximum height of the individual radially curved structures present on the surface of the cured product, and the average height may be 1 μm to 30 μm, and more specifically, the average height is 2 μm to 25 μm. , 5㎛ to 20㎛, 1㎛ to 10㎛, 10㎛ to 15㎛, 10㎛ to 20㎛, 15㎛ to 30㎛, 20㎛ to 30㎛, 5㎛ to 12㎛, 13㎛ to 21㎛ or 15 It may be from μm to 19 μm.

In addition, the radial bending structure may be formed at a certain frequency, for example, a certain number in a unit area, to improve physical properties such as surface glossiness, contamination resistance (specifically, iodine resistance) of the cured layer, and the radial bending structure The number of may be the same as the number of central portions of the radially curved structure present in the unit area. In addition, the radial bending structure may be 2 to 400 per unit area (1 mm X 1 mm) of the surface of the cured layer, specifically 10 to 350 per unit area (1 mm X 1 mm), 10 to 300 Dogs, 10 to 250, 10 to 200, 10 to 150, 100 to 400, 100 to 350, 150 to 350, 250 to 350, 200 to 400, 30 to 100, 5 to 180 Dogs, 5 to 150, 5 to 120, 10 to 100, 10 to 80, 10 to 50, 20 to 50, 40 to 60, 80 to 120, 140 to 180, 30 to 40 Dogs, 5 to 15, 10 to 20, 5 to 16, or 5 to 20.

For example, the cured layer may include 80 to 120 dendrite shapes having an average diameter of 60 to 70 μm and a surface roughness (Rz) of 18 to 22 μm per unit area (1 mm X 1 mm) on the surface. have.

In addition, the non-foaming flooring according to the present invention has a high curing density of the outermost layer of the cured layer, so that a low proportion of double bonds may remain on the surface of the cured layer. For example, the cured layer has a low distribution of double bonds remaining on the surface, and the intensity of the first peak (I _p1 ) in the range of 810 ± 10 cm ^-1 , which represents the double bond of acrylate when measured by infrared (IR) spectroscopy. And a ratio (I _p1 / I _p2 ) of the intensity (I _p2 ) of the second peak, which is a reference peak present in the range of 1720 ± 10 cm ^-1 , may satisfy a range of 0.020 to 0.055. More specifically, the intensity ratio (I _p1 / I _p2 ) of the first peak and the second peak is 0.020 to 0.035, 0.020 to 0.045, 0.020 to 0.043, 0.025 to 0.050, 0.030 to 0.045, 0.035 to 0.043, 0.038 to 0.043 , 0.040 to 0.055, or 0.041 to 0.042. The present invention minimizes the absorption or binding of contaminants such as iodine to the surface by satisfying the ratio (I _p1 / I _p2 ) of the first peak and the second peak in the above range when performing infrared (IR) spectroscopy measurement on the surface of the cured layer. It can improve the stain resistance.

As an example, the non-foaming flooring contaminates the outermost layer of the cured layer with 1% by volume of iodine solution at a humidity of 22 ± 1 ° C and 50 ± 5% RH, and after 5 minutes of curing, wipe the surface with a Kim's wipe and then surface When the area of iodine remaining in the eye is visually confirmed, the area of iodine remaining on the basis of the initial contamination area may be less than 1%, specifically, 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, or 0.5% or less In some cases, iodine on the surface may be removed, and the residual area may be 0%.

Furthermore, the non-foaming flooring according to the present invention can realize a significantly low gloss even if an additive such as a matting agent is not used or a very small amount is provided by providing the radially curved structure as described above. Specifically, the radially curved structure induces scattering of light incident on the surface of the non-foaming flooring material, so that a low gloss can be imparted to the surface even when a small amount of a matting agent is not used. As one example, the non-foaming type flooring may have a surface glossiness of less than 10 when measuring 60 ° glossiness (gloss 60 ° condition) using a gloss meter, and specifically, an upper limit of 9 or less, 8 or less, 7.5 or less, 7 or less, 6.5 or less, 6 or less, or 5 or less, and the lower limit may be 0.1 or more, 0.5 or more, 1 or more, 1.5 or more, 2 or more, 2.5 or more, or 3 or more. As one example, the surface gloss of the non-foaming flooring is 1 to 9, 2 to 9, 4 to 9, 1 to 8, 1 to 7, 1 to 6, 4 to 8, 5 to 8, 4 to 6, 4 to 7, 7 to 9, 7.2 to 8.7, 2 to 6, 4 to 6, 2 to 5, or 3.2 to 4.7.

