KR20200027139A - Low gloss non-foaming floorings having radial flexure structure on surface - Google Patents

Abstract

The present invention relates to: a low-gloss and non-foaming flooring material having a radial flexure structure on the surface thereof; and a method for manufacturing the same. The non-foaming flooring material uses a specific range of short wavelength light in an acrylic resin composition by stages under different conditions to comprise a cured layer having the radial flexure structure on the surface thereof, thereby being able to realize a low surface gloss of less than 10 based on 60° gloss-meter, and excellent iodine resistance, and thus having excellent non-slip properties of the surface.

Description

Low gloss non-foaming floorings having radial flexure structure on surface}

The present invention relates to a low-gloss, non-foaming flooring having a radially curved structure on the surface and a method for manufacturing the same, in detail by inducing a radially curved structure on the surface by using a specific range of short wavelength light stepwise under different conditions during curing. It relates to a non-foaming type flooring material and a method of manufacturing the same, which can realize low glossiness without a matting agent and exhibit excellent iodine resistance and non-slip resistance.

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 material has a scratch resistance. However, in this case, there is a problem in that the safety of the pedestrian is significantly lowered because the surface of the flooring layer is smooth and the non-slip property is reduced. In addition, in the case of a conventional flooring material, it is difficult to provide natural gloss like natural materials while maintaining high iodine resistance. Specifically, when the existing flooring material is contaminated by contaminants such as iodine, the gloss is erased above 10 based on the 60-degree gloss-meter, but if it is less than 10, it cannot function. There is a problem in that the iodine resistance is rapidly decreased due to wear of silicone contained in the ultraviolet curing surface treatment agent for treating the surface. In addition, the conventional UV curing surface treatment agent includes a silica content of about 10% by weight based on the total weight as a matting agent in order to lower the gloss of the treated flooring material, but the silica is porous and has a very low apparent specific gravity. As it increases, dirt, moisture, grease, etc. are more easily adsorbed, so the stain resistance is drastically reduced, and marks such as hand and foot sweat marks remain on the surface of the surface-treated flooring material. Cloudiness will occur.

Accordingly, while eliminating a matting agent including inorganic particles or using a very small amount, realizing low gloss of the flooring material, and simultaneously controlling surface roughness, improves iodine resistance so that contaminants do not easily adhere to the flooring surface, and non- There is an urgent need for the development of flooring materials with improved safety for pedestrians by improving slip properties.

Republic of Korea Patent Publication No. 2014-0089074

The object of the present invention is to improve the iodine resistance while reducing the surface contact area by controlling the surface roughness while realizing low gloss of the flooring while excluding a matting agent including inorganic particles or using a very small amount while simultaneously controlling the surface roughness. It is to provide a non-foaming type flooring with improved properties.

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 bend structure has an average diameter of 5 μm to 500 μm;

It provides a non-foaming flooring having an average surface roughness (Rz) of 10 µm to 40 µm.

In addition, the present invention in one embodiment,

A first light irradiation step of activating the composition by irradiating the acrylic resin composition with light having a wavelength less than 300 nm 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

Provided is a method of manufacturing a non-foaming flooring comprising a third light irradiation step of irradiating light having a wavelength of 200 nm to 400 nm under an inert gas condition to a primary cured composition, thereby secondaryly curing the composition.

The non-foaming flooring according to the present invention comprises a cured layer having a radially curved structure on the surface by using a short range of light in a specific range in different stages in an acrylic resin composition, thereby forming a 60 ° gloss-meter (60 ° Gloss-Meter) It has the advantage of being able to achieve low surface gloss and excellent iodine resistance of less than 10, and excellent surface non-slip properties.

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 scanning electron microscope (SEM) images of the surfaces of the cured layers of Examples 1 and 3 according to the present invention.
4 is a scanning electron microscope (SEM) image of the surface of the cured layer of Comparative Example 3 according to the present invention.

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.

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

The present invention relates to a low-gloss, 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 iodine resistance of the flooring are imparted.

However, in this case, the surface treatment layer has a problem that the safety of pedestrians is lowered because the surface of the flooring material becomes smooth and the non-slip property decreases, and the conventional flooring material provides natural gloss like natural materials while maintaining high iodine resistance. Things have difficult limits.

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

The non-foaming flooring according to the present invention comprises a cured layer having a radially curved structure on the surface by using a short range of light in a specific range in different stages in an acrylic resin composition, thereby forming a 60 ° gloss-meter (60 ° Gloss-Meter) It can realize low surface gloss and excellent iodine resistance of less than 10, and can be usefully used as an interior material for industrial use because it has the advantage of excellent non-slip property.

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, rubber flooring, or polyvinyl chloride (PVC) materials used in offices, etc., in the form of a single layer sheet (SLS). It may be a tile 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 have surface properties, specifically, surface glossiness, iodine resistance, non-slip property, etc., controlled by its size or height, and for this purpose, the radial bend structure has a specific range of average diameters. It can be controlled to have. Specifically, the average diameter of the radial curved structure indicates the average size of the individual radial curved structures present on the surface of the hardened layer, and the average diameter may be 5 μm to 500 μm, more specifically 5 μm to 450 μm, 5 μm to 400 μm, 5 μm to 350 μm, 5 μm to 300 μm, 5 μm to 250 μm, 5 μm to 200 μm, 5 μm to 150 μm, 5 μm to 100 μm, 5 μm to 50 μm, 50 μm To 200 µm, 50 µm to 100 µm, 100 µm to 500 µm, 100 µm to 300 µm, 100 µm to 200 µm, 80 µm to 150 µm, 20 µm to 100 µm, 25 µm to 60 µm, 40 µm to 80 Μm, 80 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 μm, 15 μm to 30 μm, 15 μm to 25 μm, 20 μm to 30 μm, 1 μm to 10 μm, 2 μm to 10 μm, 4 μm to 10 μm, 5 μm to 10 μm, 7.5 μm To 10 μm, 8 μm to 10 μm¸ 0.5 μm to 7.5 μm , 0.5 μm to 5 μm, 0.5 μm to 3 μm, 0.5 μm to 2 μm, 0.5 μm to 1 μm, 1 μm to 5 μm¸ 1 μm to 3 μm, 1 μm to 2 μm, 2 μm to 5 μm, 2 Μm to 3.5 μm, 4 μm to 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 cured layer may have a radially curved structure formed on the surface to have a constant surface roughness. Specifically, the cured layer may have an average value of the surface roughness "Rz" of the radially curved structure existing on the surface of 10 µm to 40 µm, more specifically 10 µm to 35 µm, 10 µm to 30 µm, 10 ㎛ to 25㎛, 15㎛ to 40㎛, 20㎛ to 40㎛, 25㎛ to 40㎛, 15㎛ to 30㎛, 15㎛ to 25㎛, 18㎛ to 30㎛, 18㎛ to 25㎛, 15㎛ to It may be 24 μm, 18 μm to 24 μm, or 19 μm to 23 μm.

In addition, the radial curved structure may be formed at a predetermined frequency, for example, a predetermined number in a unit area, and the number of the radial curved structures may be equal to the number of centers of the radial 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 have 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).

The non-foaming flooring according to the present invention is provided with a hardened layer including a radially curved structure having the above-described shape and frequency as the outermost layer, thereby facilitating physical properties such as surface glossiness, iodine resistance, and non-slip property. Can be adjusted.

As one example, the non-foaming flooring according to the present invention induces the scattering of light incident on the surface through a radially curved structure formed on the surface of the cured layer, so that the total weight of the cured layer is 100 parts by weight (for example, the total weight of the acrylic resin composition). Less than 9 parts by weight, more specifically 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 parts by weight or less, 5 parts by weight or less, or 5 parts by weight or less of a matting agent is used separately, or in some cases, quenching Significantly low gloss can be achieved without the use of agents. For 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, 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.

As another example, the non-foaming flooring according to the present invention has a non-slip property that is improved, so that a grade of an inclination angle at which slip occurs during a ramp test according to DIN 51130 may be R10 or more, and specifically It may be R11 or more, or R10 to R11. Here, R10 represents a case where the angle of the inclination angle at which the slip is generated is 10 ° or more and less than 19 °, and R11 represents a case where the angle of the inclination angle at which the slip is generated is 19 ° or more and less than 27 °.

As another example, the non-foaming flooring according to the present invention has improved surface iodine resistance, contaminated with a 1% by volume iodine solution at a humidity of 22 ± 1 ℃, 50 ± 5% RH, and washed after 20 minutes. At the time, 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. All of the iodine is removed, so the residual area may be 0%.

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

Specifically, the acrylic oligomer means an oligomer obtained using a monomer containing an acrylic group, and the monomer includes methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth). It may be one or more (meth) acrylates selected from the group consisting of acrylates, pentyl (meth) acrylates, hexyl (meth) acrylates, heptyl (meth) acrylates, octyl (meth) acrylates and benzyl acrylates. have. For example, the acrylic oligomer is methyl acrylate, (meth) acrylate, ethyl acrylate, benzyl acrylate or a mixture of 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.