Meanwhile, the acrylic resin composition formed on the cured layer may include a urethane acrylic oligomer, a monomer including at least one polymerizable reactor, and an initiator.

Specifically, the urethane acrylic oligomer means an oligomer containing an acrylic group as a polymerizable functional group together with the urethane group. The urethane acrylic oligomer may have a weight average molecular weight of 100 to 50,000, more specifically 500 to 30,000, 1,000 to 10,000, or 1,000 to 5,000. The present invention can further improve the durability of the cured layer by adjusting the weight average molecular weight of the urethane acrylic oligomer to the above range.

In addition, the monomer containing at least one polymerizable reactor may be an acrylate-based monomer. For example, the monomers include (meth) acrylate, benzyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate , 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate or 2-hydroxypropylene glycol (meth) acrylate, acrylic acid, meta Acrylic acid, 2- (meth) acryloyloxyacetic acid, 3- (meth) acryloyloxypropyl acid, 4- (meth) acryloyloxybutyl acid, 1,6-hexanediol diacrylate (1, 6-HDDA), acrylic acid doublets, itaconic acid, maleic acid, caprolactone modified hydroxyl acrylate (CHA), tetraethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylic Late, triethylene glycol Diacrylate, pentaerythritol tri it can include acrylate, trimethylolpropane ethoxy triacrylate, and N- vinylpyrrolidone one or more selected from the group consisting of (N-vinylpyrrolidone).

In addition, the acrylic resin composition may include 100 parts by weight of an acrylic oligomer and 50 to 150 parts by weight of a monomer containing one or more polymerizable reactors, and specifically, 100 parts by weight of an acrylic oligomer, and a polymerizable reactor 1 50 to 140 parts by weight, 50 to 130 parts by weight, 50 to 120 parts by weight, 50 to 110 parts by weight, 50 to 100 parts by weight, 50 to 90 parts by weight, 50 to 80 parts by weight, 75 to 150 Parts by weight, 90 to 150 parts by weight, 100 to 150 parts by weight, 120 to 150 parts by weight, 130 to 150 parts by weight, 75 to 95 parts by weight, 90 to 105 parts by weight, 105 to 120 parts by weight, 115 to 130 parts by weight , 120 to 140 parts by weight, or 135 to 150 parts by weight.

In addition, the acrylic resin composition is 10 parts by weight or less, specifically 8 parts by weight or less, 6 parts by weight or less, 3 parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, 2 based on 100 parts by weight of the acrylic oligomer and monomer Less than 1 part by weight or less than 1 part by weight of initiator. The present invention can exhibit a high cure density even when a small amount of the initiator is included in the above range by using a short range of light in a specific range stepwise under different conditions when curing the composition. As an example, the curing rate of the cured layer according to the present invention is 80% or more, 85% or more, 90% or more, 83% to 98%, 88% to 97%, 81% to 87%, 86% to 91%, 93% to 99%, 85% to 95%, 90% to 98% or 88% to 96%.

Furthermore, the composition according to the present invention may further include a filler having a high hardness in order to improve durability while performing a part of a dendrite-shaped seed formed on the surface of the cured layer. For example, as the filler, one that can improve the surface hardness without affecting the gloss of the cured layer after curing the composition may be used. Specifically, colloidal silica, alumina, glass beads, organic beads (polymer particles, etc.) may be used as the filler, and their average diameter may be 1 μm to 15 μm, more specifically 1 μm to 12 μm. Μm, 1 μm to 10 μm, 2 μm to 13 μm, 3 μm to 10 μm, 3 μm to 7 μm, 9 μm to 12 μm, 11 μm to 15 μm, 4 μm to 11 μm, or 6 μm to 9 μm You can. In the present invention, by controlling the average diameter of the filler to the above range, it is possible to prevent cracking of the cured layer and increase the adhesion between the cured layer and other layers to improve durability. In addition, the filler may be included in less than 10 parts by weight based on 100 parts by weight of the composition. For example, the filler may contain 10 parts by weight or less based on 100 parts by weight of the composition, and more specifically, the content of the filler has an upper limit of less than 10 parts by weight, less than 9 parts by weight, less than 8 parts by weight, and 7 parts by weight It may be less than 6 parts by weight, less than 5 parts by weight, or less than 4 parts by weight, and the lower limit may be 0.01 parts by weight or more, 0.05 parts by weight or more, 0.1 parts by weight or more, 0.5 parts by weight or more, or 1 part by weight or more. As one example, the filler may be 0.1 to 3 parts by weight, 0.1 to 2.5 parts by weight, 0.5 to 2.5 parts by weight, 1 to 3 parts by weight, 1.5 to 3 parts by weight, 2.5 to 3 parts by weight, 1.5 to 2 parts by weight, 2 to 2.5 parts by weight, or 2.2 to 2.7 parts by weight. The present invention can increase the adhesion of the cured layer while properly inducing a dendrite-shaped radial bend structure on the surface of the cured layer by controlling the content of the filler to the above range, it is possible to suppress the durability decrease due to cracking.

In addition, the average thickness of the cured layer can be adjusted to an appropriate range that does not affect durability. For example, the cured layer may have an average thickness of 3 μm to 50 μm so as not to be torn or lost by external stimuli, more specifically 3 μm to 30 μm, 3 μm to 15 μm, 3 μm to 10 μm , 10㎛ to 20㎛, 10㎛ to 30㎛, 25㎛ to 50㎛, 30㎛ to 50㎛, 20㎛ to 40㎛, 15㎛ to 20㎛, 15㎛ to 25㎛, 11㎛ to 24㎛ or 18 It may be from µm to 28 µm. The average thickness of the cured layer referred to in the present invention may mean the average thickness (T _aver ) of the cured layer excluding the height of dendrites as shown in FIG. 2, and in some cases, the dendrite height is excluded It may mean a thickness including 1/2 of the average thickness (T _aver ) of the layer and the average maximum height (R _max ) of the dendrites.

Method for manufacturing non-foaming flooring

In addition, the present invention in one embodiment,

A first light irradiation step of activating the composition by irradiating light having a wavelength of less than 300 nm to an acrylic resin composition located on the base layer under inert gas conditions;

A second light irradiation step of irradiating the activated composition with light having a wavelength of 200 nm to 400 nm under air conditions to firstly cure the composition; And

A third light irradiation step of irradiating light having a wavelength of 200 nm to 400 nm under an inert gas condition to the primary cured composition to secondary-cure the composition to form a cured layer,

Infrared (IR) spectroscopy of the cured layer, the intensity of the first peak (I _p1 ) in the range of 810 ± 10 cm ^{-1 and} the intensity of the second peak (I _p1 ) in the range of 1720 ± 10 cm ^-1 _It provides a method for producing a non-foaming flooring having a ratio of _p2 ) (I _p1 / I _p2 ) of 0.020 to 0.055.

The method for manufacturing a non-foaming flooring according to the present invention includes the step of irradiating an acrylic resin composition with a short range of light in a specific range in three steps under different conditions, and performing the stepwise light curing process as described above. The ratio of the double bond on the surface of the cured layer formed on the base layer is in the range of the intensity of the first peak (I _p1 ) and the range of 1720 ± 10 cm ^{-1 in the} range of 810 ± 10 cm ^-1 when measured by infrared (IR) spectroscopy. It is possible to control the double bond ratio low so that the ratio (I _p1 / I _p2 ) of the intensity (I _p2 ) of the second peak to satisfy 0.020 to 0.055; Any point present on the surface of the cured layer is used as the center, and a radially curved structure in which radial irregularities that extend from the center to the periphery but decrease in height from the center to the periphery can be easily formed.

Specifically, the first light irradiation step is a first step of irradiating light to the composition applied on the substrate layer, and the surface of the composition and / or the cured layer to which the excimer generated by the irradiated light is applied is contracted This is a step of increasing the scattering rate of light incident on the surface by forming wrinkles. The present invention can significantly improve the stain resistance of the surface, specifically, iodine resistance, and increase the scattering rate of light by shrinking the surface of the composition and / or the cured layer into the above-described radial bending structure using an excimer. Surface gloss can be reduced by using no matting agent or using a very small amount. To this end, the first light irradiation step includes nitrogen (N ₂ ) containing a small amount of oxygen (O ₂ ) using light having a wavelength of less than 300 nm, specifically, 100 to 200 nm or 150 to 195 nm with high energy. May be performed in an atmosphere. Specifically, the concentration of oxygen (O ₂ ) contained in the nitrogen (N ₂ ) in the first light irradiation step may be 10 to 30,000ppm, specifically 10 to 20,000ppm, 10 to 5,000ppm, 1,000 to 2,000ppm , 2,000 to 3,000 ppm, 3,000 to 4,000 ppm, 4,000 to 5,000 ppm, 10 to 2,000 ppm, 10 to 1,000 ppm, 10 to 500 ppm, 100 to 300 ppm, 10 to 200 ppm, 50 to 150 ppm, 80 to 120 ppm, 4,000 to 6,000 ppm , 4,500 to 5,500 ppm or 4,800 to 5,200 ppm. In addition, the distance between the composition and the light source in the first light irradiation step may be 5 to 100 mm, specifically 5 to 80 mm, 5 to 60 mm, 5 to 40 mm, 10 to 70 mm, 10 to 50 mm, 10 It may be ˜30 mm, 20-80 mm, 20-60 mm, 20-50 mm, 20-30 mm, 25-75 mm, 50-80 mm, 40-60 mm or 45-55 mm.