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 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 acrylic oligomer in the above range.

In addition, the monomer containing at least one polymerizable reactor may be an acrylic monomer. For example, the monomers include (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxy Hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate or 2-hydroxypropylene glycol (meth) acrylate, acrylic acid, methacrylic acid, 2 -(Meth) acryloyloxyacetic acid, 3- (meth) acryloyloxypropyl acid, 4- (meth) acryloyloxybutyl acid, 1,6-hexanediol diacrylate, acrylic acid duplex, itaconic acid , Maleic acid, caprolactone modified hydroxyacrylate (CHA), polyethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, triethyl Renglycol diacrylate, pentaerythritol triacrylate, trimethylolpropaneethoxytriacrylate, acryloyl morpholine, glycidyl metacrylate, N-vinylpyrrolidone ( N-vinylpyrrolidone) and benzyl acrylate.

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 curing rate even when a small amount of the initiator is included in the above range by stepwise use of a short range of light in a specific range at different conditions during curing of the composition. As an example, the curing rate of the cured layer according to the present invention is 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, 65% to 98%, 65% to 95%, 65% to 90%, 65% to 85%, 65% to 80%, 65% to 75%, 65% to 70%, 70% to 80%, 70% to 90%, 85% to 95%, 90% To 98% or 68% to 76%.

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. The present invention can improve the durability by controlling the average diameter of the filler in the above range to prevent cracking of the cured layer without increasing the gloss of the cured layer and to increase the adhesion between the cured layer and other layers. In addition, the filler may be included in less than 10 parts by weight based on 100 parts by weight of the composition so as not to impair the glossiness and iodine resistance of the cured layer. 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.

Meanwhile, the average thickness of the cured layer according to the present invention 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 the acrylic resin composition with light of a wavelength less than 300nm 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

Provided is a method of manufacturing a non-foaming flooring comprising a third light irradiation step of irradiating light having a wavelength of 200 nm to 400 nm under an inert gas condition to a primary cured composition, thereby secondaryly curing the composition.

The method for producing a non-foaming flooring according to the present invention has a step of curing an acrylic resin composition in three stages under different conditions by irradiating short-wavelength light in a specific range.

Specifically, the first light irradiation step is a first step of irradiating light to the composition applied on the substrate, 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 increase the scattering rate of light by shrinking the surface of the composition and / or the cured layer into the above-described radially curved structure using an excimer, so that the gloss of the cured layer can be reduced without using a matting agent. 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 not only improves the curing rate 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 hardening is performed, but also ozone of oxygen molecules (O ₂ ). Through the (O ₃ ) conversion, the effect of cleaning the surface of the cured layer can be induced.

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.

Meanwhile, the composition used in the present invention is 1,000 to 1,500 cps at 25 ° C, specifically 1,000 to 1,450 cps, 1,000 to 1,400 cps, 1,000 to 1,350 cps, 1,000 to 1,300 cps, 1,000 to 1,250 cps, 1,000 to 1,200 cps, It may have a low viscosity of 1,250 to 1,500 cps, 1,300 to 1,500 cps, 1,300 to 1,400 cps, 1,350 to 1,450 cps, 1,100 to 1,300 cps, or 1,050 to 1,200 cps. The composition has the advantage of excellent workability by controlling the viscosity in the above range.

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.

40 parts by weight of methyl (meth) acrylate oligomer (molecular weight: 2,200 ± 100), 20 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of benzyl acrylate, and 20 parts by weight of polyethylene glycol diacrylate and benzophenone as an initiator A composition comprising 5 parts by weight, and a filler, colloidal silica (average diameter: 5 ± 0.5 μm), was applied to a 10 cm × 10 cm vertical polyvinylchloride (PVC) substrate and structured as shown in FIG. It was fixed to the light curing device. 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 20 ± 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 8 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 condition (O ₂ 5,000 ppm or less) N ₂ condition
(O ₂ 5,000 ppm or less) N ₂ condition
(O ₂ 5,000 ppm or less) N ₂ condition
(O ₂ 5,000 ppm or less) N ₂ condition
(O ₂ 5,000 ppm or less) 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 68% 70% 70% 70% 70%

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 8 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 100 ± 1 mm 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 not to have a finely curved structure on the surface. In addition, referring to Figure 4, the first light curing step is performed, but the specimen of Comparative Example 3, which has a significant amount of light irradiation, includes a curved structure on the surface, but the degree of bending is large and does not include a central portion, so the height from the central portion to the peripheral portion is low. It has been found that paper has no radial structure.