As one example, the first light irradiation step is 5 ~ 100 in nitrogen (N ₂ ) conditions containing 100ppm of oxygen (O ₂ ) of light having a wavelength of 172 ± 2nm in the composition to form an excimer in the composition. It can be performed by irradiating for a very short time of 1 to 2 seconds with a light amount of mJ / cm 2.

The present invention can easily control the average diameter, height and / or frequency of the randomly-cured finely curved structure formed on the surface of the cured layer by controlling the gas conditions and the distance between the composition and the light source when performing the first light irradiation step. can do.

In addition, in the first light irradiation step, the light irradiation amount may be 1 mJ / cm 2 to 100 mJ / cm 2, specifically 1 mJ / cm 2 to 80 mJ / cm 2, 1 mJ / cm 2 to 60 mJ / cm 2 ¸ 1 mJ / Cm2 to 40 mJ / cm2, 1 mJ / cm2 to 35 mJ / cm2, 1 mJ / cm2 to 30 mJ / cm2 to 1 mJ / cm2 to 20 mJ / cm2, 1 mJ / cm2 to 10 mJ / cm2, 5 mJ / Cm2 to 10 mJ / cm2, 5 mJ / cm2 to 20 mJ / cm2, 5 mJ / cm2 to 25 mJ / cm2, 5 mJ / cm2 to 35 mJ / cm2, 5 mJ / cm2 to 50 mJ / cm2, 15 mJ / Cm 2 to 25 mJ / cm 2, 25 mJ / cm 2 to 35 mJ / cm 2, 25 mJ / cm 2 to 50 mJ / cm 2, 40 mJ / cm 2 to 60 mJ / cm 2, 70 mJ / cm 2 to 100 mJ / cm 2 or 5 mJ / Cm 2 to 33 mJ / cm 2. The present invention can easily control the average diameter, height and / or frequency of the randomly-radiated finely curved structure formed on the surface of the cured layer by controlling the light irradiation amount of the first light irradiation step to the above range.

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

In addition, the second light irradiation step is a step of temporarily curing by applying ultraviolet (UV) energy to the composition and / or cured layer of the surface shrinkage, wavelengths of 200 to 400nm or more, specifically 250 to 380nm, 280 to 380nm , 250-350 nm, or 280-320 nm light may be performed by irradiating in air conditions. At this time, the surface temperature of the provisionally cured composition and / or cured layer may be 20 to 90 ℃, specifically 20 to 80 ℃ or 30 to 70 ℃.

As an example, the second light irradiation step may be performed by irradiating the composition and / or the cured layer with light having a wavelength of 300 ± 5 nm for a very short time of 1 to 2 seconds at a light amount of 20 to 800 mJ / cm 2 under air conditions. Where the distance between the composition and / or the cured layer and the light source can be 0.5 to 10 mm.

In addition, the third light irradiation step is a step of additionally irradiating ultraviolet (UV) to the provisionally cured composition and / or the cured layer to perform the hardening, a wavelength of 400nm or less, specifically, 100 to 400nm, 200 Nitrogen (N ₂ ) atmosphere containing a small amount of oxygen (O ₂ ) using light at a wavelength of from 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 performed in. Here, the concentration of oxygen (O ₂ ) contained in the nitrogen (N ₂ ) may be 10 to 30,000ppm, specifically 10 to 5,000ppm, 1,000 to 2,000ppm, 2,000 to 3,000ppm, 3,000 to 4,000ppm, 4,000 To 5,000 ppm, 100 to 1,000 ppm, 100 to 500 ppm, 100 to 200 ppm, 10 to 2,000 ppm, 10 to 1,000 ppm, 10 to 500 ppm, 100 to 300 ppm, 10 to 200 ppm, 50 to 150 ppm, 80 to 120 ppm, 15,000 to 25,000 ppm, 17,000 to 23,000 ppm, 19,000 to 21,000 ppm, or 19,500 to 20,500 ppm. The present invention can improve the curing density of the composition and / or the cured layer by controlling the concentration of oxygen (O ₂ ) in the above range in the third light irradiation step in which the photocuring is performed, as well as ozone of oxygen molecules (O ₂ ) The effect of cleaning the surface of the cured layer can be induced through (O ₃ ) conversion.

As one example, the third light irradiation step may be performed by irradiating the composition and / or cured layer with light having a wavelength of 300 ± 5 nm for a very short time of 1 to 2 seconds with a light amount of 100 ~ 3,000 mJ / ㎠ In this case, the distance between the composition and / or the cured layer and the light source may be 50 ± 10 mm.

The light irradiated in the present invention can 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, which is a UV region, may be irradiated using a mercury or metal halide lamp or the like.

In addition, the time for which light is irradiated in the present invention may be a very short time of 1 to 2 seconds, which is controlled by the speed at which the composition moves during light irradiation, such as the rate of movement of the composition coated on the substrate. Can be. For example, the composition and / or the movement speed of 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.

On the other hand, the composition used in the present invention does not contain a matting agent for reducing the gloss of the cured layer compared to the existing composition, 100 to 1,500 cps at 25 ° C, specifically 100 to 1,200 cps, 100 to 1,000 cps, 100 It may have a low viscosity of 800 to 500 cps, 100 to 500 cps, 100 to 400 cps, 150 to 350 cps, 200 to 350 cps, 250 to 350 cps, or 280 to 300 cps, and a filler may be used to improve the durability of the cured layer. Even further, it may exhibit a low viscosity of 350 cps or less. The composition has the advantage of excellent workability by having a low viscosity of 350 cps or less.

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

However, the following Examples and Experimental Examples are only illustrative of the present invention, and the content of the present invention is not limited to the following Examples and Experimental Examples.

Examples 1 to 5.

60 parts by weight of methyl urethane acrylate oligomer (molecular weight: 2,200 ± 100), 30 parts by weight of hydroxyethyl acrylate, and 10 parts by weight of 1,6-hexanediol diacrylate, 5 parts by weight of initiator benzophenone and colo as filler This month, a composition comprising silica (average diameter: 5 ± 0.5 μm) was applied to a 10 cm wide 10 cm long polyvinylchloride (PVC) substrate and fixed to a photocuring device having a structure as shown in FIG. 1. Then, as shown in Table 1 below, while moving the substrate at a moving speed of 9 ± 0.5 m / min, light irradiation was performed stepwise to prepare a non-foamed tile flooring specimen of SLS type. At this time, the average thickness of the cured layer was 15 ± 1㎛.

Example 1 Example 2 Example 3 Example 4 Example 5 Filler content [total composition
100 parts by weight] 3 parts by weight 3 parts by weight 3 parts by weight 3 parts by weight 5 parts by weight First light irradiation Wavelength range 172 ± 5 nm 172 ± 5 nm 172 ± 5 nm 172 ± 5 nm 172 ± 5 nm Dose 32 mJ / ㎠ 18 mJ / ㎠ 7 mJ / ㎠ 32 mJ / ㎠ 32 mJ / ㎠ With light source
Street 50 ± 1 mm 50 ± 1 mm 50 ± 1 mm 50 ± 1 mm 50 ± 1 mm Gas condition N ₂ conditions (O ₂ 5,000 ppm) N ₂ condition
(O ₂ 5,000 ppm) N ₂ condition
(O ₂ 5,000 ppm) N ₂ condition
(O ₂ 5,000 ppm) N ₂ condition
(O ₂ 5,000 ppm) Second light irradiation Wavelength range 200-400 nm 200-400 nm 200-400 nm 200-400 nm 200-400 nm Dose 280 mJ / ㎠ 280 mJ / ㎠ 280 mJ / ㎠ 280 mJ / ㎠ 280 mJ / ㎠ With light source
Street 2 ± 1㎜ 2 ± 1㎜ 2 ± 1㎜ 2 ± 1㎜ 2 ± 1㎜ Gas condition Air condition Air condition Air condition Air condition Air condition Third light irradiation Wavelength range 200-400 nm 200-400 nm 200-400 nm 200-400 nm 200-400 nm Dose 600 mJ / ㎠ 600 mJ / ㎠ 600 mJ / ㎠ 600 mJ / ㎠ 600 mJ / ㎠ With light source
Street 100 ± 1 mm 50 ± 1 mm 50 ± 1 mm 50 ± 1 mm 50 ± 1 mm Gas condition N ₂ condition
(O ₂ 10,000 ppm) N ₂ condition
(O ₂ 10,000 ppm) N ₂ condition
(O ₂ 10,000 ppm) N ₂ condition
(O ₂ 10,000 ppm) N ₂ condition
(O ₂ 10,000 ppm) Curing rate 85% 85% 82% 86% 85%

Comparative Examples 1 to 4.