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 glossiness, iodine resistance and non-slip resistance of the non-foaming type flooring according to the present invention, the surface roughness, glossiness, and iodine contamination of the specimens prepared in Examples 1 to 4 and Comparative Examples 1 to 3 The resulting color coordinate deviation and non-slip test were measured. The specific measurement method is as follows, and the measured results are shown in Table 3 below:

A) Surface roughness evaluation

Surface roughness (Rz) of the cured layer provided in the specimens of Examples and Comparative Examples was measured based on ISO 4287.

B) gloss rating

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

C) Evaluation of iodine

Arbitrary 3 points A to C were selected on the surface of the specimen, and the color coordinates in the CIE color space were measured for the selected points to obtain average color coordinates and color coordinate deviations. Specifically, by dropping 1-2 drops of iodine (I ₂ ) test solution (reagent name: iodine tincture) dissolved in methanol at a concentration of 1% by volume on the surface of the specimen at a humidity of 22 ± 1 ° C and 50 ± 5% RH. After confirming the spread, and after 20 minutes, rubbed twice with a tissue to remove the iodine on the surface, and then visually evaluated the state of the point where the iodine (I ₂ ) was buried. At this time, the evaluation was confirmed whether the specimen was positioned 10 cm in front of the evaluator's eyes and viewed in a bright place under a fluorescent lamp to change the shape of the cured layer (e.g., peeling or breaking, etc.), and to change the gloss and color. As follows:

-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%).

D) Non-slip evaluation

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

- R9: The angle of the inclination angle at which slip occurs is 6 ° or more and less than 10 °

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

- R11: Angle of inclination at which slip occurs is more than 19 ° and less than 27 °

- R12: Angle of inclination at which slipping occurs is more than 27 ° but less than 35 °

- R13: Angle of inclination at which slip occurs is more than 35 °

Surface roughness (Rz) Glossiness Iodine evaluation Non-slip Example 1 21 6 ± 0.5 4 R10 Example 2 20 6 ± 0.5 4 R10 Example 3 17 8 ± 0.5 3 R9 Example 4 22 6 ± 0.5 4 R10 Example 5 20 5 ± 0.5 3 R10 Comparative Example 1 13 12 ± 0.5 2 R9 Comparative Example 2 13 12 ± 0.5 One R9 Comparative Example 3 14 12 ± 0.5 4 R9 Comparative Example 4 20 9 ± 0.5 One R10

As shown in Table 3, the non-foaming type flooring according to the present invention exhibits low gloss even if the composition does not contain a matting agent by irradiating and curing the short-wavelength light in a specific range step by step under different conditions. Able to know.

Specifically, the non-foaming flooring specimens of Examples 1 to 4 have a gloss of less than 10 under a gloss 60 ° condition even when a small amount of a matting agent is used, and excellent in iodine resistance, as well as changing the shape of the surface before and after iodine contamination, as well as gloss. There was no color change. In addition, it was confirmed that the specimens of Examples 1 to 4 did not generate slippage at an inclination angle of less than 19 °.

From these results, when curing the composition by photo-curing a specific range of short-wavelength light step by step under different conditions, not only the curing rate of the composition is improved, but the glossiness of the cured layer is reduced, iodine resistance, and non-slip It can be seen that the sex is improved at the same time. 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 (13)

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 bend structure has an average diameter of 5 μm to 500 μm;
Non-foaming flooring having an average surface roughness (Rz) of 10 µm to 40 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,
Non-foaming flooring with a surface gloss of less than 10 under Gloss 60 ° conditions.
According to claim 1,
The cured layer is a non-foaming flooring material having an inclination angle rating of R10 or higher when slipping occurs according to a DIN 51130 lamp test.
According to claim 1,
The cured layer is contaminated with 1% by volume of iodine solution at a humidity of 22 ± 1 ℃ and 50 ± 5% RH, and after 20 minutes of washing, a non-foaming flooring having an area of iodine remaining less than 1% based on the initial contamination area.
According to claim 1,
Acrylic resin composition,
100 parts by weight of an acrylic oligomer; 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 6,
The non-foaming flooring having an average diameter of the filler is 1 μm to 15 μm.
The method of claim 6,
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 the acrylic resin composition with light having a wavelength less than 300 nm 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 method of manufacturing a non-foaming flooring comprising a third light irradiation step of irradiating light having a wavelength of 200 nm to 400 nm under an inert gas condition to a primary cured composition to secondary-cure the composition.
The method of claim 11,
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 11,
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.

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