SLS type non-foaming tile flooring specimens were prepared in the same manner as in Example 1, except that the composition was cured under the curing conditions in Table 2 below.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Filler content [total composition
100 parts by weight] 3 parts by weight 3 parts by weight 3 parts by weight 5 parts by weight First
ore
Research Wavelength range 172 ± 5 nm - 172 ± 5 nm - Dose 3 mJ / ㎠ - 118 mJ / ㎠ - With light source
Street 50 ± 1 mm - 10 ± 1㎜ - Gas condition N ₂ conditions (O ₂ 5,000 ppm) - N ₂ condition
(O ₂ 5,000 ppm) - 2nd
ore
Research Wavelength range - 200-400 nm 200-400 nm 200-400 nm Dose - 280 mJ / ㎠ 280 mJ / ㎠ 280 mJ / ㎠ With light source
Street - 100 ± 1 mm 2 ± 1㎜ 100 ± 1 mm Gas condition - Air condition Air condition Air condition The third
ore
Research Wavelength range 200-400 nm 200-400 nm 200-400 nm 200-400 nm Dose 600 mJ / ㎠ 600 mJ / ㎠ 600 mJ / ㎠ 600 mJ / ㎠ With light source
Street 100 ± 1 mm 100 ± 1 mm 100 ± 1 mm 100 ± 1 mm Gas condition N ₂ condition
(O ₂ 10,000 ppm) N ₂ condition
(O ₂ 10,000 ppm) N ₂ condition
(O ₂ 10,000 ppm) N ₂ condition
(O ₂ 10,000 ppm)

Experimental Example 1

Scanning electron microscope (SEM) analysis was performed on the non-foaming flooring specimens prepared in Examples 1 and 3 and Comparative Examples 2 and 3 to confirm the surface structure of the cured layer, which is the outermost layer of the non-foaming flooring according to the present invention. The results are shown in Figures 2 to 4.

2 and 3, the specimens of Examples 1 and 3 according to the present invention were found to include a radially curved structure at a certain size and frequency on the surface, and the radially curved structure was lower in height from the center to the periphery. It can be seen that the paper has a structure.

In addition, when looking at the laminated films of Examples 1 and 3, the cured layer of the laminated film is formed with a fine bend stronger as the amount of light irradiation in the first photocuring step becomes stronger, and the size of the random-radial fine-bending structure formed on the surface (that is, , Diameter), it was confirmed that the height and frequency of the center increased. Specifically, in Example 1, the average size of the radially curved structure is 50 ± 2 μm, the center has a height of 19 ± 1 μm, and includes 140 to 165 dendrite shapes per unit area (1 mm X 1 mm). , In the case of Example 3, the average size of the radially curved structure was 70 ± 2 μm, the height of the center was 12 ± 1 μm, and it was found to include 40 to 60 per unit area (1 mm X 1 mm).

On the other hand, the specimen of Comparative Example 2, which did not perform the first photo-curing step, was found to have no micro-curved structure on the surface. Referring to FIG. 4, the first photo-curing step was performed, but the amount of light irradiation was significantly higher. It was confirmed that the specimen of Example 3 does not have a radial structure that includes a curved structure on the surface, but does not include a central portion due to a large degree of bending, so that the height decreases from the central portion to the peripheral portion.

From these results, the first light irradiation step of irradiating light with a wavelength of less than 200 nm generates an excimer, and the generated excimer generates short-wave UV, thereby rapidly promoting surface hardening of the composition and / or cured layer, and thus the composition And / or the surface of the cured layer can be seen that shrinkage occurs to form a fine curved structure. In other words, it can be seen that the shape of the fine bend structure can be controlled by adjusting the performance condition of the first light irradiation step to a specific condition.

Experimental Example 2

In order to evaluate the fouling resistance of the non-foaming flooring according to the present invention, infrared (IR) spectroscopy of the cured layer surface was measured on the non-foaming flooring specimens prepared in Example 4 and Comparative Example 2.

As a result, it can be seen that the non-foaming flooring according to the present invention contains a low proportion of double bonds on the outermost layer of the cured layer. Specifically, the specimens of Example 4 and Comparative Example 2 are both the first peak present in the 810 ± 10 cm ⁻¹ range and the second reference peak present in the 1720 ± 10 cm ⁻¹ range, which represents a double bond of acrylate. It can be confirmed that a peak exists. However, the specimen of Example 4 has a high cure density of the cured layer, so the ratio of double bonds present on the surface of the cured layer is low, so the intensity ratio (I _p1 / I _p2 ) of the first peak and the second peak is 0.020 to 0.055. , In the specimen of Comparative Example 2 in which the first light irradiation step was not performed, the intensity ratio (I _p1 / I _p2 ) of the first peak and the second peak was found to exceed 0.055.

From these results, it can be seen that the non-foaming flooring according to the present invention contains a double bond at a low rate on the surface of the cured layer, which is the outermost layer.

Experimental Example 3.

To evaluate the performance of the non-foaming flooring according to the present invention, the non-foaming flooring specimens prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were subjected to glossiness, sensory evaluation according to iodine contamination, and surface hardness. The specific measurement method is as follows, and the measured results are shown in Table 3 below:

A) Glossiness evaluation

The gloss meter (Gloss Meter) was used to measure the gloss of 60 ° (60 gloss conditions).

B) Evaluation of iodine resistance

At 22 ± 1 ° C and 50 ± 5% RH humidity, 3 drops (approximately 10 μl) of 1% by volume of iodine solution were respectively contaminated on the surface of the specimen and contaminated. After 5, 10 and 15 minutes, Kim's Wipe 3 After washing the ash, the surface washed with the naked eye was observed to evaluate the degree of iodine solution remaining on the basis of the following grades:

-Grade 1: Peeling or breaking of the cured layer

(The area of iodine remaining in the initial contamination area is 40% or more),

-Grade 2: Significant change in shape of the hardened layer and significant change in gloss or color

(The area of iodine remaining in the initial contamination area is less than 40% and less than 20%),

-Grade 3: There is no or little change in the shape of the cured layer, and a significant change in gloss or color occurs.

(The area of iodine remaining in the initial contamination area is less than 5% and less than 20%),

-Grade 4: slight change in gloss or color without changing the shape of the cured layer

(The area of iodine remaining on the basis of the initial contamination area is less than 1% and less than 5%),

-Grade 5: No change in shape, luster and color of cured layer

(The area of iodine remaining in the initial contamination area is less than 1%).

C) Hardness evaluation

The hardness of the laminated film was measured according to ISO 4586-2 using a scratch tester (Erichsen scratch tester 413). Specifically, after the diamond tip mounted on the tester draws a circle (revolution: 5 times / min) with a load of 0 to 1 N and passes through the film surface, it is determined whether the tip has scratched the film surface. Did. At this time, in determining the presence or absence of scratches, the conditions for observing the presence or absence of scratches on the film, that is, the distance between the evaluator's eyes and the film are not officially determined, but when the laminated film is positioned 10 cm in front of the evaluator's eyes and viewed in a bright place under a fluorescent lamp It was confirmed that the load does not occur.

Glossiness Iodine resistance evaluation Hardness 5 minutes 10 minutes 15 minutes Example 1 2.5 ± 0.5 4 3 3 0.3 N Example 2 3.3 ± 0.5 4 3 3 0.3 N Example 3 5.0 ± 0.5 4 2 2 0.2 N Example 4 2.5 ± 0.5 4 4 3 0.3 N Example 5 2.5 ± 0.5 4 3 3 0.3 N Comparative Example 1 7.0 ± 0.5 2 One One 0.2 N Comparative Example 2 9.3 ± 0.5 One 0 0 0.2 N Comparative Example 3 2.0 ± 0.5 4 4 3 0.3 N Comparative Example 4 4.0 ± 0.5 One 0 0 0.2 N

As shown in Table 3, it can be seen that the non-foaming flooring according to the present invention exhibits low gloss and has excellent stain resistance (especially iodine resistance) and surface hardness.

Specifically, the non-foaming type flooring materials of Examples 1 to 4 were confirmed to have a gloss of 6 or less at a gloss of 60 ° even when a small amount of a matting agent was used. In addition, the flooring materials have excellent stain resistance, and it has been found that almost no change in surface shape as well as gloss or color change occurs before and after iodine contamination. Despite the formation, it was confirmed that the surface hardness of the cured layer improved to 0.25 to 0.35 N depending on the primary light irradiation conditions.

From these results, it is possible to optimize the curing density of the cured layer while inducing a radially curved structure on the surface by irradiating and curing the short-wavelength light in a specific range under different conditions when curing the cured layer light. It can be seen that not only can the glossiness be lowered, but also the stain resistance (especially iodine resistance) and surface hardness can be improved. Furthermore, the cured layers tended to have a lower gloss as the average size of the radially curved structure implemented on the surface, the height of the center portion, and the frequency per unit area increased. This means that the radially curved structure affects the surface properties of the cured layer.

100: light curing device
110: light irradiation chamber
111: first light irradiator (UV irradiator)
112: second light irradiator (UV irradiator)
113: third light irradiator (UV irradiator)
120: irradiated light
130: conveyor belt
140: gas septum
150: Psalms
200: cross-sectional structure of non-foaming flooring
210: hardened layer
220: substrate layer
211: dendrites

Claims (12)

Base layer; And
The surface includes a cured layer of an acrylic resin composition having a dendrite shape which is a radially curved structure extending from the center to the periphery with one point as the center,
The radial bending structure satisfies any one or more of conditions 1 and 2,
In infrared (IR) spectroscopy, the ratio of the intensity of the first peak (I _p1 ) in the range of 810 ± 10 cm ^-1 and the intensity of the second peak (I _p2 ) in the range of 1720 ± 10 cm ^-1 ( Non-foaming flooring with I _p1 / I _p2 ) of 0.020 to 0.055:
[Condition 1] The average diameter of the radially curved structure is 5 µm to 500 µm; And
[Condition 2] The radially curved structure is lower in height from the center to the periphery, but the average height of the center is 1 μm to 30 μm.
According to claim 1,
Non-foaming flooring with 2 to 400 radial curved structures present per unit area (1 mm X 1 mm) of the surface.
According to claim 1,
The cured layer is 22 ± 1 ℃, 50 ± 5% RH at a humidity of 1% by volume of iodine solution, and after washing for 5 minutes, the area of iodine remaining on the basis of the initial contamination area is less than 1%.
According to claim 1,
Non-foaming flooring with a surface gloss of less than 10 under Gloss 60 ° conditions.
According to claim 1,
Acrylic resin composition,
Urethane acrylic oligomer 100 parts by weight; And
50 to 150 parts by weight of a monomer containing at least one polymerizable reactor,
A non-foaming flooring material comprising 10 parts by weight or less of an initiator based on 100 parts by weight of an acrylic oligomer and a monomer.
According to claim 1,
The acrylic resin composition is a non-foaming type flooring material further comprising at least one filler selected from the group consisting of silica, alumina, glass beads, and organic beads.
The method of claim 5,
The non-foaming flooring having an average diameter of the filler is 1 μm to 15 μm.
The method of claim 5,
The content of the filler is a non-foaming type flooring material having less than 10 parts by weight based on 100 parts by weight of the composition.
According to claim 1,
The non-foaming flooring having an average thickness of the cured layer is 3 μm to 50 μm.
A first light irradiation step of activating the composition by irradiating light having a wavelength of less than 300 nm to an acrylic resin composition located on the base layer under inert gas conditions;
A second light irradiation step of irradiating the activated composition with light having a wavelength of 200 nm to 400 nm under air conditions to firstly cure the composition; And
A third light irradiation step of irradiating light having a wavelength of 200 nm to 400 nm under an inert gas condition to the primary cured composition to secondary-cure the composition to form a cured layer,
Infrared (IR) spectroscopy of the cured layer, the intensity of the first peak (I _p1 ) in the range of 810 ± 10 cm ^{-1 and} the intensity of the second peak (I _p1 ) in the range of 1720 ± 10 cm ^-1 _p2 ) ratio (I _p1 / I _p2 ) of 0.020 to 0.055 non-foaming method of manufacturing a flooring.
The method of claim 10,
The first light irradiation step is 1 mJ / ㎠ to 100 mJ / ㎠ method of manufacturing a non-foaming flooring characterized in that it is performed with a light irradiation amount.
The method of claim 10,
The first light irradiation step and the third light irradiation step, the concentration of oxygen (O ₂ ) The method of manufacturing a non-foaming type flooring, characterized in that performed under nitrogen (N ₂ ) conditions of 10 ppm to 30,000 ppm.

Images